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Emergence of Nonlinear Optical Activity by Incorporation of a Linker Carrying the p-Nitroaniline Motif in MIL-53 Frameworks
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† Centre for Surface Chemistry and Catalysis, Faculty of Bioscience Engineering, University of Leuven, 3001 Leuven, Belgium
‡ Institut für Anorganische Chemie, Christian-Albrechts-Universität zu Kiel, 24118 Kiel, Germany
§ K. Gumiński Department of Theoretical Chemistry, Jagiellonian University, Romana Ingardena 3, 30-060 Kraków, Poland
∥ Unité de Chimie Physique Théorique et Structurale, University of Namur, 5000 Namur, Belgium
⊥ Molecular Imaging and Photonics, KU Leuven − University of Leuven, 3001 Leuven, Belgium
# Catalysis Engineering, Department of Chemical Engineering, Delft University of Technology, 2629 Delft, The Netherlands
*M.A.v.d.V.: Tel: + 31-15-2786458. E-mail: [email protected]
*N.S.: Tel: + 49-431-8801675. E-mail: [email protected]
*B.C.: Tel: + 32-81-724554. E-mail: [email protected]
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The Journal of Physical Chemistry C

Cite this: J. Phys. Chem. C 2017, 121, 45, 25509–25519
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https://doi.org/10.1021/acs.jpcc.7b09190
Published October 17, 2017

Copyright © 2017 American Chemical Society. This publication is licensed under CC-BY-NC-ND.

Abstract

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p-Nitroaniline presents the typical motif of a second-order nonlinear optically (NLO) active molecule. However, because of its crystallization in an antiparallel and hence centrosymmetric structure, the NLO activity is lost. In this contribution, the p-nitroaniline motif was built successfully into the MIL-53 metal–organic framework. More precisely, MIL-53 was synthesized with 2-amino-5-nitroterephthalate as organic linker, with Al3+, Ga3+, or In3+ as inorganic cation. The Al and Ga structures are polar, as confirmed by second-harmonic generation microscopy, yielding stable NLO materials. Indeed, they contain a 22–36% surplus of the dipolar 2-amino-5-nitro-terephthalate oriented in a parallel fashion. The indium compound was shown to be less crystalline and centrosymmetric. Ab initio modeling of the second-order NLO response shows that the Al and Ga materials show a response comparable to typical inorganic commercial NLO materials such as KDP. As a hybrid material, capable of low-temperature synthesis and processing and the ultrafast NLO responses associated with organic materials, this material can potentially provide an interesting venue for applications with respect to traditional inorganic NLO materials.

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Introduction

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Polar crystalline materials can be used for a wide range of applications because they possess characteristics such as piezoelectricity, pyroelectricity, second-order nonlinear optical (SONLO) activity, and, in the case of reversible polarity, ferroelectricity. (1-3) SONLO activity specifically can be applied for telecommunication, information storage, optical switching, and signal processing. (4) Currently, mainly polar inorganic materials are used in commercial applications. However, inorganics have several limitations, with the limitations depending on the envisioned application. (5) A general limitation of inorganic crystals is that their properties can hardly be fine-tuned through chemical synthesis. Organic materials, on the contrary, are tunable and can be processed in more versatile ways. (5, 6) However, organic polar molecules have the disadvantage of typically crystallizing in an antiparallel orientation due to the optimization of dipole–dipole interactions, which cancels the overall dipole moment. (5, 7, 8) To achieve polar alignment of the organic entities, methods such as poling of polymers, Langmuir–Blodgett films, or self-assembled monolayers are required. (9-14) Crystal engineering methods can also be used to bypass the problem of centrosymmetric organization in organic materials. This is achieved by, for example, crystallization of chiral compounds (15) or by cocrystallization with chiral components resulting in noncentrosymmetric polymorphs. (16-18)
Metal–organic frameworks (MOFs) or porous coordination polymers (PCPs) are a promising category of materials that are highly tunable and that can circumvent the tendency of organic molecules to organize in a nonpolar fashion. (5) MOFs are porous hybrid materials composed of metal ions or metal clusters and organic linkers. MOFs are tunable because the metal nodes can be varied, the organic linkers can be chemically engineered, and the adsorbates in the pores can be exchanged. Polar organization in MOFs can be attained via several strategies. A first strategy to obtain noncentrosymmetric and potentially polar MOFs is to choose a metal–organic coordination bond geometry that does not allow centrosymmetric organization. Typical examples of this strategy are diamonoid frameworks (7, 19) and MOFs with nicotinate as a linker. (20) As a second strategy, polar linkers can potentially organize in a polar fashion due to optimal interactions and steric hindrance keeping the linkers in place. An example of this strategy is the insertion of 2-aminoterephtalate in MIL-53. (21) A third strategy to obtain polarity in MOFs is via polar ordering of guest species in the frameworks’ pores, as seen in perovskite structure type MOFs, where nitrogen-containing cations are ordered in a polar way in the cavities. (22-25) Also, neutral polar species, such as water, can organize in a polar fashion in MOFs. (26, 27) A fourth strategy to create polar MOFs is the incorporation of an electronegative ion in the framework structure. An example exploiting this strategy is the fluoride doping of MIL-53(Fe), which, together with the guest molecules, results in polar organization. (28)
In this research, we want to incorporate the well-studied polar p-nitroaniline (PNA) motif in a MOF to potentially organize the linker in a polar organization that can be maintained. The organic PNA molecule is the poster-child polar push–pull molecule for second-order nonlinear optics, generating frequency doubled light. However, crystallization of the molecule leads to the aforementioned antiparallel organization, removing the polarity. (29, 30) To obtain a polar material benefiting from the SONLO properties of PNA, researchers successfully adsorbed PNA molecules into zeolites, leading to overall polarity. (31-36) However, zeolites have limited chemical modification and processing possibilities. MOFs can alleviate these issues, as they offer tunability, combined with ease of processing and the possibility to obtain polarity. In addition, when a flexible framework such as MIL-53 is chosen, opportunities arise to fine-tune the polarization by variation of the pore openings. In this contribution, for the first time, a polar organization of the well known PNA motif was created via the strategy of creating a linker carrying the PNA motif and incorporating it in several MIL-53 frameworks, yielding highly stable polar and second-order nonlinear optically active materials.

Experimental Section

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Synthesis

The chemicals used for the synthesis were commercially available and were used without further purification. Gallium and indium salts were purchased at ABCR and used as received. The 2-amino-5-nitroterephthalic acid (H2BDC-NH2/NO2) linker was synthesized by a three-step synthesis procedure based on literature published by Skibo et al. (37) Following the literature procedure, starting with the hydrolysis of dimethyl aminoterephthalate to 2-aminoterephthalic acid, the product was reacted with formamide (HC(O)NH2) to give 2-formamido terephthalic acid. After nitration of this intermediate, the final H2BDC-NH2/NO2 linker was obtained by deprotection. Following the synthesis procedure, single crystals of 2-amino-5-nitroterephthalic acid could be obtained after recrystallization from hot water. The purity of the H2BDC-NH2/NO2 linker was confirmed by 1H NMR spectroscopy. More details of the synthesis and characterization can be found in the Supporting Information (SI) (Figures S1–S5). A flowchart displaying synthesis pathways, sample treatments and corresponding sample names is shown in Figure 1.

Figure 1

Figure 1. Flowchart of experiments showing synthesis pathways, sample treatments, and corresponding sample names.

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Using three different metals (aluminum, gallium, indium), discovery and synthesis optimization of MIL-53 frameworks was carried out employing our 24-high-throughput (HT) reactor system for solvothermal reactions, allowing a fast and efficient determination of optimal reaction parameters. (38-41) The reactor system contains custom-made Teflon reaction vessels with a maximum volume of 2 mL. For our M3+/H2BDC-NH2/NO2/solvent/additive (M = Al, Ga, In) system the following parameters were investigated: the molar ratio M3+:H2BDC-NH2/NO2, reaction solvents, volumetric ratio of solvent/water mixture, reaction temperature, reaction time, reaction vessel size, and the addition of 2 M HNO3 or 2 M NaOH solution. Detailed information on the reactions carried out can be found in Tables S1–S4. MIL-53(Al)-NH2/NO2 was synthesized by two different routes: one using DMF/H2O as solvent and one with ethanol/H2O as solvent. MIL-53(Al)-NH2/NO2 in DMF, denoted as MIL-53(Al)-NH2/NO2(1), was synthesized with the following optimized synthesis conditions: To a mixture of 44.2 μL of 2 M AlCl3·6H2O (88.4 μmol) in H2O and 20 mg 2-amino-5-nitroterephthalic acid (H2BDC-NH2/NO2, 88.4 μmol), 60 μL of DMF (0.78 mmol), 32.5 μL of H2O (1.8 mmol), and 13.3 μL of 1 M NaOH (13.3 μmol) in H2O were added to a 2 mL Teflon reactor. The reactor was sealed carefully and heated to 150 °C within 1 h, held at this temperature for 36 h, and then cooled to room temperature within 1 h. The product was filtered off, stirred in 10 mL of N,N-dimethylformamide (DMF) at room temperature for 2 h, filtered off again, and dried under ambient conditions. As an alternative route, MIL-53(Al)-NH2/NO2 was prepared in ethanol, denoted as MIL-53(Al)-NH2/NO2(2), with the following optimized synthesis conditions: 21.4 mg of AlCl3·6H2O (88.4 μmol), 20 mg of H2BDC-NH2/NO2, (88.4 μmol), 125 μL (2.1 mmol) of ethanol, and 25 μL (1.4 mmol) of H2O were added in a 2 mL Teflon reactor. The reactor was heated to 150 °C within 1 h, held at this temperature for 36 h, and cooled to room temperature within 1 h. Obtained products were filtered off and dried under ambient conditions. Compound MIL-53(Ga)-NH2/NO2(3) was synthesized with the following optimized synthesis conditions: To a mixture of 21.4 μL of 2 M Ga(NO3)3·H2O (43 μmol) in H2O and 20 mg H2BDC-NH2/NO2 (88.4 μmol), 60 μL of DMF (0.78 mmol), 25.8 μL of ethanol (0.44 mmol), and 20 μL of 1 M HNO3 (20 μmol) in H2O were added in a 2 mL Teflon reactor. The reactor was sealed carefully and heated to 150 °C within 1 h, held at this temperature for 16 h, and then cooled to room temperature within 1 h. The product was filtered off and dried under ambient conditions. Compound MIL-53(In)-NH2/NO2(4) was synthesized with the following optimized synthesis conditions: To a mixture of 44.2 μL of 2 M In(NO3)3·H2O (88.4 μmol) in DMF and 10 mg H2BDC-NH2/NO2 (44.2 μmol), 85.8 μL of DMF (1.12 mmol) and 20 μL of ethanol (0.34 mmol) were added in a 2 mL Teflon reactor. The reactor was sealed carefully and heated to 150 °C within 1 h, held at this temperature for 16 h, and then cooled to room temperature within 1 h. The product was filtered off and dried under ambient conditions.

Thermal Activation

Prior to the sorption experiments the samples 1–4 were activated at 200 °C for 16 h under reduced pressure (10–2 kPa). For MIL-53(Al)-NH2/NO2 (1) this activation procedure was carried out twice, ultimately resulting in MIL-53(Al)-NH2/NO2_vnp (5), the very narrow pore form of MIL-53(Al)-NH2/NO2 (1).

Structural Characterization

The high-throughput PXRD measurements were performed in transmission geometry using a STOE HT diffractometer equipped with a xy stage and an image plate detector system (Cu Kα1 radiation). Collection of high-resolution powder diffraction data was performed with a STOE Stadi-P powder diffractometer equipped with a MYTHEN1K detector system (Cu Kα1 radiation). Single-crystal X-ray diffraction data were collected on a Bruker P4 diffractometer equipped with a IPSD detector using Mo Kα radiation. The structural models for the Rietveld refinement for MIL-53(Al)-NH2/NO2 (1) and MIL-53(Ga)-NH2/NO2 (3) were obtained as follows: The cell parameters were obtained by indexing laboratory high-resolution X-ray powder diffraction data using TOPAS Academic v4.1, (42) indicating strong similarity of the title compound with the hydrated form of Al-MIL-53-np. (43) Using the Accelrys Materials Studio 4.1 software package, the BDC2– molecule in MIL-53 was exchanged by BDC-NH2/NO22–. (44) The lattice parameters were fixed to the experimentally determined values, and energy minimization calculations were carried out using the universal force-field (UFF) as implemented in the Forcite module of Materials Studio. (44)

General Characterization

Scanning electron microscopy (SEM) images were recorded on a JSM-6010PLUS/LA instrument from JEOL after sputter coating with palladium–gold. 1H NMR spectroscopy was carried out on a Bruker DRX 500 at 200 MHz. Thermogravimetric analyses were performed using a NETZSCH STA 409 CD analyzer. The samples were heated in Al2O3 crucibles at a rate of 4 K min–1 under a flow of synthetic air (75 mL·min–1). The TG data were corrected for buoyancy and current effects. A HEKAtech Euro Elemental Analyzer was used for elemental analysis. Sorption experiments were carried out using a Belsorp-max instrument (BEL JAPAN). The characterization of the compounds was carried out using as-synthesized (for 2 to 4) or washed samples (for 1).

SONLO Measurements

The compounds were always measured in their as-synthesized form, unless mentioned otherwise. Second harmonic generation (SHG) scanning microscopy images were recorded on a multiphoton laser scanning microscope (FV1200MPE, BX61WI frame, Olympus) in transmission mode. The microscope was equipped with a 50× long working distance objective (SLMPlan N, NA = 0.35, Olympus) and a visible-light condenser (NA = 0.9, Olympus). To select the 400 nm SHG light a dichroic mirror and band-pass filter combination was used (T425lpxr-et405/10bp of Chroma). As the laser source, a femtosecond tunable laser operating at a wavelength of 800 nm was used (∼100 fs pulse duration, 80 MHz pulse rate) (Insight DeepSee, Spectra-Physics). The laser light was linearly polarized using a Glan-Taylor polarizer, and the plane of polarization was controlled via a zero-order half-wave plate from Thorlabs. The quantification of the second-order NLO activity was done using a customized inverted wide-field SHG microscope (IX71 frame, Olympus), which operates in transmission mode. To be able to consider the incident light as a collimated beam, a long focal length lens (f = 75 mm, NA = 0.013) was used. Images were formed by a 15× long working distance objective (LMU-15×-NUV, NA = 0.32, Thorlabs) and recorded with an EM-CCD camera (Hamamatsu). To select the 400 nm SHG light a filter set consisting of a bandpass filter (BG39, 2 mm, Schott) and an interference filter (F10-100, center wavelength 400 nm, fwhm 10 nm, Melles Griot) was used. As the laser source, a Ti:sapphire laser operating at a wavelength of 800 nm was used (∼100 fs pulse duration, 80 MHz pulse rate) (Tsunami, Spectra-Physics) combined with a pump laser (Millenia Pro, Spectra-Physics). The laser light was linearly polarized using a Glan-Taylor polarizer, and the plane of polarization was controlled via a zero-order half-wave plate from Thorlabs. All SHG images were processed with ImageJ and Fiji software.

Multiscale Ab Initio/Local Field Theory Calculations to Determine ⟨deff⟩

For both MIL-53(Al)-NH2/NO2 and MIL-53(Ga)-NH2/NO2 compounds two crystal phases (A and C, see Figure 4) were considered in the calculations for ⟨deff⟩. These phases (as well as vnp MIL-53(Al)-NH2) were first considered as independent pure phases for geometry optimization using periodic boundary conditions (PBC) within the CRYSTAL14 package. (45, 46) The optimizations were performed at the density functional theory (DFT) level of theory with the B3LYP exchange-correlation functional and the 6-31G(d,p) basis set. Only the fractional coordinates were optimized with the cell parameters kept fixed at their experimental values. Using these optimized geometries, the calculations of the molecular properties, the polarizability, α, and the first hyperpolarizability, β, were performed for the individual cations and anions within their embedding crystal field. These fields were simulated with a 100 Å radius sphere of Mulliken point charges obtained from PBC/B3LYP calculations at the optimized crystal geometries. (47) The static (λ = ∞) responses were computed at the second-order Møller–Plesset (MP2) level of theory with 6-311++G(d,p) basis set. The dynamic MP2 responses were then calculated following a multiplicative approximation that combines static and dynamic B3LYP/6-311++G(d,p) responses to describe frequency dispersion. (48) All of the molecular property calculations were performed with Gaussian09 software. (49) Using the molecular properties, the linear susceptibilities, χ(1), and therefore the refractive indices, n, and the second-order nonlinear susceptibilities, χ(2), were then calculated by employing the local field theory (LFT) methodology, (50-55) recently applied to MOFs. (48) Finally, the effective values, ⟨deff⟩, were evaluated after accounting for the weights of the different crystal forms for phase-matching conditions as well as for the averaging over all light polarization orientations with respect to the crystal grains. The deff values are related to the χ(2) tensors by the following equation(1)where , , and are the light-wave polarization vectors, r is the optical path length (symbolizing the grain size in the calculation), and(2)is the phase mismatch related to the difference of refractive indices. The indices 1, 2, and 3 in Equation 2 refer the crystal axes. Equation 1 accounts for (i) the biaxial nature of the crystal and the fact that nonpolarized light beams split into two perpendicularly polarized [called (+) and (−)] beams propagating at different speeds and for (ii) the interaction between the incident light at fundamental frequency [(+) or (−)] and the generated light [also (+) or (−)] at twice its frequency. Finally, all possible orientations of the light-wave polarizations with respect to the crystal grains, defined by the polar angles (θ, ϕ), are taken into account to estimate the average ⟨deff⟩ quantities. More details of the whole multiscale method, including the evaluation of the local field, the treatment of the frequency dependence of the linear and nonlinear responses, (48, 56) and the selection of the charges to describe the in-crystal polarization field (47) are provided in the SI.

Results and Discussion

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For our purpose to create functional polar crystals by incorporation of the PNA motif into a MOF, we started by designing a suitable linker molecule. As the aimed framework structure, we chose MIL-53 because the flexibility of the framework can potentially allow fine-tuning of the polarization by variation of the pore opening. For the linker molecule to benefit from similar polar and SONLO properties as PNA, the linker was designed containing an extended π-conjugated system with amino and nitro donor and acceptor groups. To ensure that the linker can form metal coordination bonds to create a MIL-53 framework, opposing carboxylate ends were added to the aromatic ring. This resulted in the 2-amino-5-nitroterephthalic acid (H2BDC-NH2/NO2) molecule (Figure 2).

Figure 2

Figure 2. 2-amino-5-nitroterephthalic acid (H2BDC-NH2/NO2) linker molecule.

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After successful synthesis of the 2-amino-5-nitroterephthalic acid linker (Figures S1–S5), three different metals were used as the nodes to build up the aimed MIL-53 frameworks: aluminum, gallium, and indium. All frameworks were synthesized with DMF/H2O as the solvent, and for the aluminum MOF also a synthesis in ethanol/H2O was tested. The resulting synthesized compounds are denoted as follows: MIL-53(Al)-NH2/NO2 (1) for the aluminum compound synthesized in DMF, MIL-53(Al)-NH2/NO2 (2) for the aluminum compound synthesized in ethanol, MIL-53(Ga)-NH2/NO2 (3) for the gallium compound synthesized in DMF, and MIL-53(In)-NH2/NO2 (4) for the indium compound synthesized in DMF. The syntheses of the aluminum compounds 1 and 2 both resulted in microcrystalline powders, with the crystals from the DMF synthesis (1) having a more or less rectangular shape with lengths around 10 μm and thicknesses around 2 μm or a cubic shape between 0.5 and 2 μm in size (Figure 3a). The synthesis of the aluminum compound in ethanol (2) resulted in longer (between 10 and 50 μm) and thicker (∼8 μm) crystals than the DMF synthesis (Figure 3b). The gallium compound 3 was also obtained as a microcrystalline powder, seemingly composed of aggregates of rectangular crystals grown alongside each other, with the larger aggregates having a length between 20 and 30 μm and a thickness around 20 μm (Figure 3c). The indium compound 4 appeared to be less crystalline, as the PXRD pattern did exhibit fewer well-resolved reflections (Figure 3d and Figure S10 PXRD). Additional SEM images can be found in the SI (Figures S17–S20).

Figure 3

Figure 3. SEM images of H2BDC-NH2/NO2 containing MOFs: (a) MIL-53(Al)-NH2/NO2 (1), (b) MIL-53(Al)-NH2/NO2 (2), (c) MIL-53(Ga)-NH2/NO2 (3), and (d) MIL-53(In)-NH2/NO2 (4). Note that the first image has a scale bar of 10 μm, whereas the other images have a scale bar of 50 μm.

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Crystal Structures

To determine whether the crystal structures of compounds 1–4 are polar, PXRD measurements were performed to refine the structures using the Rietveld method because the compounds could only be obtained as microcrystalline powders. MIL-53(Al)-NH2/NO2 (1) and MIL-53(Ga)-NH2/NO2 (3) were confirmed to crystallize in the polar monoclinic space group Cc (Figures S6 and S8, containing Rietveld and Pawley refinements). The pattern of MIL-53(Al)-NH2/NO2 (2) exhibited fewer well-resolved reflections (Figure S7) and therefore a reliable refinement by Rietveld methods was not possible. However, corresponding to the Pawley refinements, the cell parameters of MIL-53(Al)-NH2/NO2 (2) hardly differ from those of MIL-53(Al)-NH2/NO2 (1) (Table 1). Because of the lower crystallinity of MIL-53(In)-NH2/NO2 (4), only the cell parameters could be obtained via indexing the powder pattern and refining them using the Pawley method (Figure S10). Because no structural refinement was possible, the indium compound could not be unambiguously assigned to a centrosymmetric or noncentrosymmetric space group. The crystallographic data of the different MIL-53-NH2/NO2 compounds are summarized in Table 1.
Table 1. Crystallographic Data of the Title Compounds
 MIL-53(Al)-NH2/NO2 (1)MIL-53(Al)-NH2/NO2 (2)MIL-53(Ga)-NH2/NO2 (3)MIL-53(In)-NH2/NO2 (4)
formula sum[Al(OH)(BDC-NH2/NO2)][Al(OH)(BDC-NH2/NO2)][Ga(OH)(BDC-NH2/NO2)][In(OH)(BDC-NH2/NO2)]
methodRietveldPawleyRietveldPawley
wavelengthCu Kα1Cu Kα1Cu Kα1Cu Kα1
a/Å17.5669(8)17.565(5)17.460(1)16.870(8)
b/Å13.3691(7)13.469(3)14.1006(7)13.948(7)
c/Å6.6105(2)6.616(2)6.7350(2)7.235(4)
β/deg112.125(3)112.273(8)112.712(6)90
spacegroupCcCcCcImam or Ima2
Rwp (%)5.573.797.414.20
RBragg (%)1.56 2.81 
GoF2.111.742.001.54
According to the results of the Rietveld refinement, structures 1, 2, and 3 are disordered and hence have multiple linker alignments. Therefore, ab initio calculations were performed to optimize potential framework models. As all carbon atoms of the aromatic ring are crystallographically independent in the observed noncentrosymmetric space group, depending on the substitution pattern of the linker, four different possible orientations result for the periodic crystal structure. This leads to four models, as shown in Figure 4, each containing one orientation of amino and nitro groups. Note that Figure 4 represents only a 2D projection of the linker; in the 3D framework the linker molecules are fixed regarding orientation, and thus four different polymorphs can be observed.

Figure 4

Figure 4. Different positions of the amino and nitro groups in the BCD2– anion postulated in the MIL-53-(Al)-NH2/NO2 structure.

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Consecutively, PXRD patterns were simulated from these models and compared against the Rietveld refinements of the experimental PXRD data. The comparison revealed that two of these models were reasonably well matching the experimental PXRD data, namely, phases A and C. As a last step, the occurrence of combinations of phase A and C was considered. The phase percentages were obtained by refining the occupancy factors and led to the conclusion that the A phase is present in excess over the C phase, which represents its oppositely oriented counterpart, respectively. Optimization of the MIL-53(Al)-NH2/NO2 (1) structure resulted in the prediction of a 61:39 ratio of phases A and C (respectively) of linker organization (Figure 5). For MIL-53(Al)-NH2/NO2 (2) the modeling procedure could not be performed, as a reliable Rietveld refinement was not possible for the experimental PXRD pattern. For MIL-53(Ga)-NH2/NO2 (3) a 68:32 ratio of phases A and C (respectively) of linker organization resulted in the best fit with the experimental PXRD patterns (Figures S8 and S9).

Figure 5

Figure 5. Crystal structure of MIL-53(Al)-NH2/NO2 (1) along [001]. The disorder (above) of the linker molecules in the structure contains 61% of the NO2 groups of the linker molecules showing out of the plane and 39% pointing in plane. Carbon atoms are shown in gray, oxygen in red, nitrogen in blue and AlO6 polyhedra in orange.

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Additional Characterization

To further characterize the new MIL-53-NH2/NO2 compounds, the composition and thermal stability of 1–4 were verified by elemental analysis and TG measurements. All samples are stable up to ca. 300 °C, and up to this temperature occluded solvent molecules are removed from the framework (Figures S13–S15). The thermal stability is in the same range as known for other as-synthesized functionalized MIL-53 derivatives (−Cl, −Br, CH3, NO2, −NH2, −OH). (57) The sum formulas of the compounds deduced from the TG measurements are in good agreement with the values obtained by elemental analyses (Table S6). Solution 1H NMR spectra show that 15% of the amino groups of 2 were ethylated during synthesis (Figures S21–S23). Because there is a large interest for the use of MOFs in sorption applications, the sorption properties of the new MIL-53 compounds 1–4 were also assessed. Prior to the sorption experiments all samples were activated by means of a temperature treatment to remove the guest molecules. Nitrogen sorption measurements reveal a Type I isotherm for MIL-53(Al)-NH2/NO2 (1), with a specific surface area (BET) of as,BET = 287 m2g–1 and a micropore volume of Vmic,BET = 0.11 cm3g–1 (Figure S24). When MIL-53(Al)-NH2/NO2 (1) was subjected to two consecutive activation treatments instead of one treatment, a very narrow pore form of MIL-53(Al)-NH2/NO2 (1) was achieved (Figure 1), as shown by the PXRD pattern (Figure S11; Table S5) and denoted as MIL-53(Al)-NH2/NO2_vnp (5). (58) One activation cycle probably leads to an incomplete removal of the occluded solvent molecules and the channels of the flexible framework remain accessible. Two activation cycles fully remove all guest molecules, which leads to a framework contraction, most likely induced by attractive forces between adjacent linker molecules. These intraframework interactions are apparently exceeded by host–guest interactions in the solvent-filled MOF. Nitrogen sorption measurements for this very narrow pore form 5 show that the values reduce to as,BET = 92 m2 g–1 and Vmic,BET = 0.04 cm3 g–1. Immersion of the very narrow pore compound 5 in DMF results in a re-establishment of the structure to the as-synthesized MIL-53(Al)-NH2/NO2 (1) structure with the wider pores (Figure S12). Additionally, water, CO2, and hydrogen sorption experiments were performed on compound 1 (Figures S25–S27), starting from the sample that received one activation treatment. The measurements reveal a very hydrophilic character of compound 1, with a total uptake of 12 wt % H2O (at 1 bar and 298 K), whereas 9 wt % of CO2 (1 bar, 298 K) and 0.7 wt % of hydrogen (1 bar, 77 K) can be adsorbed. The uptake of CO2 of ca. 90 mg/g in MIL-53(Al)-NH2/NO2 (1) is comparable to the reported uptake of MIL-53(Al) of ∼106 mg/g and MIL-53(Al)-NH2 of ∼98.6 mg/g. (59, 60) Compounds 2–4 did not show any uptake of N2; therefore, no other types of sorption measurements were carried out for these compounds.

Second Harmonic Generation Activity

The PXRD refinements revealed that polar symmetries are achieved due to a net polar organization of the linkers in compounds MIL-53(Al)-NH2/NO2 (1), MIL-53(Al)-NH2/NO2 (2), and MIL-53(Ga)-NH2/NO2 (3). Because polar materials can display interesting second harmonic generation (SHG) activity, the occurrence of SHG was probed locally through SHG microscopy on single crystals of the compounds.
SHG is a nonlinear optical process, taking place when high-intensity laser light interacts with materials possessing a noncentrosymmetric organization. (61) This noncentrosymmetric requirement for SHG to occur is a consequence of the nature of the process. The SHG process converts the energy and momentum of two photons into one photon with doubled frequency, by a coherent process, meaning phase relations between the photons are important. By consequence, destructive interference of SHG occurs in centrosymmetric organized materials, as the related third-rank tensor for the second-order nonlinear susceptibility χ(2) becomes zero. For noncentrosymmetric organizations, constructive interference of the SHG process occurs, and an SHG signal can be detected. Therefore, SHG microscopy can be used as a tool to distinguish noncentrosymmetric from centrosymmetric organizations. In our case, this allows us to locally probe areas in the crystals where noncentrosymmetric linker alignments are occurring.
Complementary to the SHG images, two-photon fluorescence (2PF) images were recorded. Two-photon fluorescence also is a nonlinear optical process, taking place when fluorophores are irradiated with high-intensity laser light. (61) In 2PF, two photons nearly simultaneously excite a fluorophore, which, in turn, emits a fluorescence photon. The process is an incoherent process because the excitation and emission events are separated in time and phase relations between the emitted versus exciting photons are absent. Because there is no symmetry requirement for the process to occur, fluorophores can be visualized regardless of their organization. (62) In our case, the linker with PNA motif acts as the fluorophore. By comparing SHG and 2PF images, areas with noncentrosymmetric linker organizations (visible in both SHG and 2PF images) can be distinguished from areas with random linker organizations (only visible in 2PF images).
From Figure 6 it is clear that compounds MIL-53(Al)-NH2/NO2 (1), MIL-53(Al)-NH2/NO2 (2), and MIL-53(Ga)-NH2/NO2 (3) contain areas displaying SHG activity. Those areas thus contain noncentrosymmetric linker organizations, more specifically polar alignments, as determined by the PXRD refinements. Comparison of SHG and 2PF images clearly shows that the two-photon fluorescence signal is more homogeneously distributed than the SHG signal. This means that an overall polar linker organization is not present throughout the entire crystals. In contrast with compounds 1–3, MIL-53(In)-NH2/NO2 (4) does not display SHG activity (Figure S30). Apart from the non-SHG active powder, a single particle shows SHG activity in the image. This is likely due to an impurity or minority phase. The apolar symmetry of the indium compound can be explained by the larger M–O distances in the MOF in comparison with the Al and Ga compounds (Al–O: 1.8 to 1.9 Å; (43) Ga–O: 1.8 to 2.0 Å; (63) In–O: 2.1 to 2.2 Å (64)), which allow a possible rotation, and hence randomization, of the linker molecules.

Figure 6

Figure 6. From left to right: optical, two-photon fluorescence, and second-harmonic generation images. From top to bottom: as synthesized MIL-53(Al)-NH2/NO2 (1), MIL-53(Al)-NH2/NO2 (2), and MIL-53(Ga)-NH2/NO2 (3). The SHG images display the average intensity of linearly polarized laser light, calculated over 60 images, each image being 3° apart in polarization direction of the incident polarized beam. The scale bars indicate a distance of 10 μm for each image.

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To quantify the SHG activity of compounds 1–3, the effective second-order nonlinear optical coefficient ⟨deff⟩ was determined experimentally for each compound. The ⟨deff⟩ value of a material represents the average SHG activity of a collection of crystals of the material, oriented differently in the measurements’ coordinate system. Averaging over all orientations allows quantification of the SHG activity of materials for which measurements along a specific crystal axis are not straightforward, as is the case for small crystals. To obtain an absolute value for ⟨deff⟩, the sample crystals are measured against a reference crystal, of which the d value is known (in our case a BBO crystal was used as the reference). Using the ⟨deff⟩ value for the quantification of the SHG activity of a compound, differences in crystal size and refractive index are taken into account. (65) A detailed description of the ⟨deff⟩ calculation is given in the SI. The experimentally determined ⟨deff⟩ values of compounds 1–3 are summarized in Table 2.
Table 2. Experimental ⟨deff⟩ Values
 ⟨deff⟩ (pm V–1)
MIL-53-(Al)-NH2/NO2 (1)0.02 ± 0.01
MIL-53-(Al)-NH2/NO2 (2)0.05 ± 0.02
MIL-53-(Ga)-NH2/NO2 (3)0.02 ± 0.01
For the aluminum compound 1 and the gallium compound 3, equal ⟨deff⟩ values were measured (0.02 pm·V–1). The aluminum compound synthesized in ethanol 2 displayed a higher SHG activity, with a ⟨deff⟩ value of 0.05 pm·V–1. An explanation for the higher SHG activity of this compound could be a higher A/C fraction (Figure 4), which would lead to more noncentrosymmetrically organized linkers. However, as mentioned previously, we could not determine the A/C fraction for compound 2 through structure refinements, as a reliable structure refinement was not possible for this compound.
Comparing the ⟨deff⟩ values of the MIL-53-NH2/NO2 MOFs 1–3 with the reported ⟨deff⟩ value of MIL-53(Al)-NH2 (0.05 ± 0.02 pm V–1), (21) for which the terephthalic acid linker is functionalized solely with an amino group, it can be concluded that the SHG activities are in the same range, despite their differences in linker functionalization. This seems counterintuitive, as a higher SHG activity for the compounds with the amino/nitro functionalized linkers could be expected because this linker possesses a more efficient donor–acceptor system, resulting in a higher hyperpolarizability, which could lead to a higher SHG activity. However, an important determining factor of the SHG efficiency is how the linkers are organized in the crystal structure. The occurrence of several phases of linker organization can lead to (partial) cancellation of the SHG activity. Additionally, MIL-53-NH2/NO2 and MIL-53(Al)-NH2 reabsorb the wavelength at which SHG is generated (400 nm) most likely to a different extent (see Figure S34 and ref 66). In fact, a rough estimate of the amount of reabsorbed SHG-light is calculated in the SI for a crystal containing the PNA motif, with the same linker density as for MIL-53(Al)-NH2/NO2 (1) and a height of 2 μm. This estimation predicts a transmittance of only 2.1 × 10–4% of generated 400 nm SHG light through the sample. Whereas the calculation is based on the extinction coefficient of PNA in water, rather than 2-amino-5-nitro-terephthalate build into MIL-53, the majority of the generated SH-light can be expected to be reabsorbed by the MIL-53(Al)-NH2/NO2. To gain more insight into the differences between the MIL-53-NH2/NO2 compounds and the previously reported MIL-53(Al)-NH2 compound, they need to be investigated off-resonance, which is also directly relevant for NLO applications. Hence we theoretically determined the ⟨deff⟩ values using ab initio calculations on the crystal structures in the next section.

Analysis of MIL-53(Al)-NH2/NO2 (1), MIL-53(Ga)-NH2/NO2 (3), and MIL-53(Al)-NH2 SHG Activity by Ab Initio Calculations

Multiscale numerical simulations were carried out to predict and interpret the ⟨deff⟩ values of MIL-53(Al)-NH2/NO2 (1), MIL-53(Ga)-NH2/NO2 (3), and MIL-53(Al)-NH2. To account for the occurrence of a combination of A and C linker phases in compounds MIL-53(Al)-NH2/NO2 (1) and MIL-53(Ga)-NH2/NO2 (3), first the χ(1) and χ(2) tensors for the pure phases of linker organization A and C were calculated. Consecutively, the final χ(1) and χ(2) tensors were obtained by accounting for the A/C phase ratios, as determined from the powder diffraction refinement, that is, 61:39 for MIL-53(Al)-NH2/NO2 (1) and 68:32 for MIL-53(Ga)-NH2/NO2 (3).
The resulting χ(1) and χ(2) tensors and ⟨deff⟩ values for MIL-53(Al)-NH2/NO2, MIL-53(Ga)-NH2/NO2, and MIL-53(Al)-NH2 are presented in Table 3 (See also the SI for additional data on the refractive indices as well as linear and nonlinear responses for other incident wavelengths, Tables S7 and S8). It is clear that the tensors for the pure A and C phases are almost equal in magnitude but opposite in sign, especially for the aluminum compound MIL-53(Al)-NH2/NO2 (1). This means that the SHG-generating part (mostly the organic linker) is practically oriented antiparallel in phase A versus phase C. Moreover, if a material would contain equal amounts of phases A and C, on a scale below the diffraction limit, then practically no SHG would be generated, as the phases would cancel each other out. Because MIL-53(Al)-NH2/NO2 (1) and MIL-53(Ga)-NH2/NO2 (3) were experimentally found to contain, respectively, 61:39 and 68:32 ratios of phases A:C, the tensor components and therefore also the SHG activity are not completely canceled out, but the values are lower than those of the pure phases. Considering the largest χ(2) tensor components of the pure phases, this reduction attains a factor of 4 to 5 for M = Al and 2 to 3 for M = Ga. Still, relatively high maximum tensor components are found for the compounds containing mixed phases: 29.3 pm V–1 for (M = Al) and 105.0 pm V–1 for (M = Ga).
Table 3. MP2/LFT Results for MIL-53(Al)-NH2/NO2, MIL-53(Ga)-NH2/NO2, and MIL-53(Al)-NH2 (in the very narrow pore phase) Calculated for an Incident Wavelength of 1064 nm (Selected χ(2) Tensor Components (in pm V–1) and ⟨deff⟩ (in pm V–1))a
     ⟨deff⟩⟨deff⟩⟨deff⟩
compound/phaseχ333(2)χ111(2)χ133(2)χ113(2)r = 0 μmr = 3 μmr = 10 μm
MIL-53(Al)-NH2/NO2 Phase A133.9–1.5–16.3–2.13.4090.5830.215
MIL-53(Al)-NH2/NO2 Phase C–134.21.516.22.13.3940.5760.212
MIL-53(Al)-NH2/NO2A/C (61:39)29.3–0.3–3.6–0.50.7510.1310.048
MIL-53(Ga)-NH2/NO2 Phase A–4.4222.2–6.913.32.9520.5410.209
MIL-53(Ga)-NH2/NO2 Phase C4.3–147.17.0–4.93.0890.8280.332
MIL-53(Ga)-NH2/NO2 A/C (68:32)–1.3105.0–3.21.91.2210.2720.107
MIL-53(Al)-NH2(vnp)6.2–15.8–6.6–2.62.1300.4400.178
a

For MIL-53(M)-NH2/NO2, results are listed for the pure A and C phases as well as for the A:C ratios obtained from PXRD analysis.

However, when calculating the ⟨deff⟩ values for the mixed compounds, the responses are strongly reduced, and this effect is enhanced when combined with the phase mismatch factor. These two effects can be analyzed separately by considering first the results for a hypothetical zero grain size (r = 0 in Table 3) because they include the averaging over the polar angles but not the phase-matching effects and then the results for r = 3 and 10 μm, where both effects are accounted for.
First, when only averaging deff over the polar angles to get ⟨deff⟩, the SHG response drops by more than 1 order of magnitude with respect to the dominant χ(2) tensor components (see column r = 0 μm in Table 3). This reduction is supported by the polar maps of deff(θ, ϕ) (Figure S31 of SI), which highlight the (θ, ϕ) domains that result in large ⟨deff⟩(θ, ϕ) values and the fact that many (θ, ϕ) domains are associated with much smaller SHG responses. Then, while accounting for the grain size, ⟨deff⟩ drops quite rapidly with r (Figure 7). For r = 3 μm, the responses are already reduced by about one order of magnitude with respect to the situation without phase mismatch and by another factor of two to three when going from r = 3 to 10 μm. Figures S32–S33 of the SI describe the phase-matching effects on the polar maps of ⟨deff⟩(θ, ϕ) for r = 3 μm and r = 10 μm.

Figure 7

Figure 7. Grain size dependence of the calculated ⟨deff⟩ values for MIL-53(Al)-NH2/NO2, MIL-53(Ga)-NH2/NO2, and MIL-53(Al)-NH2(vnp). For MIL-53(M)-NH2/NO2, results are listed for the pure A and C phases as well as for the A:C ratios obtained from PXRD analysis.

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This ultimately leads to relatively low theoretical ⟨deff⟩ values for MIL-53(Al)-NH2/NO2 (1) and MIL-53(Ga)-NH2/NO2 (3), with respect to the potential χ(2) or deff values if pure phase compounds could be created. Then, these final ⟨deff⟩ results, that is, when incorporating for all effects, show that the pure A and C phases of compound 1/2 and 3 are characterized by larger values of ⟨deff⟩ than compound 4 and that the differences between the A and C phases are larger for the Ga derivative. The comparison of these results with the experimental values also suggests that compound (2) is characterized by a much more ordered structure and thus higher χ(2) than compound 1.
The ⟨deff⟩ values for the optical path of 10 μm of the mixed AC phases of compound (1)/(2) (0.048 pm V–1) and (3) (0.107 pm V–1) and that of vnp structure of MIL-53(Al)-NH2 (0.178 pm V–1) compare quite well with experimental values (0.02, 0.02, and 0.05 pm V–1, respectively). Although many effects were accounted for in the calculations, several factors need to be taken under consideration. First of all, the polydispersity of the studied materials hinders a direct comparison of the experimental value with single points (r values) of Figure 7.
The second important factor is the absorption of the SH signal and the associated resonance enhancement, larger in the case of MIL-53(Al/Ga)-NH2/NO2 species than in the case of the amino derivative. This could lead to a conclusion that the final results obtained for MIL-53(Al/Ga)-NH2/NO2 are somewhat underestimated and the true structure of these materials does not disfavor the χ(2). Indeed, the overall values of the phase-matched mixed A/C crystals (0.75 pm V–1 for Al and 1.22 pm V–1 for Ga compound) are comparable to those of commercial inorganic NLO materials such as KDP (0.38–0.41 pm V–1 at 1064 nm), KTP (deff 1.7–3.5 pm V–1 at 800 nm) or BBO (deff 1.76–1.83 pm V–1 at 800 nm). (67) Moreover, the calculated χ(2) tensors are considerable, which suggests that the investigated materials are of potential interest.

Conclusions

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For the first time a polar organization of the well known PNA motif was achieved by incorporation of the motif in MOF structures. To be able to incorporate the motif in several MIL-53 MOFs, a linker was designed possessing an extended π-conjugated system with amino donor- and nitro acceptor-groups, as in PNA. Combining this linker with three different cations as nodes (Al, Ga, In), several MIL-53 frameworks were created. MIL-53(Al)-NH2/NO2 and MIL-53(Ga)-NH2/NO2 displayed a net polar and thus SHG-active organization of the linkers, whereas the MIL-53(In)-NH2/NO2 compound did not display SHG activity, indicating that no polar organization was obtained.
The SHG activity of the aluminum and gallium compounds was experimentally determined to be in the same range as that of the previously reported MIL-53(Al)-NH2, where only an amino donor group resides on the terephthalate linker. Ab initio calculations revealed that while the terephthalate linker with the amino and nitro functionalization is more NLO efficient than the linker with sole amino functionalization, the occurrence of multiple phases of linker organization in MIL-53(M)-NH2/NO2 structures leads to partial cancellation of the SHG activity. Therefore, the SHG activities of MIL-53(Al)-NH2/NO2 and MIL-53(Ga)-NH2/NO2 lie in the same range as that of MIL-53(Al)-NH2. Moreover, theoretical calculations revealed that the SHG activity of the MIL-53(M)-NH2/NO2 structures decreases with increasing grain size and that for the smallest grain size, where perfect phase matching occurs, the theoretical SHG activity is comparable to that of commercial inorganic NLO materials, such as KDP. This means that the investigated materials are of potential interest.
This research shows that the creation of MOFs containing linkers that mimic interesting SONLO properties of organic molecules in their motif can be a promising strategy to obtain functional polar crystals.

Supporting Information

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpcc.7b09190.

  • Detailed information about the linker synthesis, TG measurements, EA analyses, NMR spectra, and so on. (PDF)

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Author Information

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  • Corresponding Authors
  • Authors
    • Karen Markey - Centre for Surface Chemistry and Catalysis, Faculty of Bioscience Engineering, University of Leuven, 3001 Leuven, Belgium
    • Martin Krüger - Institut für Anorganische Chemie, Christian-Albrechts-Universität zu Kiel, 24118 Kiel, Germany
    • Tomasz Seidler - K. Gumiński Department of Theoretical Chemistry, Jagiellonian University, Romana Ingardena 3, 30-060 Kraków, Poland;  Unité de Chimie Physique Théorique et Structurale, University of Namur, 5000 Namur, Belgium
    • Helge Reinsch - Institut für Anorganische Chemie, Christian-Albrechts-Universität zu Kiel, 24118 Kiel, Germany;  Orcidhttp://orcid.org/0000-0001-5288-1135
    • Thierry Verbiest - Molecular Imaging and Photonics, KU Leuven − University of Leuven, 3001 Leuven, Belgium
    • Dirk E. De Vos - Centre for Surface Chemistry and Catalysis, Faculty of Bioscience Engineering, University of Leuven, 3001 Leuven, Belgium
  • Author Contributions

    K.M., M.K., and T.S. contributed equally.

  • Funding

    M.K. was financially supported by the Deutsche Forschungsgemeinschaft (DFG) (STO 643/10-1). K.M., T.S., D.E.D.V., and B.C. are grateful to Belspo for funding in the IAP project Functional Supramolecular Systems. D.E.D.V., T.V., and M.A.v.d.V. are grateful for the financial support from the Hercules Foundation and to FWO. This work was supported by funds from the Francqui Foundation (BC).The ab initio calculations were performed on the computers of the Consortium des Equipements de Calcul Intensif, including those of the Technological Platform of High-Performance Computing, for which we gratefully acknowledge the financial support of the FNRS-FRFC (convention nos. 2.4.617.07.F and 2.5020.11) and of the University of Namur. This research was supported in part by PL-Grid Infrastructure.

  • Notes
    The authors declare no competing financial interest.

References

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This article references 67 other publications.

  1. 1
    Ye, Z.-G. Handbook of Dielectric, Piezoelectric and Ferroelectric Materials: Synthesis, Properties and Applications; Woodhead Pub. and Maney Pub. on behalf of The Institute of Materials, Minerals & Mining, 2008.
    Google Scholar
    There is no corresponding record for this reference.
  2. 2
    Curtin, D. Y.; Paul, I. C. Chemical Consequences of the Polar Axis in Organic Solid-State Chemistry Chem. Rev. 1981, 81, 525– 541 DOI: 10.1021/cr00046a001
    Google Scholar
    2
    Chemical consequences of the polar axis in organic solid-state chemistry
    Curtin, David Y.; Paul, Iain C.
    Chemical Reviews (Washington, DC, United States) (1981), 81 (6), 525-41CODEN: CHREAY; ISSN:0009-2665.
    The concept and consequences in org. chem. of the polar axis are reviewed with 59 refs.
  3. 3
    Asadi, K.; van der Veen, M. A. Ferroelectricity in Metal-Organic Frameworks: Characterization and Mechanisms Eur. J. Inorg. Chem. 2016, 2016, 4332– 4344 DOI: 10.1002/ejic.201600932
    Google Scholar
    3
    Ferroelectricity in Metal-Organic Frameworks: Characterization and Mechanisms
    Asadi, Kamal; van der Veen, Monique Ann
    European Journal of Inorganic Chemistry (2016), 2016 (27), 4332-4344CODEN: EJICFO; ISSN:1434-1948. (Wiley-VCH Verlag GmbH & Co. KGaA)
    Ferroelec. metal-org. frameworks are emerging as an exciting field of research and have witnessed great progress in the last decade. In this contribution, we briefly discuss ferroelectricity and its means of demonstration. Three mechanisms that lead to ferroelectricity are identified and critically discussed. On the basis of the shortcomings present in the literature, we present a protocol for the study of ferroelectricity in MOF compds.
  4. 4
    Fainman, Y.; Ma, J.; Lee, S. H. Non-Linear Optical Materials and Applications Mater. Sci. Rep. 1993, 9, 53– 139 DOI: 10.1016/0920-2307(93)90008-3
    Google Scholar
    4
    Non-linear optical materials and applications
    Fainman, Y.; Ma, J.; Lee, S. H.
    Materials Science Reports (1993), 9 (2-3), 53-139CODEN: MSREEL; ISSN:0920-2307.
    A review, with 219 refs., of the present status of the non-linear optical materials and devices, and their applications for optical signal processing and computing. The primary motivation behind this review is to introduce the different areas involved, paying special attention to their interfaces. First, the optical non-linearities in semiconductor materials, semiconductor microstructures and photorefractive materials are introduced. For the semiconductors, authors discuss the third-order non-linear susceptibilities due to virtual transitions (e.g., bound electrons in intrinsic semiconductors and non-linear motion and energy relaxation of free carriers in doped semiconductors) and due to real transitions (e.g. valence-to-conduction-band transitions, free-carrier transitions, impurity transitions and transitions in excitons and excitonic complexes). Recent advances in engineering semiconductor microstructures are discussed and shown to enhance their third-order non-linear optical susceptibilities in comparison with the bulk semiconductors. The mechanism of the photorefractive effect is next introduced and analyzed in conjunction with several engineering approaches to enhance the performances of the photorefractive non-linearities (e.g., non-stationary recording, multiphoton excitation, combination of the photorefractive effect with the electrorefractive non-linearities near the band edge, etc.). Using the photorefractive materials as an example, authors define a set of figures of merit based on the requirements from the optical devices for system applications. Using these figures of merit authors evaluate and discuss the optimization of different photorefractive materials: ferroelec. oxides (e.g., LiNbO3, BaTiO3, KNbO3, tungsten bronze family, etc.), compd. semiconductors (e.g., GaAs, GaP, InP, CdS, CdSe, CdTe, etc.), sillenites (e.g., Bi12SiO20, Bi12GeO20), and ceramics. Finally, the applications of non-linear optical materials are discussed using the photorefractive materials as an example. Two types of devices are distinguished: passive devices that are based on vol. holog. storage of information and active devices that are based on continuous two-wave and four-wave mixing of optical information carrying waves. These devices are evaluated and their optimization is discussed in conjunction with applications to analog and digital optical signal processing and computing. Examples of analog (e.g., inverse filter and linear algebra processor) and digital (e.g., parallel access optical memories and reconfigurable interconnects) optical computing applications will be also discussed.
  5. 5
    Hollingsworth, M. D. Crystal Engineering: From Structure to Function Science 2002, 295, 2410– 2413 DOI: 10.1126/science.1070967
    Google Scholar
    5
    Crystal engineering: from structure to function
    Hollingsworth, Mark D.
    Science (Washington, DC, United States) (2002), 295 (5564), 2410-2413CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)
    A review. Modern crystal engineering has emerged as a rich discipline whose success requires an iterative process of synthesis, crystallog., crystal structure anal., and computational methods. By focusing on the mol. recognition events during nucleation and growth, chemists have uncovered new ways of controlling the internal structure and symmetry of crystals and of producing materials with useful chem. and phys. properties.
  6. 6
    Mingabudinova, L. R.; Vinogradov, V. V.; Milichko, V. A.; Hey-Hawkins, E.; Vinogradov, A. V. Metal–Organic Frameworks as Competitive Materials for Non-Linear Optics Chem. Soc. Rev. 2016, 45, 5408– 5431 DOI: 10.1039/C6CS00395H
    Google Scholar
    6
    Metal-organic frameworks as competitive materials for non-linear optics
    Mingabudinova, L. R.; Vinogradov, V. V.; Milichko, V. A.; Hey-Hawkins, E.; Vinogradov, A. V.
    Chemical Society Reviews (2016), 45 (19), 5408-5431CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)
    The last five years have witnessed a huge breakthrough in the creation and the study of the properties of a new class of compds. - metamaterials. The next stage of this technol. revolution will be the development of active, controllable, and non-linear metamaterials, surpassing natural media as platforms for optical data processing and quantum information applications. However, scientists are constantly faced with the need to find new methods that can ensure the formation of quantum and non-linear metamaterials with higher resoln. One such method of producing metamaterials in the future, which will provide scalability and availability, is chem. synthesis. Meanwhile, the chem. synthesis of organized 3D structures with a period of a few nanometers and a size of up to a few millimeters is not an easy task and is yet to be resolved. The most promising avenue seems to be the use of highly porous structures based on metal-org. frameworks that have demonstrated their unique properties in the field of non-linear optics (NLO) over the past three years. Thus, the aim of this review is to examine current progress and the possibilities of using metal-org. frameworks in the field of non-linear optics as chem. obtained metamaterials of the future. The review begins by presenting the theor. principles of phys. phenomena represented by math. descriptions for clarity. Major attention is paid to the second harmonic generation (SHG) effect. In this section we compare inorg. single crystals, which are most commonly used to study the effect in question, to org. materials, which also possess the required properties. Based on these data, we present a rationale for the possibility of studying the non-linear optical properties of metal-org. structures as well as describing the use of synthetic approaches and the difficulties assocd. with them. The second part of the review explicitly acquaints the reader with a new class of materials which successfully combines the pos. properties of org. and inorg. materials. Using recently synthesized metal-org. frameworks and coordination polymers in the field of non-linear optics as an example, we consider synthetic approaches used for obtaining materials with desired properties and the factors to be considered in this case. Finally, probable trends towards improving the quality of the synthesized materials with regards to their further use in the field of non-linear optical effects are described.
  7. 7
    Evans, O. R.; Lin, W. Crystal Engineering of NLO Materials Based on Metal–Organic Coordination Networks Acc. Chem. Res. 2002, 35, 511– 522 DOI: 10.1021/ar0001012
    Google Scholar
    7
    Crystal Engineering of NLO Materials Based on Metal-Organic Coordination Networks
    Evans, Owen R.; Lin, Wenbin
    Accounts of Chemical Research (2002), 35 (7), 511-522CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)
    A review. Crystal engineering, the ability to predict and control the packing of mol. building units in the solid state, has attracted much attention over the past three decades owing to its potential exploitation for the synthesis of technol. important materials. The authors present here the development of crystal-engineering strategies toward the synthesis of noncentrosym. infinite coordination networks for use as 2nd-order nonlinear optical (NLO) materials. Work performed mainly in the authors' lab. demonstrated that noncentrosym. solids based on infinite networks can be rationally synthesized by combining unsym. bridging ligands and metal centers with well-defined coordination geometries. Specifically, coordination networks based on 3-dimensional diamondoid and 2-dimensional grid structures can be successfully engineered with a high degree of probability and predictability to crystallize in noncentrosym. space groups. The authors have also included noncentrosym. solids based on 1-dimensional chains and related helical structures for comparison.
  8. 8
    Shi, Y.; Zhang, C.; Zhang, H.; Bechtel, J. H.; Dalton, L. R.; Robinson, B. H.; Steier, W. H. Low (Sub-1-V) Halfwave Voltage Polymeric Electro-Optic Modulators Achieved by Controlling Chromophore Shape Science 2000, 288, 119– 122 DOI: 10.1126/science.288.5463.119
    Google Scholar
    8
    Low (sub-1-volt) halfwave voltage polymeric electro-optic modulators achieved by controlling chromophore shape
    Shi, Yongqiang; Zhang, Cheng; Zhang, Hua; Bechtel, James H.; Dalton, Larry R.; Robinson, Bruce H.; Steier, William H.
    Science (Washington, D. C.) (2000), 288 (5463), 119-122CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)
    Electrooptic (EO) modulators encode elec. signals onto fiber optic transmissions. High drive voltages limit gain and noise levels. Typical polymeric and Li niobate modulators operate with halfwave voltages of 5 V. Sterically modified org. chromophores were used to reduce the attenuation of elec. field poling-induced electrooptic activity caused by strong intermol. electrostatic interactions. Such modified chromophores, incorporated into polymer hosts, were used to fabricate EO modulators with halfwave voltages of 0.8 V (at a telecommunications wavelength of 1318 nm) and to achieve a halfwave voltage-interaction length product of 2.2 V- centimeters. Optical push-pull poling and driving were also used to reduce halfwave voltage. This study, together with recent demonstrations of exceptional bandwidths (more than 110 GHz) and ease of integration (with very large scale integration semiconductor circuitry and ultra-low-loss passive optical circuitry) demonstrates the potential of polymeric materials for next generation telecommunications, information processing, and radio frequency distribution.
  9. 9
    Burland, D. M.; Miller, R. D.; Walsh, C. A. Second-Order Nonlinearity in Poled-Polymer Systems Chem. Rev. 1994, 94, 31– 75 DOI: 10.1021/cr00025a002
    Google Scholar
    9
    Second-order nonlinearity in poled-polymer systems
    Burland, Donald M.; Miller, Robert D.; Walsh, Cecilia A.
    Chemical Reviews (Washington, DC, United States) (1994), 94 (1), 31-75CODEN: CHREAY; ISSN:0009-2665.
    A review with 290 refs. discussed the macroscopic second-order nonlinearity, the development and decay of the elec. field poled order responsible for the nonlinearity, methods of detg. of this nonlinearity, and the chem. nature of the polymeric systems identified as promising second-order materials.
  10. 10
    Marks, T. J.; Ratner, M. A. Design, Synthesis, and Properties of Molecule-Based Assemblies with Large Second-Order Optical Nonlinearities Angew. Chem., Int. Ed. Engl. 1995, 34, 155– 173 DOI: 10.1002/anie.199501551
    Google Scholar
    There is no corresponding record for this reference.
  11. 11
    Ashwell, G. J.; Jackson, P. D.; Crossland, W. A. Non-Centrosymmetry and Second-Harmonic Generation in Z-Type Langmuir-Blodgett Films Nature 1994, 368, 438– 440 DOI: 10.1038/368438a0
    Google Scholar
    There is no corresponding record for this reference.
  12. 12
    Penner, T. L.; Motschmann, H. R.; Armstrong, N. J.; Ezenyilimba, M. C.; Williams, D. J. Efficient Phase-Matched Second-Harmonic Generation of Blue Light in an Organic Waveguide Nature 1994, 367, 49– 51 DOI: 10.1038/367049a0
    Google Scholar
    There is no corresponding record for this reference.
  13. 13
    Lin, W. W.; Lin, W. W.; Wong, G. K.; Marks, T. J. Supramolecular Approaches to Second-Order Nonlinear Optical Materials. Self-Assembly and Microstructural Characterization of Intrinsically Acentric [(Aminophenyl)azo]pyridinium Superlattices J. Am. Chem. Soc. 1996, 118, 8034– 8042 DOI: 10.1021/ja960395f
    Google Scholar
    13
    Supramolecular Approaches to Second-Order Nonlinear Optical Materials. Self-Assembly and Microstructural Characterization of Intrinsically Acentric [(Aminophenyl)azo]pyridinium Superlattices
    Lin, Wenbin; Lin, Weiping; Wong, George K.; Marks, Tobin J.
    Journal of the American Chemical Society (1996), 118 (34), 8034-8042CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    The synthesis and characterization of self-assembled 2nd-order nonlinear optical multilayer materials contg. the high-hyperpolarizability [(aminophenyl)azo]pyridinium chromophore are described. The chromophoric multilayers are assembled on clean glass or single crystal Si substrates via the following iterative reaction sequence: (1) treatment with 4-ClCH2C6H4SiCl3, 3-BrC3H6SiCl3, or 3-IC3H6SiI3 to afford a self-assembled coupling layer; (2) quaternization of 4-[[4-[N,N-bis(hydroxylethyl)amino]phenyl]azo]pyridine in a topotactic fashion to generate an [(aminophenyl)azo]pyridinium chromophore layer; (3) crosslinking with Cl(SiCl2O)2SiCl3 to afford a capping layer (which regenerates surface hydroxyl groups for subsequent layer deposition). The new chromophore precursor 4-[[4-[N,N-bis(hydroxylethyl)amino]phenyl]azo]pyridine was synthesized by diazotization of 4-aminopyridine followed by coupling with N-phenyldiethanolamine and was characterized by elemental anal., mass spectrometry, and IR, UV-visible, and NMR spectroscopies. The chromophoric multilayers were characterized by x-ray photoelectron and transmission optical spectroscopies, spectroscopic ellipsometry, x-ray reflectivity, advancing contact angle measurements, and polarized 2nd harmonic generation (SHG). The good structural regularity of the chromophoric multilayers is indicated by the linear dependence of the [(aminophenyl)azo]pyridinium chromophore longitudinal HOMO → LUMO charge-transfer excitation absorbance at 572 nm and the ellipsometry- and x-ray reflectivity-derived multilayer thicknesses on the no. of assembled trilayers, while the uniform polar order of the stacked chromophoric multilayers is evidenced by the quadratic dependence of the 2nd harmonic generation intensities on the no. of trilayers. The [(aminophenyl)azo]pyridinium multilayers are photochem. stable, have very high structural regularities, and exhibit a 2nd-order nonlinear optical susceptibility (χ(2)) of ∼3.6 × 10-7 esu (∼150 pm/V) at a fundamental λ = 1064 nm. At. force microscopy reveals that the surfaces of the self-assembled multilayers are smooth (root mean square roughness = 12 Å for a 10 trilayer sample), undoubtedly reflecting the high 3-dimensional structural regularities of the individual layers.
  14. 14
    Katz, H. E.; Wilson, W. L.; Scheller, G. Chromophore Structure, Second Harmonic Generation, and Orientational Order in Zirconium Phosphonate/Phosphate Self-Assembled Multilayers J. Am. Chem. Soc. 1994, 116, 6636– 6640 DOI: 10.1021/ja00094a019
    Google Scholar
    14
    Chromophore Structure, Second Harmonic Generation, and Orientational Order in Zirconium Phosphonate/Phosphate Self-Assembled Multilayers
    Katz, H. E.; Wilson, W. L.; Scheller, G.
    Journal of the American Chemical Society (1994), 116 (15), 6636-40CODEN: JACSAT; ISSN:0002-7863.
    Two new phosphono-terminated polar azo dyes, the rigid 1-(4-phosphonophenyl)-4-[4-[4-(2-hydroxyethylsulfonyl)phenylazo]phenyl]piperazine (I) and 3-[4-[[4-[2-cyano-2-(hydroxyethoxycarbonyl)ethenyl]phenylazo]phenyl]-N-methylamino]propylphosphonic acid (II) with a large mol. hyperpolarizability, were designed and incorporated into Zr-based surface multilayers. Second harmonic generation (SHG) was obsd. from the multilayers as a function of incident and polarization angles and compared with that from a previously reported aminophenylazophenylphosphonic acid chromophore. I and II were analogous to moieties commonly used in elec. field-poled polymers, allowing comparisons between the polymers and the multilayers. Apparent order parameters 〈cos3θ〉 were >0.2 for I and ∼0.16 for II. Because of local field effects, the value for I was probably a lower limit. Use of other dyes that were both rigid and highly polar led to H-aggregation. Insertion of a nonpolar chromophore layer among the polar layers had no effect on SHG. The syntheses involved several novel reactions, involving the prepn. of an unsym. substituted diphenylpiperazine, an anilinoalkyl phosphonate, and the deprotected phosphonic acids themselves.
  15. 15
    Zyss, J.; Nicoud, J. F.; Coquillay, M. Chirality and Hydrogen Bonding in Molecular Crystals for Phase-Matched Second-Harmonic Generation: N-(4-Nitrophenyl)-(L)-Prolinol (NPP) J. Chem. Phys. 1984, 81, 4160 DOI: 10.1063/1.448134
    Google Scholar
    15
    Chirality and hydrogen bonding in molecular crystals for phase-matched second-harmonic generation: N-(4-nitrophenyl)-(L)-prolinol (NPP)
    Zyss, J.; Nicoud, J. F.; Coquillay, M.
    Journal of Chemical Physics (1984), 81 (9), 4160-7CODEN: JCPSA6; ISSN:0021-9606.
    The higher 2nd-harmonic efficiency, of powders, of a new org. mol. crystal N-(4-nitrophenyl)-(L)-prolinol (NPP) is reported. Electronic polarizability of NPP mols. relates to that of other p-nitroaniline-like structures such as that of previously reported N-(2,4-dinitrophenyl)methyl alaninate, and the increase in cryst. nonlinear efficiency by one order of magnitude above the latter is ascribed to an optimized cryst. structure rather than to minor changes of the mol. hyperpolarizability. The simultaneous chiral and H-bonding character of the prolinol electron-donating group leads to a quasioptimal angle, with respect to quadratic phase-matched nonlinear interactions, between the mol. transition dipole moments and the 2-fold axis of the monoclinic P21 crystal structure. Based on a simple oriented gas description of the quasiplanar structure of the crystal, 2 possible mutually exclusive 2nd-harmonic phase-matched configurations are evidenced and promote the optimized nonlinear tensor coeff.
  16. 16
    Gryl, M.; Krawczuk, A.; Stadnicka, K. Polymorphism of Urea-Barbituric Acid Co-Crystals Acta Crystallogr., Sect. B: Struct. Sci. 2008, 64, 623– 632 DOI: 10.1107/S0108768108026645
    Google Scholar
    16
    Polymorphism of urea-barbituric acid co-crystals
    Gryl, Marlena; Krawczuk, Anna; Stadnicka, Katarzyna
    Acta Crystallographica, Section B: Structural Science (2008), 64 (5), 623-632CODEN: ASBSDK; ISSN:0108-7681. (International Union of Crystallography)
    The crystal structures of three polymorphs found for the addn. complex of urea and barbituric acid are described and compared. Two polymorphs are monoclinic, space groups P21/c and Cc, whereas the 3rd is triclinic, P‾1. The displacement of electron d. towards the mesomeric forms, corresponding to the tautomeric forms of higher stability, of the barbituric acid mol. seem to influence the type of H bonds formed, which in turn dets. the different packing topol. in the polymorphs. While the polymorphic forms can be easily differentiated at the 1st-level graph-set anal. of their H-bonding patterns, a higher-level anal. enables important features of the mutual spatial arrangement of the structural components to be revealed. Crystallog. data are given.
  17. 17
    Gryl, M.; Kozieł, M.; Stadnicka, K.; Matulková, I.; Němec, I.; Tesařová, N.; Němec, P. Lidocaine Barbiturate: A Promising Material for Second Harmonic Generation CrystEngComm 2013, 15, 3275 DOI: 10.1039/c3ce00059a
    Google Scholar
    There is no corresponding record for this reference.
  18. 18
    Gryl, M.; Seidler, T.; Stadnicka, K.; Matulkova, I.; Nemec, I.; Tesarova, N.; Nemec, P. The Crystal Structure and Optical Properties of a Pharmaceutical Co-Crystal - the Case of the Melamine-Barbital Addition Compound CrystEngComm 2014, 16, 5765– 5768 DOI: 10.1039/c4ce00178h
    Google Scholar
    There is no corresponding record for this reference.
  19. 19
    Evans, O. R.; Xiong, R.; Wang, Z.; Wong, G. K.; Lin, W. Crystal Engineering of Acentric Diamondoid Metal-Organic Coordination Networks Angew. Chem., Int. Ed. 1999, 38, 536– 538 DOI: 10.1002/(SICI)1521-3773(19990215)38:4<536::AID-ANIE536>3.0.CO;2-3
    Google Scholar
    There is no corresponding record for this reference.
  20. 20
    Mendiratta, S.; Lee, C. H.; Lee, S. Y.; Kao, Y. C.; Chang, B. C.; Lo, Y. H.; Lu, K. L. Structural Characteristics and Non-Linear Optical Behaviour of a 2-Hydroxynicotinate-Containing Zinc-Based Metal-Organic Framework Molecules 2015, 20, 8941– 8951 DOI: 10.3390/molecules20058941
    Google Scholar
    20
    Structural characteristics and non-linear optical behaviour of a 2-hydroxynicotinate-containing zinc-based metal-organic framework
    Mendiratta, Shruti; Lee, Cheng-Hua; Lee, Sih-Ying; Kao, Ya-Chuan; Chang, Bor-Chen; Lo, Yih-Hsing; Lu, Kuang-Lieh
    Molecules (2015), 20 (5), 8941-8951CODEN: MOLEFW; ISSN:1420-3049. (MDPI AG)
    Materials with non-linear optical (NLO) properties play an important role in the construction of electronic devices for optical communications, optical data processing and data storage. With this aim in mind, a Zn(II)-based metal-org. framework {[Zn2(nica)2(bpy)1.5(H2O)]·0.5(bpy)·3H2O}n (1), was synthesized using 4,4'-bipyridine (bpy) and a potentially bidentate ligand, 2-hydroxynicotinic acid (H2nica) with a salicylate binding moiety. A single-crystal X-ray diffraction anal. revealed that compd. 1 crystd. in the orthorhombic space group Fdd2 and was composed of a three dimensional porous framework. Since Fdd2 belonged to a class of non-centrosym. space groups, we therefore investigated the non-linear optical behavior of compd. 1. Photoluminescence studies revealed that compd. 1 exhibited a blue light emission with a maxima at 457 nm.
  21. 21
    Serra-Crespo, P.; van der Veen, M. A.; Gobechiya, E.; Houthoofd, K.; Filinchuk, Y.; Kirschhock, C. E. A.; Martens, J. A.; Sels, B. F.; De Vos, D. E.; Kapteijn, F. NH2-MIL-53(Al): A High-Contrast Reversible Solid-State Nonlinear Optical Switch J. Am. Chem. Soc. 2012, 134, 8314– 8317 DOI: 10.1021/ja300655f
    Google Scholar
    21
    NH2-MIL-53(Al): A High-Contrast Reversible Solid-State Nonlinear Optical Switch
    Serra-Crespo, Pablo; van der Veen, Monique A.; Gobechiya, Elena; Houthoofd, Kristof; Filinchuk, Yaroslav; Kirschhock, Christine E. A.; Martens, Johan A.; Sels, Bert F.; De Vos, Dirk E.; Kapteijn, Freek; Gascon, Jorge
    Journal of the American Chemical Society (2012), 134 (20), 8314-8317CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    The metal-org. framework NH2-MIL-53(Al) is the 1st solid-state material displaying nonlinear optical switching due to a conformational change upon breathing. A switching contrast of at least 38 was obsd. This transition originates in the restrained linker mobility in the very narrow pore configuration.
  22. 22
    Jain, P.; Dalal, N. S.; Toby, B. H.; Kroto, H. W.; Cheetham, A. K. Order-Disorder Antiferroelectric Phase Transition in a Hybrid Inorganic-Organic Framework with the Perovskite Architecture J. Am. Chem. Soc. 2008, 130, 10450– 10451 DOI: 10.1021/ja801952e
    Google Scholar
    22
    Order-Disorder Antiferroelectric Phase Transition in a Hybrid Inorganic-Organic Framework with the Perovskite Architecture
    Jain, Prashant; Dalal, Naresh S.; Toby, Brian H.; Kroto, Harold W.; Cheetham, Anthony K.
    Journal of the American Chemical Society (2008), 130 (32), 10450-10451CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    [(CH3)2NH2]Zn(HCOO)3, adopts a structure that is analogous to that of a traditional perovskite, ABX3, with A = [(CH3)2NH2], B = Zn, and X = HCOO. The hydrogen atoms of the di-Me ammonium cation, which hydrogen bond to oxygen atoms of the formate framework, are disordered at room temp. X-ray powder diffraction, dielec. const., and sp. heat data show that [(CH3)2NH2]Zn(HCOO)3 undergoes an order-disorder phase transition on cooling below ∼156 K. We present evidence that this is a classical paraelec. to antiferroelec. phase transition that is driven by ordering of the hydrogen atoms. This sort of elec. ordering assocd. with order-disorder phase transition is unprecedented in hybrid frameworks and opens up an exciting new direction in rational synthetic strategies to create extended hybrid networks for applications in ferroic-related fields.
  23. 23
    Jain, P.; Ramachandran, V.; Clark, R. J.; Zhou, H. D.; Toby, B. H.; Dalal, N. S.; Kroto, H. W.; Cheetham, A. K. Multiferroic Behavior Associated with an Order–Disorder Hydrogen Bonding Transition in Metal–Organic Frameworks (MOFs) with the Perovskite ABX3 Architecture J. Am. Chem. Soc. 2009, 131, 13625– 13627 DOI: 10.1021/ja904156s
    Google Scholar
    23
    Multiferroic Behavior Associated with an Order-Disorder Hydrogen Bonding Transition in Metal-Organic Frameworks (MOFs) with the Perovskite ABX3 Architecture
    Jain, Prashant; Ramachandran, Vasanth; Clark, Ronald J.; Zhou, Hai Dong; Toby, Brian H.; Dalal, Naresh S.; Kroto, Harold W.; Cheetham, Anthony K.
    Journal of the American Chemical Society (2009), 131 (38), 13625-13627CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    Multiferroic behavior in perovskite-related metal-org. frameworks of general formula [(CH3)2NH2]M(HCOO)3, where M = Mn, Fe, Co, and Ni, is reported. All four compds. exhibit paraelec.-antiferroelec. phase transition behavior in the temp. range 160-185 K (Mn: 185 K, Fe: 160 K; Co: 165 K; Ni: 180 K); this is assocd. with an order-disorder transition involving the hydrogen bonded dimethylammonium cations. On further cooling, the compds. become canted weak ferromagnets below 40 K. This research opens up a new class of multiferroics in which the elec. ordering is achieved by means of hydrogen bonding.
  24. 24
    Zhang, W.; Cai, Y.; Xiong, R. G.; Yoshikawa, H.; Awaga, K. Exceptional Dielectric Phase Transitions in a Perovskite-Type Cage Compound Angew. Chem., Int. Ed. 2010, 49, 6608– 6610 DOI: 10.1002/anie.201001208
    Google Scholar
    24
    Exceptional Dielectric Phase Transitions in a Perovskite-Type Cage Compound
    Zhang, Wen; Cai, Ying; Xiong, Ren-Gen; Yoshikawa, Hirofumi; Awaga, Kunio
    Angewandte Chemie, International Edition (2010), 49 (37), 6608-6610, S6608/1-S6608/5CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
    The authors presented a new org.-inorg. hybrid cage compd. with the perovskite-type architecture. The compd. is a novel org.-inorg. hybrid cage compd. (HIm)2[KFe(CN)6] (where Him = imidazolium) with a perovskite-type structure, in which the order-disorder behavior of the Hlm polar guests give rise to striking dielec. anomalies. It exhibits two phase transitions at 158 K and 187 K. An order-disorder mechanism is found in the structural transformations owing to the motions of the cationic guests under different temps. The compds. represents a new class of switchable mol. dielecs. that shows striking dielec. anomalies and anisotropy. Investigations on such systems can shed light on the understanding of structural phase transitions of switchable mol. dielecs. and afford a useful strategy in searching for new elec. ordering materials.
  25. 25
    Xu, G.-C.; Ma, X.-M.; Zhang, L.; Wang, Z.-M.; Gao, S. Disorder-Order Ferroelectric Transition in the Metal Formate Framework of [NH4][Zn(HCOO)3] J. Am. Chem. Soc. 2010, 132, 9588– 9590 DOI: 10.1021/ja104263m
    Google Scholar
    25
    Disorder-Order Ferroelectric Transition in the Metal Formate Framework of [NH4][Zn(HCOO)3]
    Xu, Guan-Cheng; Ma, Xiao-Ming; Zhang, Li; Wang, Zhe-Ming; Gao, Song
    Journal of the American Chemical Society (2010), 132 (28), 9588-9590CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    A three-dimensional chiral metal formate framework compd., [NH4][Zn(HCOO)3], undergoes a paraelec.-ferroelec. phase transition at 191 K triggered by the disorder-order transition of NH4+ cations within the structure. Crystallog. data are given.
  26. 26
    Cui, H.; Zhou, B.; Long, L.-S.; Okano, Y.; Kobayashi, H.; Kobayashi, A. A Porous Coordination-Polymer Crystal Containing One-Dimensional Water Chains Exhibits Guest-Induced Lattice Distortion and a Dielectric Anomaly Angew. Chem., Int. Ed. 2008, 47, 3376– 3380 DOI: 10.1002/anie.200705846
    Google Scholar
    There is no corresponding record for this reference.
  27. 27
    Dong, X.-Y.; Li, B.; Ma, B.-B.; Li, S.-J.; Dong, M.-M.; Zhu, Y.-Y.; Zang, S.-Q.; Song, Y.; Hou, H.-W.; Mak, T. C. W. Ferroelectric Switchable Behavior through Fast Reversible De/adsorption of Water Spirals in a Chiral 3D Metal-Organic Framework J. Am. Chem. Soc. 2013, 135, 10214– 10217 DOI: 10.1021/ja403449k
    Google Scholar
    27
    Ferroelectric Switchable Behavior through Fast Reversible De/adsorption of Water Spirals in a Chiral 3D Metal-Organic Framework
    Dong, Xi-Yan; Li, Bo; Ma, Bin-Bin; Li, Shi-Jun; Dong, Ming-Ming; Zhu, Yan-Yan; Zang, Shuang-Quan; Song, You; Hou, Hong-Wei; Mak, Thomas. C. W.
    Journal of the American Chemical Society (2013), 135 (28), 10214-10217CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    A polar homochiral 3-dimensional MOF [{Co2(L)(bpe)(H2O)}·5H2O]n constructed with cobalt(II) and a new ligand N-(1,3-dicarboxy-5-benzyl)-carboxymethylglycine (H4L) accommodates ordered helical water streams in its helical grooves. It provides the 1st example of switchable ferroelec. and optical behavior through two-step reversible single-crystal to single-crystal transformation (SCSC) upon desorption/adsorption of water spirals and coordinated water mols., resp.
  28. 28
    Markey, K.; Putzeys, T.; Horcajada, P.; Devic, T.; Guillou, N.; Wübbenhorst, M.; Van Cleuvenbergen, S.; Verbiest, T.; De Vos, D. E.; van der Veen, M. A. Second Harmonic Generation Microscopy Reveals Hidden Polar Organization in Fluoride Doped MIL-53(Fe) Dalt. Trans. 2016, 45, 4401– 4406 DOI: 10.1039/C5DT04632G
    Google Scholar
    28
    Second harmonic generation microscopy reveals hidden polar organization in fluoride doped MIL-53(Fe)
    Markey, Karen; Putzeys, Tristan; Horcajada, Patricia; Devic, Thomas; Guillou, Nathalie; Wubbenhorst, Michael; Cleuvenbergen, Stijn Van; Verbiest, Thierry; De Vos, Dirk E.; van der Veen, Monique A.
    Dalton Transactions (2016), 45 (10), 4401-4406CODEN: DTARAF; ISSN:1477-9226. (Royal Society of Chemistry)
    Polar metal-org. frameworks have potential applications as functional nonlinear optical, piezoelec., pyroelec. and ferroelec. materials. Using 2nd harmonic generation microscopy fluoride doping of the microporous Fe(III) terephthalate MOF MIL-53(Fe) induces a polar organization in its structure, which was not previously detected with XRD. The polar order is only obsd. when both fluoride and guest mols. are present, and may be related to a complex interplay between the adsorbates and the framework, leading to a modification of the positioning of fluoride in the inorg. Fe-chains. Combined polarized 2nd harmonic generation microscopy and scanning pyroelec. microscopy show that the polar axis is unidirectional and of the same sense over the whole crystal, extending up to 100 μm. This finding shows how MOF materials can be endowed with useful properties by doping MOFs with fluoride.
  29. 29
    Abrahams, S. C.; Robertson, J. M. The Crystal Structure of P-Nitroaniline, NO2.C6H4.NH2 Acta Crystallogr. 1948, 1, 252– 259 DOI: 10.1107/S0365110X48000673
    Google Scholar
    29
    The crystal structure of p-nitroaniline
    Abrahams, S. C.; Robertson, J. Monteath
    Acta Crystallographica (1948), 1 (), 252-9CODEN: ACCRA9; ISSN:0365-110X.
    cf. C.A. 42, 1779e. p-Nitroaniline forms monoclinic crystals, space group C52h - P21/n, a = 12.34 ± 0.02, b = 6.02 ± 0.02, c = 8.63 ± 0.02 A., β = 91°40', with 4 asymmetric mols. in the unit cell. Fourier methods using 250 reflections from the axial zones yielded the coordinates of the atoms, the mol. dimensions, and intermol. distances. The nitro group is sym. and lies in the plane of the benzene ring. Hydrogen bridges connect the O atoms of the NO2 to the NH2 of adjoining mols. There is a very close approach (2.7-3.0 A.) between one of the NO2 oxygen atoms and three of the aromatic C atoms of an adjoining mol. This new intermol. attraction may be responsible for the formation of many mol. compds. between aromatic nitro compds. and polycyclic hydrocarbons.
  30. 30
    Donohue, J.; Trueblood, K. The Crystal Structure of P-Nitroaniline Acta Crystallogr. 1956, 9, 960– 965 DOI: 10.1107/S0365110X56002680
    Google Scholar
    There is no corresponding record for this reference.
  31. 31
    Wübbenhorst, M.; Klap, G. J.; Jansen, J. C.; van Bekkum, H.; van Turnhout, J. Glass Transition of One-Dimensional Molecular Chains of P-Nitroaniline Confined in AlPO4–5 Nanopores Revealed by Dielectric Spectroscopy J. Chem. Phys. 1999, 111, 5637– 5640 DOI: 10.1063/1.479864
    Google Scholar
    There is no corresponding record for this reference.
  32. 32
    van der Veen, M. A.; Van Noyen, J.; Sels, B. F.; Jacobs, P. A.; Verbiest, T.; De Vos, D. E. Mapping of the Organization of P-Nitroaniline in SAPO-5 by Second-Harmonic Generation Microscopy Phys. Chem. Chem. Phys. 2010, 12, 10688 DOI: 10.1039/c0cp00257g
    Google Scholar
    There is no corresponding record for this reference.
  33. 33
    van der Veen, M. A.; Sels, B. F.; De Vos, D. E.; Verbiest, T. Localization of P-Nitroaniline Chains Inside Zeolite ZSM-5 with Second-Harmonic Generation Microscopy J. Am. Chem. Soc. 2010, 132, 6630– 6631 DOI: 10.1021/ja101614w
    Google Scholar
    33
    Localization of p-Nitroaniline Chains Inside Zeolite ZSM-5 with Second-Harmonic Generation Microscopy
    van der Veen, Monique A.; Sels, Bert F.; De Vos, Dirk E.; Verbiest, Thierry
    Journal of the American Chemical Society (2010), 132 (19), 6630-6631CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    For the 1st time, 2nd-harmonic generation microscopy (SHGM) was employed to study zeolites. Large ZSM-5 crystals filled with p-nitroaniline (PNA) dipoles were visualized. SHGM can discriminate between the straight b-pores and the sinusoidal a-pores of this zeolite, thus revealing the intergrown structure of these crystals. Also, dipole chains are formed not only in the b-pores but also in the a-pores. PNA only assembles into dipole chains of parallel orientation in those pores that are directly accessible from the outer surface. The area in which this PNA ordering prevails is limited to a strip near the outer surface of the zeolite crystal. A rationalization for these two observations is offered.
  34. 34
    Marlow, F.; Wübbenhorst, M.; Caro, J. Pyroelectric Effects on Molecular Sieve Crystals Loaded with Dipole Molecules J. Phys. Chem. 1994, 98, 12315– 12319 DOI: 10.1021/j100098a029
    Google Scholar
    There is no corresponding record for this reference.
  35. 35
    Klap, G. J.; van Klooster, S. M.; Wübbenhorst, M.; Jansen, J. C.; van Bekkum, H.; van Turnhout, J. Polarization Reversal in AlPO4-5 Crystals Containing Polar or Nonpolar Organic Molecules: A Scanning Pyroelectric Microscopy Study J. Phys. Chem. B 1998, 102, 9518– 9524 DOI: 10.1021/jp982816g
    Google Scholar
    There is no corresponding record for this reference.
  36. 36
    Klap, G. J.; Wübbenhorst, M.; Jansen, J. C.; van Koningsveld, H.; van Bekkum, H.; van Turnhout, J. Polar Growth and Directional Adsorption of Large AlPO4-5 Crystals Determined by Scanning Pyroelectric Microscopy Chem. Mater. 1999, 11, 3497– 3503 DOI: 10.1021/cm991043l
    Google Scholar
    There is no corresponding record for this reference.
  37. 37
    Skibo, E. B.; Gilchrist, J. H. Synthesis and Electrochemistry of Pyrimidoquinazoline-5,10-Diones. Design of Hydrolytically Stable High Potential Quinones and New Reductive Alkylation Systems J. Org. Chem. 1988, 53, 4209– 4218 DOI: 10.1021/jo00253a010
    Google Scholar
    There is no corresponding record for this reference.
  38. 38
    Stock, N. Hochdurchsatzmethoden Zur Entdeckung Und Optimierung Kristalliner Poröser Materialien Chem. Ing. Tech. 2010, 82, 1039– 1047 DOI: 10.1002/cite.201000029
    Google Scholar
    38
    High-throughput methods for discovery and optimization of crystalline porous materials
    Stock, N.
    Chemie Ingenieur Technik (2010), 82 (7), 1039-1047CODEN: CITEAH; ISSN:0009-286X. (Wiley-VCH Verlag GmbH & Co. KGaA)
    High throughput (HD) methods allow a systematic and efficient anal. of complex parameter areas such as obsd. in solvothermal synthesis. Their application is used to find new compds. to optimize synthesis conditions and reaction trends. Some HD methods were developed with a different degree of parallelism, miniaturization and automation of individual steps within the last decade to obtain the use of new outstanding microporous compds. in the field of zeolites, ZIFs (zeolitic imidazolate frameworks) and MOFs (metal-org. frameworks).
  39. 39
    Stock, N. High-Throughput Investigations Employing Solvothermal Syntheses Microporous Mesoporous Mater. 2010, 129, 287– 295 DOI: 10.1016/j.micromeso.2009.06.007
    Google Scholar
    39
    High-throughput investigations employing solvothermal syntheses
    Stock, Norbert
    Microporous and Mesoporous Materials (2009), 129 (3), 287-295CODEN: MIMMFJ; ISSN:1387-1811. (Elsevier Inc.)
    High-throughput (HT) methods applied to solvothermal reaction systems are a powerful technique for the rapid systematic investigation of large parameter spaces in a short time, giving rise to the accelerated discovery of new compds. and optimization of synthesis parameters. Large amts. of data can be generated in a short period of time, which provides the opportunity to ext. relevant reaction trends and contribute to a better understanding of the role of reaction parameters. While the primary driving forces in the development of high-throughput methods were com. considerations to cut down the time to market for new or improved products, the methodol. is also well suited for investigations in academia. The fields of application range from the discovery of new compds., the optimization of syntheses conditions to the extn. of synthesis trends. Examples demonstrating the power of HT methods will be based on different classes of compds. such as zeolites, inorg.-org. hybrid compds. such as ZIFs, MOFs, and MILs and will range from the investigation of two-dimensional to multi-dimensional parameter spaces.
  40. 40
    Stock, N.; Biswas, S. Synthesis of Metal-Organic Frameworks (MOFs): Routes to Various MOF Topologies, Morphologies, and Composites Chem. Rev. 2012, 112, 933– 969 DOI: 10.1021/cr200304e
    Google Scholar
    40
    Synthesis of Metal-Organic Frameworks (MOFs): Routes to Various MOF Topologies, Morphologies, and Composites
    Stock, Norbert; Biswas, Shyam
    Chemical Reviews (Washington, DC, United States) (2012), 112 (2), 933-969CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
    A review. The synthesis of metal-org. frameworks (MOFs) has attracted immense attention during the last 2 decades due to the possibility to obtain a large variety of aesthetically interesting structures that could also be of great interest for applications in a no. of fields related to porous materials. This includes the more traditional areas of storage, sepn., and catalysis, which are based on the pore size and shape as well as the host guest interactions involved. In addn., biomedical applications or the use as sensor materials are currently intensively investigated. Although MOF synthesis was originally set out for making new compds. and structures with interesting properties, the field has matured and is broadening its scope. This holds for the synthesis methods applied as well as the areas of application. While conventional syntheses methods have been widely used, the fields of mechano-, sono-, and electrochem. synthesis as well as microwave-assisted syntheses are just emerging. They have demonstrated to be applicable for some compds., often under milder reaction conditions, yielding materials with different particle sizes and properties. This could be of interest for up-scaling of syntheses and the application of MOFs.
  41. 41
    Bauer, S.; Stock, N. Hochdurchsatz-Methoden in Der Festkörperchemie. Schneller Zum Ziel. Chem Chem. Unserer Zeit 2007, 41, 390– 398 DOI: 10.1002/ciuz.200700404
    Google Scholar
    41
    Quicker to achieve the goal. High through-put method in solid state chemistry
    Bauer, Sebastian; Stock, Norbert
    Chemie in Unserer Zeit (2007), 41 (5), 390-398CODEN: CUNZAW; ISSN:0009-2851. (Wiley-VCH Verlag GmbH & Co. KGaA)
    A review. High-throughput (HT) methods applied to materials discovery have attracted much attention over the last few years because they permit a fast and efficient investigation of parameter space while consuming only small amts. of starting materials. Nowadays, many different HT techniques in solid state science are employed to accelerate the discovery and optimization of materials. The degree of parallelization, automation, and miniaturization dets. the efficiency of a HT methodol. Systematic investigation of parameter space and careful data anal. allow the identification of reaction trends and may give important guidance in better understanding of reaction systems. The described HT methodol. for solvothermal reactions allows the systematic investigation of 48 different hydrothermal reactions at a time. The methodol. includes automatic dispensing of solids and liqs., followed by homogenization, pH measurement, synthesis, isolation, washing as well as automated phase anal. by x-ray diffraction without the manipulation of individual samples. The focus of this article is on the application of HT methods in the investigation of the parameter space in solid state sciences. Based on selected examples, the power of HT methods in the discovery of new compds., the optimization of reactions, the identification of reaction trends, as well as the investigation of the influence of process parameters is described. The large amt. of data obtained in a short time leads to an improvement towards the understanding of the role that synthesis and process parameters play in the formation of compds. and materials.
  42. 42
    Topas Academic 4.2; Coelho Software: Brisbane, Australia, 2007.
    Google Scholar
    There is no corresponding record for this reference.
  43. 43
    Loiseau, T.; Serre, C.; Huguenard, C.; Fink, G.; Taulelle, F.; Henry, M.; Bataille, T.; Férey, G. A Rationale for the Large Breathing of the Porous Aluminum Terephthalate (MIL-53) Upon Hydration Chem. - Eur. J. 2004, 10, 1373– 1382 DOI: 10.1002/chem.200305413
    Google Scholar
    43
    A rationale for the large breathing of the porous aluminum terephthalate (MIL-53) upon hydration
    Loiseau, Thierry; Serre, Christian; Huguenard, Clarisse; Fink, Gerhard; Taulelle, Francis; Henry, Marc; Bataille, Thierry; Ferey, Gerard
    Chemistry - A European Journal (2004), 10 (6), 1373-1382CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)
    Al 1,4-benzenedicarboxylate Al(OH)[O2CC6H4CO2][HO2C-C6H4-CO2H]0.70 or MIL-53as (Al) was hydrothermally synthesized by heating a mixt. of Al nitrate, 1,4-benzenedicarboxylic acid, and H2O, for three days at 220°. Its 3 D framework is built up of infinite trans chains of corner-sharing AlO4(OH)2 octahedra. The chains are interconnected by the 1,4-benzenedicarboxylate groups, creating 1 D rhombic-shaped tunnels. Disordered 1,4-benzenedicarboxylic acid mols. are trapped inside these tunnels. Their evacuation upon heating, between 275 and 420°, leads to a nanoporous open-framework (MIL-53ht (Al) or Al(OH)[O2CC6H4CO2]) with empty pores of diam. 8.5 Å. This solid exhibits a Langmuir surface area. of 1590(1) m2g-1 together with a remarkable thermal stability, since it starts to decomp. only at 500°. At room temp., the solid reversibly absorbs H2O in its tunnels, causing a very large breathing effect and shrinkage of the pores. Anal. of the hydration process by solid-state NMR (1H, 13C, 27Al) has clearly indicated that the trapped H2O mols. interact with the carboxylate groups through H bonds, but do not affect the hydroxyl species bridging the Al atoms. The H bonds between H2O and the O atoms of the framework are responsible for the contraction of the rhombic channels. The structures of the three forms were detd. by powder x-ray diffraction anal. Crystal data for MIL-53as (Al) are as follows: orthorhombic system, Pnma (no. 62), a 17.129(2), b 6.628(1), c 12.182(1) Å; for MIL-53ht (Al), orthorhombic system, Imma (no. 74), a 6.608(1), b 16.675(3), c 12.813(2) Å; for MIL-53lt (Al), monoclinic system, Cc (no. 9), a 19.513(2), b 7.612(1), c 6.576(1) Å, β 104.24(1)°.
  44. 44
    Materials Studio, version 5.0; Accelrys Software, Inc., 2009.
    Google Scholar
    There is no corresponding record for this reference.
  45. 45
    Dovesi, R.; Orlando, R.; Erba, A.; Zicovich-Wilson, C. M.; Civalleri, B.; Casassa, S.; Maschio, L.; Ferrabone, M.; De La Pierre, M.; D’Arco, P. CRYSTAL14: A Program for the Ab Initio Investigation of Crystalline Solids Int. J. Quantum Chem. 2014, 114, 1287– 1317 DOI: 10.1002/qua.24658
    Google Scholar
    45
    CRYSTAL14: A program for the ab initio investigation of crystalline solids
    Dovesi, Roberto; Orlando, Roberto; Erba, Alessandro; Zicovich-Wilson, Claudio M.; Civalleri, Bartolomeo; Casassa, Silvia; Maschio, Lorenzo; Ferrabone, Matteo; De La Pierre, Marco; D'Arco, Philippe; Noel, Yves; Causa, Mauro; Rerat, Michel; Kirtman, Bernard
    International Journal of Quantum Chemistry (2014), 114 (19), 1287-1317CODEN: IJQCB2; ISSN:0020-7608. (John Wiley & Sons, Inc.)
    The capabilities of the CRYSTAL14 program are presented, and the improvements made with respect to the previous CRYSTAL09 version discussed. CRYSTAL14 is an ab initio code that uses a Gaussian-type basis set: both pseudopotential and all-electron strategies are permitted; the latter is not much more expensive than the former up to the first-second transition metal rows of the periodic table. A variety of d. functionals is available, including as an extreme case Hartree-Fock; hybrids of various nature (global, range-sepd., double) can be used. In particular, a very efficient implementation of global hybrids, such as popular B3LYP and PBE0 prescriptions, allows for such calcns. to be performed at relatively low computational cost. The program can treat on the same grounds zero-dimensional (mols.), one-dimensional (polymers), two-dimensional (slabs), as well as three-dimensional (3D; crystals) systems. No spurious 3D periodicity is required for low-dimensional systems as happens when plane-waves are used as a basis set. Symmetry is fully exploited at all steps of the calcn.; this permits, for example, to investigate nanotubes of increasing radius at a nearly const. cost (better than linear scaling!) or to perform self-consistent-field (SCF) calcns. on fullerenes as large as (10,10), with 6000 atoms, 84,000 AOs, and 20 SCF cycles, on a single core in one day. Three versions of the code exist, serial, parallel, and massive-parallel. In the second one, the most relevant matrixes are duplicated, whereas in the third one the matrixes in reciprocal space are distributed for diagonalization. All the relevant vectors are now dynamically allocated and deallocated after use, making CRYSTAL14 much more agile than the previous version, in which they were statically allocated. The program now fits more easily in low-memory machines (as many supercomputers nowadays are). CRYSTAL14 can be used on parallel machines up to a high no. of cores (benchmarks up to 10,240 cores are documented) with good scalability, the main limitation remaining the diagonalization step. Many tensorial properties can be evaluated in a fully automated way by using a single input keyword: elastic, piezoelec., photoelastic, dielec., as well as first and second hyperpolarizabilies, elec. field gradients, Born tensors and so forth. Many tools permit a complete anal. of the vibrational properties of cryst. compds. The IR and Raman intensities are now computed anal. and related spectra can be generated. Isotopic shifts are easily evaluated, frequencies of only a fragment of a large system computed and nuclear contribution to the dielec. tensor detd. New algorithms have been devised for the investigation of solid solns. and disordered systems. The topol. anal. of the electron charge d., according to the Quantum Theory of Atoms in Mols., is now incorporated in the code via the integrated merge of the TOPOND package. Electron correlation can be evaluated at the Moeller-Plesset second-order level (namely MP2) and a set of double-hybrids are presently available via the integrated merge with the CRYSCOR program.
  46. 46
    Dovesi, R.; Saunders, V. R.; Roetti, C.; Orlando, R.; Zicovich-Wilson, C. M.; Pascale, F.; Civalleri, B.; Doll, K.; Harrison, N. M.; Bush, I. J.; . CRYSTAL14 User’s Manual; University of Torino: Torino, Italy, 2014.
    Google Scholar
    There is no corresponding record for this reference.
  47. 47
    Seidler, T.; Champagne, B. Which Charge Definition for Describing the Crystal Polarizing Field and the χ (1) and χ (2) of Organic Crystals? Phys. Chem. Chem. Phys. 2015, 17, 19546– 19556 DOI: 10.1039/C5CP03248B
    Google Scholar
    There is no corresponding record for this reference.
  48. 48
    Seidler, T.; Champagne, B. Second-Order Nonlinear Optical Susceptibilities of Metal–Organic Frameworks Using a Combined Local Field Theory/Charge Embedding Electrostatic Scheme J. Phys. Chem. C 2016, 120, 6741– 6749 DOI: 10.1021/acs.jpcc.6b00217
    Google Scholar
    48
    Second-Order Nonlinear Optical Susceptibilities of Metal-Organic Frameworks Using a Combined Local Field Theory/Charge Embedding Electrostatic Scheme
    Seidler, Tomasz; Champagne, Benoit
    Journal of Physical Chemistry C (2016), 120 (12), 6741-6749CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)
    The linear (χ(1)) and second-order nonlinear (χ(2)) optical properties of metal-org. frameworks (MOFs) have been evaluated and interpreted by employing the combined local field theory/charge embedding approach. Three MOFs have been selected, the isostructural bis{4-[2-(4-pyridyl)ethenyl]benzoato}-zinc(II) (PEB-Zn) and bis{4-[2-(4-pyridyl)ethenyl]benzoato}-cadmium(II) (PEB-Cd) and bis{4-[3-(4-pyridyl)ethenyl]benzoato}-cadmium(II) (PEB'-Cd). The simulations, employing the Moller-Plesset second-order perturbation theory level to describe the ion properties, conclude that (i) χ(2) of PEB-Zn (∼60 pm/V at 1064 nm) is about 10% larger than that of PEB-Cd, (ii) χ(2) of PEB'-Cd attains 100 pm/V at 1064 nm [i.e., twice more than that of PEB-Cd or an amplitude similar to that of the 4-(N,N-dimethylamino)-3-acetamidonitrobenzene (DAN) mol. crystal] and (iii) the change of crystal structure accompanying an increase of temp. from 173 to 298 K leads to a decrease of χ(2) by ca. 10%. For the isostructural PEB-Zn and PEB-Cd, the outcome of Kurtz-Perry SHG powder method has been simulated as a function of the grain size, demonstrating that differences between the two MOFs only show up for room temp. structures. A value of 1.29 was estd. for the PEB-Zn/PEB-Cd contrast ratio, in qual. agreement with expt. (1.16). This work opens the way toward a theor. based design of MOFs with outstanding second-order nonlinear optical responses.
  49. 49
    Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Gaussian 09, revision B.01; Gaussian, Inc.: Wallingford, CT, 2009.
    Google Scholar
    There is no corresponding record for this reference.
  50. 50
    MUNN, R. W. A. General Microscopic Theory of Bulk Second-Harmonic Generation from Molecular Crystals Mol. Phys. 1996, 89, 555– 569 DOI: 10.1080/002689796173903
    Google Scholar
    There is no corresponding record for this reference.
  51. 51
    Kirtman, B.; Dykstra, C. E.; Champagne, B. Major Intermolecular Effects on Nonlinear Electrical Response in a Hexatriene Model of Solid State Polyacetylene Chem. Phys. Lett. 1999, 305, 132– 138 DOI: 10.1016/S0009-2614(99)00375-9
    Google Scholar
    51
    Major intermolecular effects on nonlinear electrical response in a hexatriene model of solid state polyacetylene
    Kirtman, Bernard; Dykstra, Clifford E.; Champagne, Benoit
    Chemical Physics Letters (1999), 305 (1,2), 132-138CODEN: CHPLBC; ISSN:0009-2614. (Elsevier Science B.V.)
    Through detailed model studies, benchmarked by extensive ab initio calcns., we show (1) how sizable medium effects on mol. elec. response of polymeric solids can arise; (2) that classical electrostatics accurately reproduces a full quantum treatment; and (3) that for a large bundle of hexatriene mols. taken as a model of polyacetylene, the medium effect will lead to as much as a 95% redn. in the second hyperpolarizability and a 50% redn. in the polarizability. For designing org. materials with enhanced nonlinear optical (NLO) properties, the results reveal features that might be optimized and point to a sound model for selecting other features.
  52. 52
    Reis, H.; Papadopoulos, M. G.; Calaminici, P.; Jug, K.; Köster, A. M. Calculation of Macroscopic Linear and Nonlinear Optical Susceptibilities for the Naphthalene, Anthracene and Meta-Nitroaniline Crystals Chem. Phys. 2000, 261, 359– 371 DOI: 10.1016/S0301-0104(00)00305-0
    Google Scholar
    52
    Calculation of macroscopic linear and nonlinear optical susceptibilities for the naphthalene, anthracene and meta-nitroaniline crystals
    Reis, H.; Papadopoulos, M. G.; Calaminici, P.; Jug, K.; Koster, A. M.
    Chemical Physics (2000), 261 (3), 359-371CODEN: CMPHC2; ISSN:0301-0104. (Elsevier Science B.V.)
    The macroscopic first- to third-order susceptibilities of naphthalene, anthracene and meta-nitroaniline (mNA) are calcd. using a rigorous local field approach. Mol. (hyper)polarizabilities used as input are detd. by d. functional theory calcns. with specially designed basis sets and for mNA also by MP2 calcns. with the 6-31++G** basis set. In the case of mNA, the permanent elec. local field due to the surrounding dipoles in the crystal is taken into account for the first- and second-order susceptibility by a self-consistent approach. The mol. dipole moment and first hyperpolarizability of mNA are drastically changed by the permanent local field. In all cases the calcd. first-order susceptibility compares very favorably with exptl. data, if the mol. response is distributed over all heavy atoms in the mols. Similarly, the calcd. second-order susceptibility for mNA is in good agreement with available exptl. data, if the same distribution scheme is used and the permanent local field is taken into account properly. This implies that accurate values for the mol. second-order hyperpolarizability γ have to be available. The anisotropic Lorentz field factor approxn. yields results that are only slightly worse than the best ones of the rigorous local field theory for the first-order susceptibilities, but fails for the second-order susceptibility of mNA, due to its incapability to describe the large effect of the permanent local field on the first-order hyperpolarizability β.
  53. 53
    Seidler, T.; Stadnicka, K.; Champagne, B. Investigation of the Linear and Second-Order Nonlinear Optical Properties of Molecular Crystals within the Local Field Theory J. Chem. Phys. 2013, 139, 114105 DOI: 10.1063/1.4819769
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    53
    Investigation of the linear and second-order nonlinear optical properties of molecular crystals within the local field theory
    Seidler, Tomasz; Stadnicka, Katarzyna; Champagne, Benoit
    Journal of Chemical Physics (2013), 139 (11), 114105/1-114105/15CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)
    Modest calcns. combining 1st principles evaluations of the mol. properties with electrostatic interaction schemes to account for the crystal environment effects are reliable for predicting and interpreting the exptl. measured elec. linear and 2nd-order nonlinear optical susceptibilities of mol. crystals within the exptl. error bars. This is illustrated by considering 2 mol crystals, namely: 2-Me-4-nitroaniline and 4-(N,N-dimethylamino)-3-acetamidonitrobenzene. Three types of surrounding effects should be accounted for (i) the polarization due to the surrounding mols., described here by static elec. fields originating from their elec. dipoles or charge distributions, (ii) the intermol. interactions, which affect the geometry and particularly the mol. conformation, and (iii) the screening of the external elec. field by the constitutive mols. This study further highlights the role of electron correlation on the linear and nonlinear responses of mol. crystals and the challenge of describing frequency dispersion. (c) 2013 American Institute of Physics.
  54. 54
    Seidler, T.; Stadnicka, K.; Champagne, B. Second-Order Nonlinear Optical Susceptibilities and Refractive Indices of Organic Crystals from a Multiscale Numerical Simulation Approach Adv. Opt. Mater. 2014, 2, 1000– 1006 DOI: 10.1002/adom.201400245
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    54
    Second-order Nonlinear Optical Susceptibilities and Refractive Indices of Organic Crystals from a Multiscale Numerical Simulation Approach
    Seidler, Tomasz; Stadnicka, Katarzyna; Champagne, Benoit
    Advanced Optical Materials (2014), 2 (10), 1000-1006CODEN: AOMDAX; ISSN:2195-1071. (Wiley-VCH Verlag GmbH & Co. KGaA)
    The performance of a simple multiscale approach to rapidly screen the second-order nonlinear optical (NLO) susceptibilities [χ(2)] as well as the refractive indexes of org. crystals solely from the knowledge of their crystal structure is demonstrated. The method combines first principles calcns. of the mol. properties with a classical electrostatic interactions scheme to account for the crystal environment effects. The calcd. values reproduce closely the measured χ(2) response for 10 org. crystals, including ionic cryst. salts, covering a χ(2) range from 10 to 600 pm V-1. The agreement between calcns. and measurements is also excellent in the case of the refractive indexes. Moreover, the method allows to analyze the relationship between the macroscopic responses [χ(2)] and the mol. first hyperpolarizabilities, highlighting the effects of crystal packing and chromophore d. as well as the role played by the crystal dressing field.
  55. 55
    Seidler, T.; Stadnicka, K.; Champagne, B. Evaluation of the Linear and Second-Order NLO Properties of Molecular Crystals within the Local Field Theory: Electron Correlation Effects, Choice of XC Functional, ZPVA Contributions, and Impact of the Geometry in the Case of 2-Methyl-4-Nitroaniline J. Chem. Theory Comput. 2014, 10, 2114– 2124 DOI: 10.1021/ct5001654
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    55
    Evaluation of the Linear and Second-Order NLO Properties of Molecular Crystals within the Local Field Theory: Electron Correlation Effects, Choice of XC Functional, ZPVA Contributions, and Impact of the Geometry in the Case of 2-Methyl-4-nitroaniline
    Seidler, Tomasz; Stadnicka, Katarzyna; Champagne, Benoit
    Journal of Chemical Theory and Computation (2014), 10 (5), 2114-2124CODEN: JCTCCE; ISSN:1549-9618. (American Chemical Society)
    The linear [χ(1)] and 2nd-order nonlinear [χ(2)] optical susceptibilities of the 2-Me-4-nitroaniline (MNA) crystal are calcd. within the local field theory, which consists of 1st computing the mol. properties, accounting for the dressing effects of the surroundings, and then taking into account the local field effects. Several aspects of these calcns. are tackled with the aim of monitoring the convergence of the χ(1) and χ(2) predictions with respect to expt. by accounting for the effects of (i) the dressing field within successive approxns., of (ii) the 1st-order ZPVA corrections, and of (iii) the geometry. With respect to the ref. CCSD-based results, besides double hybrid functionals, the most reliable exchange-correlation functionals are LC-BLYP for the static χ(1) and CAM-B3LYP (and M05-2X, to a lesser extent) for the dynamic χ(1) but they strongly underest. χ(2). Double hybrids perform better for χ(2) but not necessarily for χ(1), and, also, their performances are much similar to MP2, which is known to slightly overestimate β, with respect to high-level coupled-clusters calcns. and, therefore, χ(2). Other XC functionals with less HF exchange perform poorly with overestns./underestns. of χ(1)/χ(2), whereas the HF method leads to underestns. of both. The 1st-order ZPVA corrections, estd. at the B3LYP level, are usually small but not negligible. After ZPVA corrections, the mol. polarizabilities and 1st hyperpolarizabilities increase by 2% and 5%, resp., whereas their impact is magnified on the macroscopic responses with enhancements of χ(1) by up to 5% and of χ(2) by ≤10%-12% at λ = 1064 nm. The geometry plays also a key role in view of predicting accurate susceptibilities, particularly for push-pull π-conjugated compds. such as MNA. The geometry optimized using periodic boundary conditions is characterized by an overestd. bond length alternation, which gives larger mol. properties and even larger macroscopic responses, because of the local field factor amplification effects. The best ests. based on exptl. geometries, charge dressing field, ZPVA correction, and CCSD mol. properties lead to an overestn. of χ(1) by 12% in the static limit and 7% at λ = 1064 nm. For χ(2), the difference, with respect to the expt., is satisfactory and of the order of 1 std. deviation.
  56. 56
    Seidler, T.; Stadnicka, K.; Champagne, B. Linear and Second-Order Nonlinear Optical Properties of Ionic Organic Crystals J. Chem. Phys. 2014, 141, 104109 DOI: 10.1063/1.4894483
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    Linear and second-order nonlinear optical properties of ionic organic crystals
    Seidler, Tomasz; Stadnicka, Katarzyna; Champagne, Benoit
    Journal of Chemical Physics (2014), 141 (10), 104109/1-104109/10CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)
    The linear and second-order nonlinear optical susceptibilities of three ionic org. crystals, 4-N,N-dimethylamino-4'-N'-methyl-stilbazolium tosylate (DAST), 4-N,N-dimethylamino-4'-N'-methyl-stilbazolium 2,4,6-trimethylbenzenesulfonate (DSTMS), and 4-N,N-dimethylamino-4'-N'-phenyl-stilbazolium hexafluorophosphate (DAPSH), were calcd. by adopting a two-step multi-scale procedure, which consists in calcg.: (i) the ion properties using ab initio or d. functional theory methods and then (ii) in accounting for the crystal environment effects using classical electrostatic models. Provided that the ionic properties are evaluated at the second-order Moller-Plesset level and that the dressing field effects using point charges are accounted for, the agreement with expt. is excellent and enables to explain the origin of the larger χ(2) response of DAPSH with respect to DAST and DSTMS. Also including the dressing field decreases the χ(2) response of ionic crystals whereas its effect is opposite for mol. crystals. Also, also this multi-scale approach can be used to interpret the impact of the nature and position of the counterion on the linear and nonlinear optical susceptibilities of ionic crystals. Finally, the use of a conventional exchange-correlation functional like B3LYP leads to severe overestimations of χ(1) but large underestimations of χ(2) whereas the use of homogeneous dipole field is not recommended because it usually leads to overestimations of the linear and nonlinear optical susceptibilities. (c) 2014 American Institute of Physics.
  57. 57
    Wittmann, T.; Siegel, R.; Reimer, N.; Milius, W.; Stock, N.; Senker, J. Enhancing the Water Stability of Al-MIL-101-NH2 via Postsynthetic Modification Chem. - Eur. J. 2015, 21, 314– 323 DOI: 10.1002/chem.201404654
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    57
    Enhancing the Water Stability of Al-MIL-101-NH2 via Postsynthetic Modification
    Wittmann, Thomas; Siegel, Renee; Reimer, Nele; Milius, Wolfgang; Stock, Norbert; Senker, Juergen
    Chemistry - A European Journal (2015), 21 (1), 314-323CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)
    Stabilization of the mesoporous MOF Al-MIL-101-NH2 via postsynthetic modification with Ph isocyanate is reported. In this process 86% of the amino groups were converted into phenylurea units. As a consequence, the long-term stability of Al-MIL-101-URPh in liq. water could be extended beyond a week. In water satd. atms. Al-MIL-101-URPh decompd. at least 12-times slower than the unfunctionalized analog. To study the underlying processes both materials were characterized by Ar, N2 and H2O sorption measurements, powder X-ray diffraction, thermogravimetric and chem. anal. as well as solid-state NMR and IR spectroscopy. Postsynthetic modification decreased the BET equiv. surface area from 3363 to 1555 m2 g-1 for Al-MIL-101-URPh and reduced the mean diams. of the mesopores by 0.6 nm without degrading the structure significantly and reducing thermal stability. In spite of similar water uptake capacities, the relative humidity-dependent uptake of Al-MIL-101-URPh is slowed and occurs at higher relative humidity values. In combination with 1H-27Al D-HMQC NMR spectroscopy expts. this favors a shielding mechanism of the Al clusters by the pendant Ph groups and rules out pore blocking.
  58. 58
    Ahnfeldt, T.; Gunzelmann, D.; Loiseau, T.; Hirsemann, D.; Senker, J.; Férey, G.; Stock, N. Synthesis and Modification of a Functionalized 3D Open-Framework Structure with MIL-53 Topology Inorg. Chem. 2009, 48, 3057– 3064 DOI: 10.1021/ic8023265
    Google Scholar
    58
    Synthesis and Modification of a Functionalized 3D Open-Framework Structure with MIL-53 Topology
    Ahnfeldt, Tim; Gunzelmann, Daniel; Loiseau, Thierry; Hirsemann, Dunja; Senker, Jurgen; Ferey, Gerard; Stock, Norbert
    Inorganic Chemistry (2009), 48 (7), 3057-3064CODEN: INOCAJ; ISSN:0020-1669. (American Chemical Society)
    Al aminoterephthalate Al(OH)[H2N-BDC]·0.3(H2N-H2BDC) (denoted MIL-53-NH2(as)) was synthesized under hydrothermal conditions. The activation of the compd. can be achieved in two steps. The treatment with DMF at 150° leads to Al(OH)[H2N-BDC]·0.95DMF (MIL-53-NH2(DMF)). In the 2nd step, DMF is thermally removed at 130°. Upon cooling in air, the hydrated form Al(OH)[H2N-BDC]·0.9H2O (MIL-53-NH2(lt)) was obtained. The dehydration leads to a porous compd. that exhibits hysteresis behavior in the N2 sorption expts. The MIL-53-NH2(lt) can be modified by postsynthetic functionalization using formic acid, and the corresponding amide Al(OH)[HC(O)N(H)-BDC]·H2O (MIL-53-NHCHO) is formed. All four phases were thoroughly characterized by x-ray powder diffraction, solid-state NMR and IR spectroscopy, and sorption measurements, as well as thermogravimetric and elemental anal. Based on the refined lattice parameter similar breathing behavior of the framework as found in the unfunctionalized MIL-53 can be deduced. Solid-state NMR spectra unequivocally demonstrate the guest species, as well as the successful postsynthetic functionalization.
  59. 59
    Sumida, K.; Rogow, D. L.; Mason, J. A.; McDonald, T. M.; Bloch, E. D.; Herm, Z. R.; Bae, T.; Long, J. R. Carbon Dioxide Capture in Metal–Organic Frameworks Chem. Rev. 2012, 112, 724– 781 DOI: 10.1021/cr2003272
    Google Scholar
    59
    Carbon Dioxide Capture in Metal-Organic Frameworks
    Sumida, Kenji; Rogow, David L.; Mason, Jarad A.; McDonald, Thomas M.; Bloch, Eric D.; Herm, Zoey R.; Bae, Tae-Hyun; Long, Jeffrey R.
    Chemical Reviews (Washington, DC, United States) (2012), 112 (2), 724-781CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
    An extensive review is given on progress made in the capture of CO2 from power plant emissions, briefly considering also the CO2 storage (sequestration) of the enormous quantities of CO2 that would be obtained as a result of a successful capture framework. The main existing CO2 capture technologies are discussed in the context of capture performance considerations of aq. alkanolamine solns. and porous solids such as zeolites and activated carbons. Schematic diagrams are presented of idealized temp. swing adsorption, pressure swing adsorption, and vacuum swing adsorption processes for regenerating solid adsorbent in a fixed-bed column. The structural features and CO2 adsorption characteristics of isoreticular metal-org. frameworks (MOF) are discussed in detail. The high-pressure adsorption capacities of 36 MOF and the lower-pressure adsorption capacities of many more MOF, at 293-319 K, are tabulated. The various types of functionalities that have been explored to date for prepg. materials with enhanced CO2 capture performance are outlined, including amines, strongly polarizing org. functionalities, and exposed metal cation sites. The synthesis of continuous films of MOF and their use in membranes for gas sepn. are examd., with the tabulation of the CO2 sepn. performance of MOF mixed-matrix membranes. A final section outlines main issues that need to be addressed to achieve next-generation materials capable of fulfilling the criteria required for the gas sepns. relevant to post-combustion CO2 capture, pre-combustion CO2 capture, and oxy-fuel combustion.
  60. 60
    Serra-Crespo, P.; Gobechiya, E.; Ramos-Fernandez, E. V.; Juan-Alcañiz, J.; Martinez-Joaristi, A.; Stavitski, E.; Kirschhock, C. E. a.; Martens, J. a.; Kapteijn, F.; Gascon, J. Interplay of Metal Node and Amine Functionality in NH2-MIL-53: Modulating Breathing Behavior through Intra-Framework Interactions Langmuir 2012, 28, 12916– 12922 DOI: 10.1021/la302824j
    Google Scholar
    60
    Interplay of Metal Node and Amine Functionality in NH2-MIL-53: Modulating Breathing Behavior through Intra-framework Interactions
    Serra-Crespo, Pablo; Gobechiya, Elena; Ramos-Fernandez, Enrique V.; Juan-Alcaniz, Jana; Martinez-Joaristi, Alberto; Stavitski, Eli; Kirschhock, Christine E. A.; Martens, Johan A.; Kapteijn, Freek; Gascon, Jorge
    Langmuir (2012), 28 (35), 12916-12922CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)
    Amino-functionalized MIL-53 with different metals as nodes were synthesized, NH2-MIL-53(Al, Ga, and In) derived with 2-aminoterephthalic acid. By detg. adsorption properties and spectroscopic characterization, the authors unequivocally show that the interaction between the amines of the org. linker and bridging μ2-OH of the inorg. scaffold modulates metal org. framework (MOF) flexibility. The strength of the interaction was found to correlate with the electropositivity of the metal.
  61. 61
    Boyd, R. W. Nonlinear Optics; Elsevier, 2008.
    Google Scholar
    There is no corresponding record for this reference.
  62. 62
    Le Floc’h, V.; Brasselet, S.; Roch, J.-F.; Zyss, J. Monitoring of Orientation in Molecular Ensembles by Polarization Sensitive Nonlinear Microscopy J. Phys. Chem. B 2003, 107, 12403– 12410 DOI: 10.1021/jp034950t
    Google Scholar
    62
    Monitoring of Orientation in Molecular Ensembles by Polarization Sensitive Nonlinear Microscopy
    Le Floc'h, Veronique; Brasselet, Sophie; Roch, Jean-Francois; Zyss, Joseph
    Journal of Physical Chemistry B (2003), 107 (45), 12403-12410CODEN: JPCBFK; ISSN:1520-6106. (American Chemical Society)
    The authors present high resoln. 2-photon excitation microscopy studies combining 2-photon fluorescence (TPF) and 2nd harmonic generation (SHG) to probe orientational distributions of mol. ensembles at room temp. A detailed polarization anal. of TPF and SHG signals is used to unravel the parameters of the mol. orientational statistical distribution, using a technique which can be extended and generalized to a broad variety of mol. arrangements. A polymer film contg. mols. active for TPF and/or SHG emission is studied as a model system. Polarized TPF provides information on specific properties pertaining to incoherent emission in mol. media, such as excitation transfer. SHG, being highly sensitive to a slight departure from centrosymmetry such as induced by an external elec. field in the medium, complements TPF. The response of each signal to a variable excitation polarization allows study of mol. behavior in complex environments which affect their orientations and interactions.
  63. 63
    Loiseau, T.; Muguerra, H.; Haouas, M.; Taulelle, F.; Férey, G. Hydrothermal Synthesis and Structural Characterization of a Gallium Pyromellitate Ga(OH)(btec)·0.5H2O, with Infinite Ga-(μ2-OH)-Ga Chains (MIL-61) Solid State Sci. 2005, 7, 603– 609 DOI: 10.1016/j.solidstatesciences.2005.01.014
    Google Scholar
    63
    Hydrothermal synthesis and structural characterization of a gallium pyromellitate Ga(OH)(btec).0.5H2O, with infinite Ga-(μ2-OH)-Ga chains (MIL-61)
    Loiseau, Thierry; Muguerra, Herve; Haouas, Mohamed; Taulelle, Francis; Ferey, Gerard
    Solid State Sciences (2005), 7 (5), 603-609CODEN: SSSCFJ; ISSN:1293-2558. (Elsevier B.V.)
    A new Ga carboxylate Ga(OH)(btec).0.5H2O (MIL-61) was synthesized under mild hydrothermal conditions (200°, 24 h) in the presence of 1,2,4,5-benzenetetracarboxylic (btec) acid and H2O. The crystal structure, characterized by Rietevelt refinement of powder XRD data, consists of trans chains of GaO4(OH)2 octahedra, connected to each other through a μ 2 -OH group. The three-dimensional framework is built up from these chains linked together via the org. mols. thus delimiting the cavities where the H2O mols. are encapsulated. Anal. by solid state NMR (1H and 13C) confirmed the presence within the structure of both H2O mols. and carboxylate moieties partially deprotonated. The structure of Ga(OH)(btec).0.5H2O corresponds to that of MIL-61 obtained with V replacing Ga. Crystal data for Ga4(OH)4((HO2C)2-C6H4-(CO2)2)4·2H2O: a 14.8325(10), b 6.7792(10), c 10.6726(10) Å, V = 1073.2(2) Å3, Pnma (n°62).
  64. 64
    Gándara, F.; Gomez-Lor, B.; Gutiérrez-Puebla, E.; Iglesias, M.; Monge, M. A.; Proserpio, D. M.; Snejko, N. An Indium Layered MOF as Recyclable Lewis Acid Catalyst Chem. Mater. 2008, 20, 72– 76 DOI: 10.1021/cm071079a
    Google Scholar
    64
    An Indium Layered MOF as Recyclable Lewis Acid Catalyst
    Gandara, F.; Gomez-Lor, B.; Gutierrez-Puebla, E.; Iglesias, M.; Monge, M. A.; Proserpio, D. M.; Snejko, N.
    Chemistry of Materials (2008), 20 (1), 72-76CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
    By using the bent linker 4,4'-(hexafluoroisopropylidene)bis(benzoic acid) (H2hippb), whose central atom is an sp3 carbon, a new In(III) MOF (metal-org. framework) was obtained. The structure is described as thick layers with the bent geometry of the ligand leading to the formation of square-shaped channels, which run inside the framework layers. This microporous, thermally stable compd. is an efficient heterogeneous catalyst for acetalization of aldehydes. Differences in the catalytic activity when a compd. with empty or filled channels is used demonstrate that the catalytic reactions take place inside the pores.
  65. 65
    Van Der Veen, M. A.; Verbiest, T.; De Vos, D. E. Probing Microporous Materials with Second-Harmonic Generation Microporous Mesoporous Mater. 2013, 166, 102– 108 DOI: 10.1016/j.micromeso.2012.04.051
    Google Scholar
    There is no corresponding record for this reference.
  66. 66
    Falaise, C.; Volkringer, C.; Facqueur, J.; Bousquet, T.; Gasnot, L.; Loiseau, T. Capture of Iodine in Highly Stable Metal–Organic Frameworks: A Systematic Study Chem. Commun. 2013, 49, 10320 DOI: 10.1039/c3cc43728k
    Google Scholar
    66
    Capture of iodine in highly stable metal-organic frameworks: a systematic study
    Falaise, Clement; Volkringer, Christophe; Facqueur, Jacques; Bousquet, Till; Gasnot, Laurent; Loiseau, Thierry
    Chemical Communications (Cambridge, United Kingdom) (2013), 49 (87), 10320-10322CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)
    Aluminum-based metal-org. frameworks were studied for sorption of iodine (I2) in cyclohexane. The best sorption uptake was obtained with solids decorated by electro-donor groups attached either to the org. ligand (-NH2) or the inorg. sub-network (-OH).
  67. 67
    Armstrong, D. J.; Alford, W. J.; Raymond, T. D.; Smith, A. V. Absolute Measurement of the Effective Nonlinearities of KTP and BBO Crystals by Optical Parametric Amplification Appl. Opt. 1996, 35, 2032– 2040 DOI: 10.1364/AO.35.002032
    Google Scholar
    67
    Absolute measurement of the effective nonlinearities of KTP and BBO crystals by optical parametric amplification
    Armstrong, D. J.; Alford, W. J.; Raymond, T. D.; Smith, A. V.
    Applied Optics (1996), 35 (12), 2032-2040CODEN: APOPAI; ISSN:0003-6935. (Optical Society of America)
    Abs. magnitudes of the effective nonlinearity, deff, were measured for 7 KTP and 6 BBO crystals. The deff's were derived from the parametric gain of an 800-nm signal wave in the sample crystals when they were pumped by the frequency-doubled, spatially filtered light from an injection-seeded, Q-switched Nd:YAG laser. The KTP crystals, all type II phase matched with propagation in the X-Z plane, had deff values ranging from 1.97 to 3.50 pm/V. Measurements of gain as a function of phase velocity mismatch indicate that 2 of the KTP crystals clearly contain multiple ferroelec. domains. For 5 type I phase-matched BBO crystals, deff ranged from 1.76 to 1.83 pm/V, and a single type II phase-matched BBO crystal had a deff of 1.56 pm/V. The uncertainty in the measurements of deff values is ±5% for KTP and ±10% for BBO.

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  • Abstract

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    Figure 1

    Figure 1. Flowchart of experiments showing synthesis pathways, sample treatments, and corresponding sample names.

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    Figure 2

    Figure 2. 2-amino-5-nitroterephthalic acid (H2BDC-NH2/NO2) linker molecule.

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    Figure 3

    Figure 3. SEM images of H2BDC-NH2/NO2 containing MOFs: (a) MIL-53(Al)-NH2/NO2 (1), (b) MIL-53(Al)-NH2/NO2 (2), (c) MIL-53(Ga)-NH2/NO2 (3), and (d) MIL-53(In)-NH2/NO2 (4). Note that the first image has a scale bar of 10 μm, whereas the other images have a scale bar of 50 μm.

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    Figure 4

    Figure 4. Different positions of the amino and nitro groups in the BCD2– anion postulated in the MIL-53-(Al)-NH2/NO2 structure.

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    Figure 5

    Figure 5. Crystal structure of MIL-53(Al)-NH2/NO2 (1) along [001]. The disorder (above) of the linker molecules in the structure contains 61% of the NO2 groups of the linker molecules showing out of the plane and 39% pointing in plane. Carbon atoms are shown in gray, oxygen in red, nitrogen in blue and AlO6 polyhedra in orange.

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    Figure 6

    Figure 6. From left to right: optical, two-photon fluorescence, and second-harmonic generation images. From top to bottom: as synthesized MIL-53(Al)-NH2/NO2 (1), MIL-53(Al)-NH2/NO2 (2), and MIL-53(Ga)-NH2/NO2 (3). The SHG images display the average intensity of linearly polarized laser light, calculated over 60 images, each image being 3° apart in polarization direction of the incident polarized beam. The scale bars indicate a distance of 10 μm for each image.

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    Figure 7

    Figure 7. Grain size dependence of the calculated ⟨deff⟩ values for MIL-53(Al)-NH2/NO2, MIL-53(Ga)-NH2/NO2, and MIL-53(Al)-NH2(vnp). For MIL-53(M)-NH2/NO2, results are listed for the pure A and C phases as well as for the A:C ratios obtained from PXRD analysis.

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  • References

    This article references 67 other publications.

    1. 1
      Ye, Z.-G. Handbook of Dielectric, Piezoelectric and Ferroelectric Materials: Synthesis, Properties and Applications; Woodhead Pub. and Maney Pub. on behalf of The Institute of Materials, Minerals & Mining, 2008.
      There is no corresponding record for this reference.
    2. 2
      Curtin, D. Y.; Paul, I. C. Chemical Consequences of the Polar Axis in Organic Solid-State Chemistry Chem. Rev. 1981, 81, 525– 541 DOI: 10.1021/cr00046a001
      2
      Chemical consequences of the polar axis in organic solid-state chemistry
      Curtin, David Y.; Paul, Iain C.
      Chemical Reviews (Washington, DC, United States) (1981), 81 (6), 525-41CODEN: CHREAY; ISSN:0009-2665.
      The concept and consequences in org. chem. of the polar axis are reviewed with 59 refs.
    3. 3
      Asadi, K.; van der Veen, M. A. Ferroelectricity in Metal-Organic Frameworks: Characterization and Mechanisms Eur. J. Inorg. Chem. 2016, 2016, 4332– 4344 DOI: 10.1002/ejic.201600932
      3
      Ferroelectricity in Metal-Organic Frameworks: Characterization and Mechanisms
      Asadi, Kamal; van der Veen, Monique Ann
      European Journal of Inorganic Chemistry (2016), 2016 (27), 4332-4344CODEN: EJICFO; ISSN:1434-1948. (Wiley-VCH Verlag GmbH & Co. KGaA)
      Ferroelec. metal-org. frameworks are emerging as an exciting field of research and have witnessed great progress in the last decade. In this contribution, we briefly discuss ferroelectricity and its means of demonstration. Three mechanisms that lead to ferroelectricity are identified and critically discussed. On the basis of the shortcomings present in the literature, we present a protocol for the study of ferroelectricity in MOF compds.
    4. 4
      Fainman, Y.; Ma, J.; Lee, S. H. Non-Linear Optical Materials and Applications Mater. Sci. Rep. 1993, 9, 53– 139 DOI: 10.1016/0920-2307(93)90008-3
      4
      Non-linear optical materials and applications
      Fainman, Y.; Ma, J.; Lee, S. H.
      Materials Science Reports (1993), 9 (2-3), 53-139CODEN: MSREEL; ISSN:0920-2307.
      A review, with 219 refs., of the present status of the non-linear optical materials and devices, and their applications for optical signal processing and computing. The primary motivation behind this review is to introduce the different areas involved, paying special attention to their interfaces. First, the optical non-linearities in semiconductor materials, semiconductor microstructures and photorefractive materials are introduced. For the semiconductors, authors discuss the third-order non-linear susceptibilities due to virtual transitions (e.g., bound electrons in intrinsic semiconductors and non-linear motion and energy relaxation of free carriers in doped semiconductors) and due to real transitions (e.g. valence-to-conduction-band transitions, free-carrier transitions, impurity transitions and transitions in excitons and excitonic complexes). Recent advances in engineering semiconductor microstructures are discussed and shown to enhance their third-order non-linear optical susceptibilities in comparison with the bulk semiconductors. The mechanism of the photorefractive effect is next introduced and analyzed in conjunction with several engineering approaches to enhance the performances of the photorefractive non-linearities (e.g., non-stationary recording, multiphoton excitation, combination of the photorefractive effect with the electrorefractive non-linearities near the band edge, etc.). Using the photorefractive materials as an example, authors define a set of figures of merit based on the requirements from the optical devices for system applications. Using these figures of merit authors evaluate and discuss the optimization of different photorefractive materials: ferroelec. oxides (e.g., LiNbO3, BaTiO3, KNbO3, tungsten bronze family, etc.), compd. semiconductors (e.g., GaAs, GaP, InP, CdS, CdSe, CdTe, etc.), sillenites (e.g., Bi12SiO20, Bi12GeO20), and ceramics. Finally, the applications of non-linear optical materials are discussed using the photorefractive materials as an example. Two types of devices are distinguished: passive devices that are based on vol. holog. storage of information and active devices that are based on continuous two-wave and four-wave mixing of optical information carrying waves. These devices are evaluated and their optimization is discussed in conjunction with applications to analog and digital optical signal processing and computing. Examples of analog (e.g., inverse filter and linear algebra processor) and digital (e.g., parallel access optical memories and reconfigurable interconnects) optical computing applications will be also discussed.
    5. 5
      Hollingsworth, M. D. Crystal Engineering: From Structure to Function Science 2002, 295, 2410– 2413 DOI: 10.1126/science.1070967
      5
      Crystal engineering: from structure to function
      Hollingsworth, Mark D.
      Science (Washington, DC, United States) (2002), 295 (5564), 2410-2413CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)
      A review. Modern crystal engineering has emerged as a rich discipline whose success requires an iterative process of synthesis, crystallog., crystal structure anal., and computational methods. By focusing on the mol. recognition events during nucleation and growth, chemists have uncovered new ways of controlling the internal structure and symmetry of crystals and of producing materials with useful chem. and phys. properties.
    6. 6
      Mingabudinova, L. R.; Vinogradov, V. V.; Milichko, V. A.; Hey-Hawkins, E.; Vinogradov, A. V. Metal–Organic Frameworks as Competitive Materials for Non-Linear Optics Chem. Soc. Rev. 2016, 45, 5408– 5431 DOI: 10.1039/C6CS00395H
      6
      Metal-organic frameworks as competitive materials for non-linear optics
      Mingabudinova, L. R.; Vinogradov, V. V.; Milichko, V. A.; Hey-Hawkins, E.; Vinogradov, A. V.
      Chemical Society Reviews (2016), 45 (19), 5408-5431CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)
      The last five years have witnessed a huge breakthrough in the creation and the study of the properties of a new class of compds. - metamaterials. The next stage of this technol. revolution will be the development of active, controllable, and non-linear metamaterials, surpassing natural media as platforms for optical data processing and quantum information applications. However, scientists are constantly faced with the need to find new methods that can ensure the formation of quantum and non-linear metamaterials with higher resoln. One such method of producing metamaterials in the future, which will provide scalability and availability, is chem. synthesis. Meanwhile, the chem. synthesis of organized 3D structures with a period of a few nanometers and a size of up to a few millimeters is not an easy task and is yet to be resolved. The most promising avenue seems to be the use of highly porous structures based on metal-org. frameworks that have demonstrated their unique properties in the field of non-linear optics (NLO) over the past three years. Thus, the aim of this review is to examine current progress and the possibilities of using metal-org. frameworks in the field of non-linear optics as chem. obtained metamaterials of the future. The review begins by presenting the theor. principles of phys. phenomena represented by math. descriptions for clarity. Major attention is paid to the second harmonic generation (SHG) effect. In this section we compare inorg. single crystals, which are most commonly used to study the effect in question, to org. materials, which also possess the required properties. Based on these data, we present a rationale for the possibility of studying the non-linear optical properties of metal-org. structures as well as describing the use of synthetic approaches and the difficulties assocd. with them. The second part of the review explicitly acquaints the reader with a new class of materials which successfully combines the pos. properties of org. and inorg. materials. Using recently synthesized metal-org. frameworks and coordination polymers in the field of non-linear optics as an example, we consider synthetic approaches used for obtaining materials with desired properties and the factors to be considered in this case. Finally, probable trends towards improving the quality of the synthesized materials with regards to their further use in the field of non-linear optical effects are described.
    7. 7
      Evans, O. R.; Lin, W. Crystal Engineering of NLO Materials Based on Metal–Organic Coordination Networks Acc. Chem. Res. 2002, 35, 511– 522 DOI: 10.1021/ar0001012
      7
      Crystal Engineering of NLO Materials Based on Metal-Organic Coordination Networks
      Evans, Owen R.; Lin, Wenbin
      Accounts of Chemical Research (2002), 35 (7), 511-522CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)
      A review. Crystal engineering, the ability to predict and control the packing of mol. building units in the solid state, has attracted much attention over the past three decades owing to its potential exploitation for the synthesis of technol. important materials. The authors present here the development of crystal-engineering strategies toward the synthesis of noncentrosym. infinite coordination networks for use as 2nd-order nonlinear optical (NLO) materials. Work performed mainly in the authors' lab. demonstrated that noncentrosym. solids based on infinite networks can be rationally synthesized by combining unsym. bridging ligands and metal centers with well-defined coordination geometries. Specifically, coordination networks based on 3-dimensional diamondoid and 2-dimensional grid structures can be successfully engineered with a high degree of probability and predictability to crystallize in noncentrosym. space groups. The authors have also included noncentrosym. solids based on 1-dimensional chains and related helical structures for comparison.
    8. 8
      Shi, Y.; Zhang, C.; Zhang, H.; Bechtel, J. H.; Dalton, L. R.; Robinson, B. H.; Steier, W. H. Low (Sub-1-V) Halfwave Voltage Polymeric Electro-Optic Modulators Achieved by Controlling Chromophore Shape Science 2000, 288, 119– 122 DOI: 10.1126/science.288.5463.119
      8
      Low (sub-1-volt) halfwave voltage polymeric electro-optic modulators achieved by controlling chromophore shape
      Shi, Yongqiang; Zhang, Cheng; Zhang, Hua; Bechtel, James H.; Dalton, Larry R.; Robinson, Bruce H.; Steier, William H.
      Science (Washington, D. C.) (2000), 288 (5463), 119-122CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)
      Electrooptic (EO) modulators encode elec. signals onto fiber optic transmissions. High drive voltages limit gain and noise levels. Typical polymeric and Li niobate modulators operate with halfwave voltages of 5 V. Sterically modified org. chromophores were used to reduce the attenuation of elec. field poling-induced electrooptic activity caused by strong intermol. electrostatic interactions. Such modified chromophores, incorporated into polymer hosts, were used to fabricate EO modulators with halfwave voltages of 0.8 V (at a telecommunications wavelength of 1318 nm) and to achieve a halfwave voltage-interaction length product of 2.2 V- centimeters. Optical push-pull poling and driving were also used to reduce halfwave voltage. This study, together with recent demonstrations of exceptional bandwidths (more than 110 GHz) and ease of integration (with very large scale integration semiconductor circuitry and ultra-low-loss passive optical circuitry) demonstrates the potential of polymeric materials for next generation telecommunications, information processing, and radio frequency distribution.
    9. 9
      Burland, D. M.; Miller, R. D.; Walsh, C. A. Second-Order Nonlinearity in Poled-Polymer Systems Chem. Rev. 1994, 94, 31– 75 DOI: 10.1021/cr00025a002
      9
      Second-order nonlinearity in poled-polymer systems
      Burland, Donald M.; Miller, Robert D.; Walsh, Cecilia A.
      Chemical Reviews (Washington, DC, United States) (1994), 94 (1), 31-75CODEN: CHREAY; ISSN:0009-2665.
      A review with 290 refs. discussed the macroscopic second-order nonlinearity, the development and decay of the elec. field poled order responsible for the nonlinearity, methods of detg. of this nonlinearity, and the chem. nature of the polymeric systems identified as promising second-order materials.
    10. 10
      Marks, T. J.; Ratner, M. A. Design, Synthesis, and Properties of Molecule-Based Assemblies with Large Second-Order Optical Nonlinearities Angew. Chem., Int. Ed. Engl. 1995, 34, 155– 173 DOI: 10.1002/anie.199501551
      There is no corresponding record for this reference.
    11. 11
      Ashwell, G. J.; Jackson, P. D.; Crossland, W. A. Non-Centrosymmetry and Second-Harmonic Generation in Z-Type Langmuir-Blodgett Films Nature 1994, 368, 438– 440 DOI: 10.1038/368438a0
      There is no corresponding record for this reference.
    12. 12
      Penner, T. L.; Motschmann, H. R.; Armstrong, N. J.; Ezenyilimba, M. C.; Williams, D. J. Efficient Phase-Matched Second-Harmonic Generation of Blue Light in an Organic Waveguide Nature 1994, 367, 49– 51 DOI: 10.1038/367049a0
      There is no corresponding record for this reference.
    13. 13
      Lin, W. W.; Lin, W. W.; Wong, G. K.; Marks, T. J. Supramolecular Approaches to Second-Order Nonlinear Optical Materials. Self-Assembly and Microstructural Characterization of Intrinsically Acentric [(Aminophenyl)azo]pyridinium Superlattices J. Am. Chem. Soc. 1996, 118, 8034– 8042 DOI: 10.1021/ja960395f
      13
      Supramolecular Approaches to Second-Order Nonlinear Optical Materials. Self-Assembly and Microstructural Characterization of Intrinsically Acentric [(Aminophenyl)azo]pyridinium Superlattices
      Lin, Wenbin; Lin, Weiping; Wong, George K.; Marks, Tobin J.
      Journal of the American Chemical Society (1996), 118 (34), 8034-8042CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      The synthesis and characterization of self-assembled 2nd-order nonlinear optical multilayer materials contg. the high-hyperpolarizability [(aminophenyl)azo]pyridinium chromophore are described. The chromophoric multilayers are assembled on clean glass or single crystal Si substrates via the following iterative reaction sequence: (1) treatment with 4-ClCH2C6H4SiCl3, 3-BrC3H6SiCl3, or 3-IC3H6SiI3 to afford a self-assembled coupling layer; (2) quaternization of 4-[[4-[N,N-bis(hydroxylethyl)amino]phenyl]azo]pyridine in a topotactic fashion to generate an [(aminophenyl)azo]pyridinium chromophore layer; (3) crosslinking with Cl(SiCl2O)2SiCl3 to afford a capping layer (which regenerates surface hydroxyl groups for subsequent layer deposition). The new chromophore precursor 4-[[4-[N,N-bis(hydroxylethyl)amino]phenyl]azo]pyridine was synthesized by diazotization of 4-aminopyridine followed by coupling with N-phenyldiethanolamine and was characterized by elemental anal., mass spectrometry, and IR, UV-visible, and NMR spectroscopies. The chromophoric multilayers were characterized by x-ray photoelectron and transmission optical spectroscopies, spectroscopic ellipsometry, x-ray reflectivity, advancing contact angle measurements, and polarized 2nd harmonic generation (SHG). The good structural regularity of the chromophoric multilayers is indicated by the linear dependence of the [(aminophenyl)azo]pyridinium chromophore longitudinal HOMO → LUMO charge-transfer excitation absorbance at 572 nm and the ellipsometry- and x-ray reflectivity-derived multilayer thicknesses on the no. of assembled trilayers, while the uniform polar order of the stacked chromophoric multilayers is evidenced by the quadratic dependence of the 2nd harmonic generation intensities on the no. of trilayers. The [(aminophenyl)azo]pyridinium multilayers are photochem. stable, have very high structural regularities, and exhibit a 2nd-order nonlinear optical susceptibility (χ(2)) of ∼3.6 × 10-7 esu (∼150 pm/V) at a fundamental λ = 1064 nm. At. force microscopy reveals that the surfaces of the self-assembled multilayers are smooth (root mean square roughness = 12 Å for a 10 trilayer sample), undoubtedly reflecting the high 3-dimensional structural regularities of the individual layers.
    14. 14
      Katz, H. E.; Wilson, W. L.; Scheller, G. Chromophore Structure, Second Harmonic Generation, and Orientational Order in Zirconium Phosphonate/Phosphate Self-Assembled Multilayers J. Am. Chem. Soc. 1994, 116, 6636– 6640 DOI: 10.1021/ja00094a019
      14
      Chromophore Structure, Second Harmonic Generation, and Orientational Order in Zirconium Phosphonate/Phosphate Self-Assembled Multilayers
      Katz, H. E.; Wilson, W. L.; Scheller, G.
      Journal of the American Chemical Society (1994), 116 (15), 6636-40CODEN: JACSAT; ISSN:0002-7863.
      Two new phosphono-terminated polar azo dyes, the rigid 1-(4-phosphonophenyl)-4-[4-[4-(2-hydroxyethylsulfonyl)phenylazo]phenyl]piperazine (I) and 3-[4-[[4-[2-cyano-2-(hydroxyethoxycarbonyl)ethenyl]phenylazo]phenyl]-N-methylamino]propylphosphonic acid (II) with a large mol. hyperpolarizability, were designed and incorporated into Zr-based surface multilayers. Second harmonic generation (SHG) was obsd. from the multilayers as a function of incident and polarization angles and compared with that from a previously reported aminophenylazophenylphosphonic acid chromophore. I and II were analogous to moieties commonly used in elec. field-poled polymers, allowing comparisons between the polymers and the multilayers. Apparent order parameters 〈cos3θ〉 were >0.2 for I and ∼0.16 for II. Because of local field effects, the value for I was probably a lower limit. Use of other dyes that were both rigid and highly polar led to H-aggregation. Insertion of a nonpolar chromophore layer among the polar layers had no effect on SHG. The syntheses involved several novel reactions, involving the prepn. of an unsym. substituted diphenylpiperazine, an anilinoalkyl phosphonate, and the deprotected phosphonic acids themselves.
    15. 15
      Zyss, J.; Nicoud, J. F.; Coquillay, M. Chirality and Hydrogen Bonding in Molecular Crystals for Phase-Matched Second-Harmonic Generation: N-(4-Nitrophenyl)-(L)-Prolinol (NPP) J. Chem. Phys. 1984, 81, 4160 DOI: 10.1063/1.448134
      15
      Chirality and hydrogen bonding in molecular crystals for phase-matched second-harmonic generation: N-(4-nitrophenyl)-(L)-prolinol (NPP)
      Zyss, J.; Nicoud, J. F.; Coquillay, M.
      Journal of Chemical Physics (1984), 81 (9), 4160-7CODEN: JCPSA6; ISSN:0021-9606.
      The higher 2nd-harmonic efficiency, of powders, of a new org. mol. crystal N-(4-nitrophenyl)-(L)-prolinol (NPP) is reported. Electronic polarizability of NPP mols. relates to that of other p-nitroaniline-like structures such as that of previously reported N-(2,4-dinitrophenyl)methyl alaninate, and the increase in cryst. nonlinear efficiency by one order of magnitude above the latter is ascribed to an optimized cryst. structure rather than to minor changes of the mol. hyperpolarizability. The simultaneous chiral and H-bonding character of the prolinol electron-donating group leads to a quasioptimal angle, with respect to quadratic phase-matched nonlinear interactions, between the mol. transition dipole moments and the 2-fold axis of the monoclinic P21 crystal structure. Based on a simple oriented gas description of the quasiplanar structure of the crystal, 2 possible mutually exclusive 2nd-harmonic phase-matched configurations are evidenced and promote the optimized nonlinear tensor coeff.
    16. 16
      Gryl, M.; Krawczuk, A.; Stadnicka, K. Polymorphism of Urea-Barbituric Acid Co-Crystals Acta Crystallogr., Sect. B: Struct. Sci. 2008, 64, 623– 632 DOI: 10.1107/S0108768108026645
      16
      Polymorphism of urea-barbituric acid co-crystals
      Gryl, Marlena; Krawczuk, Anna; Stadnicka, Katarzyna
      Acta Crystallographica, Section B: Structural Science (2008), 64 (5), 623-632CODEN: ASBSDK; ISSN:0108-7681. (International Union of Crystallography)
      The crystal structures of three polymorphs found for the addn. complex of urea and barbituric acid are described and compared. Two polymorphs are monoclinic, space groups P21/c and Cc, whereas the 3rd is triclinic, P‾1. The displacement of electron d. towards the mesomeric forms, corresponding to the tautomeric forms of higher stability, of the barbituric acid mol. seem to influence the type of H bonds formed, which in turn dets. the different packing topol. in the polymorphs. While the polymorphic forms can be easily differentiated at the 1st-level graph-set anal. of their H-bonding patterns, a higher-level anal. enables important features of the mutual spatial arrangement of the structural components to be revealed. Crystallog. data are given.
    17. 17
      Gryl, M.; Kozieł, M.; Stadnicka, K.; Matulková, I.; Němec, I.; Tesařová, N.; Němec, P. Lidocaine Barbiturate: A Promising Material for Second Harmonic Generation CrystEngComm 2013, 15, 3275 DOI: 10.1039/c3ce00059a
      There is no corresponding record for this reference.
    18. 18
      Gryl, M.; Seidler, T.; Stadnicka, K.; Matulkova, I.; Nemec, I.; Tesarova, N.; Nemec, P. The Crystal Structure and Optical Properties of a Pharmaceutical Co-Crystal - the Case of the Melamine-Barbital Addition Compound CrystEngComm 2014, 16, 5765– 5768 DOI: 10.1039/c4ce00178h
      There is no corresponding record for this reference.
    19. 19
      Evans, O. R.; Xiong, R.; Wang, Z.; Wong, G. K.; Lin, W. Crystal Engineering of Acentric Diamondoid Metal-Organic Coordination Networks Angew. Chem., Int. Ed. 1999, 38, 536– 538 DOI: 10.1002/(SICI)1521-3773(19990215)38:4<536::AID-ANIE536>3.0.CO;2-3
      There is no corresponding record for this reference.
    20. 20
      Mendiratta, S.; Lee, C. H.; Lee, S. Y.; Kao, Y. C.; Chang, B. C.; Lo, Y. H.; Lu, K. L. Structural Characteristics and Non-Linear Optical Behaviour of a 2-Hydroxynicotinate-Containing Zinc-Based Metal-Organic Framework Molecules 2015, 20, 8941– 8951 DOI: 10.3390/molecules20058941
      20
      Structural characteristics and non-linear optical behaviour of a 2-hydroxynicotinate-containing zinc-based metal-organic framework
      Mendiratta, Shruti; Lee, Cheng-Hua; Lee, Sih-Ying; Kao, Ya-Chuan; Chang, Bor-Chen; Lo, Yih-Hsing; Lu, Kuang-Lieh
      Molecules (2015), 20 (5), 8941-8951CODEN: MOLEFW; ISSN:1420-3049. (MDPI AG)
      Materials with non-linear optical (NLO) properties play an important role in the construction of electronic devices for optical communications, optical data processing and data storage. With this aim in mind, a Zn(II)-based metal-org. framework {[Zn2(nica)2(bpy)1.5(H2O)]·0.5(bpy)·3H2O}n (1), was synthesized using 4,4'-bipyridine (bpy) and a potentially bidentate ligand, 2-hydroxynicotinic acid (H2nica) with a salicylate binding moiety. A single-crystal X-ray diffraction anal. revealed that compd. 1 crystd. in the orthorhombic space group Fdd2 and was composed of a three dimensional porous framework. Since Fdd2 belonged to a class of non-centrosym. space groups, we therefore investigated the non-linear optical behavior of compd. 1. Photoluminescence studies revealed that compd. 1 exhibited a blue light emission with a maxima at 457 nm.
    21. 21
      Serra-Crespo, P.; van der Veen, M. A.; Gobechiya, E.; Houthoofd, K.; Filinchuk, Y.; Kirschhock, C. E. A.; Martens, J. A.; Sels, B. F.; De Vos, D. E.; Kapteijn, F. NH2-MIL-53(Al): A High-Contrast Reversible Solid-State Nonlinear Optical Switch J. Am. Chem. Soc. 2012, 134, 8314– 8317 DOI: 10.1021/ja300655f
      21
      NH2-MIL-53(Al): A High-Contrast Reversible Solid-State Nonlinear Optical Switch
      Serra-Crespo, Pablo; van der Veen, Monique A.; Gobechiya, Elena; Houthoofd, Kristof; Filinchuk, Yaroslav; Kirschhock, Christine E. A.; Martens, Johan A.; Sels, Bert F.; De Vos, Dirk E.; Kapteijn, Freek; Gascon, Jorge
      Journal of the American Chemical Society (2012), 134 (20), 8314-8317CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      The metal-org. framework NH2-MIL-53(Al) is the 1st solid-state material displaying nonlinear optical switching due to a conformational change upon breathing. A switching contrast of at least 38 was obsd. This transition originates in the restrained linker mobility in the very narrow pore configuration.
    22. 22
      Jain, P.; Dalal, N. S.; Toby, B. H.; Kroto, H. W.; Cheetham, A. K. Order-Disorder Antiferroelectric Phase Transition in a Hybrid Inorganic-Organic Framework with the Perovskite Architecture J. Am. Chem. Soc. 2008, 130, 10450– 10451 DOI: 10.1021/ja801952e
      22
      Order-Disorder Antiferroelectric Phase Transition in a Hybrid Inorganic-Organic Framework with the Perovskite Architecture
      Jain, Prashant; Dalal, Naresh S.; Toby, Brian H.; Kroto, Harold W.; Cheetham, Anthony K.
      Journal of the American Chemical Society (2008), 130 (32), 10450-10451CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      [(CH3)2NH2]Zn(HCOO)3, adopts a structure that is analogous to that of a traditional perovskite, ABX3, with A = [(CH3)2NH2], B = Zn, and X = HCOO. The hydrogen atoms of the di-Me ammonium cation, which hydrogen bond to oxygen atoms of the formate framework, are disordered at room temp. X-ray powder diffraction, dielec. const., and sp. heat data show that [(CH3)2NH2]Zn(HCOO)3 undergoes an order-disorder phase transition on cooling below ∼156 K. We present evidence that this is a classical paraelec. to antiferroelec. phase transition that is driven by ordering of the hydrogen atoms. This sort of elec. ordering assocd. with order-disorder phase transition is unprecedented in hybrid frameworks and opens up an exciting new direction in rational synthetic strategies to create extended hybrid networks for applications in ferroic-related fields.
    23. 23
      Jain, P.; Ramachandran, V.; Clark, R. J.; Zhou, H. D.; Toby, B. H.; Dalal, N. S.; Kroto, H. W.; Cheetham, A. K. Multiferroic Behavior Associated with an Order–Disorder Hydrogen Bonding Transition in Metal–Organic Frameworks (MOFs) with the Perovskite ABX3 Architecture J. Am. Chem. Soc. 2009, 131, 13625– 13627 DOI: 10.1021/ja904156s
      23
      Multiferroic Behavior Associated with an Order-Disorder Hydrogen Bonding Transition in Metal-Organic Frameworks (MOFs) with the Perovskite ABX3 Architecture
      Jain, Prashant; Ramachandran, Vasanth; Clark, Ronald J.; Zhou, Hai Dong; Toby, Brian H.; Dalal, Naresh S.; Kroto, Harold W.; Cheetham, Anthony K.
      Journal of the American Chemical Society (2009), 131 (38), 13625-13627CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      Multiferroic behavior in perovskite-related metal-org. frameworks of general formula [(CH3)2NH2]M(HCOO)3, where M = Mn, Fe, Co, and Ni, is reported. All four compds. exhibit paraelec.-antiferroelec. phase transition behavior in the temp. range 160-185 K (Mn: 185 K, Fe: 160 K; Co: 165 K; Ni: 180 K); this is assocd. with an order-disorder transition involving the hydrogen bonded dimethylammonium cations. On further cooling, the compds. become canted weak ferromagnets below 40 K. This research opens up a new class of multiferroics in which the elec. ordering is achieved by means of hydrogen bonding.
    24. 24
      Zhang, W.; Cai, Y.; Xiong, R. G.; Yoshikawa, H.; Awaga, K. Exceptional Dielectric Phase Transitions in a Perovskite-Type Cage Compound Angew. Chem., Int. Ed. 2010, 49, 6608– 6610 DOI: 10.1002/anie.201001208
      24
      Exceptional Dielectric Phase Transitions in a Perovskite-Type Cage Compound
      Zhang, Wen; Cai, Ying; Xiong, Ren-Gen; Yoshikawa, Hirofumi; Awaga, Kunio
      Angewandte Chemie, International Edition (2010), 49 (37), 6608-6610, S6608/1-S6608/5CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
      The authors presented a new org.-inorg. hybrid cage compd. with the perovskite-type architecture. The compd. is a novel org.-inorg. hybrid cage compd. (HIm)2[KFe(CN)6] (where Him = imidazolium) with a perovskite-type structure, in which the order-disorder behavior of the Hlm polar guests give rise to striking dielec. anomalies. It exhibits two phase transitions at 158 K and 187 K. An order-disorder mechanism is found in the structural transformations owing to the motions of the cationic guests under different temps. The compds. represents a new class of switchable mol. dielecs. that shows striking dielec. anomalies and anisotropy. Investigations on such systems can shed light on the understanding of structural phase transitions of switchable mol. dielecs. and afford a useful strategy in searching for new elec. ordering materials.
    25. 25
      Xu, G.-C.; Ma, X.-M.; Zhang, L.; Wang, Z.-M.; Gao, S. Disorder-Order Ferroelectric Transition in the Metal Formate Framework of [NH4][Zn(HCOO)3] J. Am. Chem. Soc. 2010, 132, 9588– 9590 DOI: 10.1021/ja104263m
      25
      Disorder-Order Ferroelectric Transition in the Metal Formate Framework of [NH4][Zn(HCOO)3]
      Xu, Guan-Cheng; Ma, Xiao-Ming; Zhang, Li; Wang, Zhe-Ming; Gao, Song
      Journal of the American Chemical Society (2010), 132 (28), 9588-9590CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      A three-dimensional chiral metal formate framework compd., [NH4][Zn(HCOO)3], undergoes a paraelec.-ferroelec. phase transition at 191 K triggered by the disorder-order transition of NH4+ cations within the structure. Crystallog. data are given.
    26. 26
      Cui, H.; Zhou, B.; Long, L.-S.; Okano, Y.; Kobayashi, H.; Kobayashi, A. A Porous Coordination-Polymer Crystal Containing One-Dimensional Water Chains Exhibits Guest-Induced Lattice Distortion and a Dielectric Anomaly Angew. Chem., Int. Ed. 2008, 47, 3376– 3380 DOI: 10.1002/anie.200705846
      There is no corresponding record for this reference.
    27. 27
      Dong, X.-Y.; Li, B.; Ma, B.-B.; Li, S.-J.; Dong, M.-M.; Zhu, Y.-Y.; Zang, S.-Q.; Song, Y.; Hou, H.-W.; Mak, T. C. W. Ferroelectric Switchable Behavior through Fast Reversible De/adsorption of Water Spirals in a Chiral 3D Metal-Organic Framework J. Am. Chem. Soc. 2013, 135, 10214– 10217 DOI: 10.1021/ja403449k
      27
      Ferroelectric Switchable Behavior through Fast Reversible De/adsorption of Water Spirals in a Chiral 3D Metal-Organic Framework
      Dong, Xi-Yan; Li, Bo; Ma, Bin-Bin; Li, Shi-Jun; Dong, Ming-Ming; Zhu, Yan-Yan; Zang, Shuang-Quan; Song, You; Hou, Hong-Wei; Mak, Thomas. C. W.
      Journal of the American Chemical Society (2013), 135 (28), 10214-10217CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      A polar homochiral 3-dimensional MOF [{Co2(L)(bpe)(H2O)}·5H2O]n constructed with cobalt(II) and a new ligand N-(1,3-dicarboxy-5-benzyl)-carboxymethylglycine (H4L) accommodates ordered helical water streams in its helical grooves. It provides the 1st example of switchable ferroelec. and optical behavior through two-step reversible single-crystal to single-crystal transformation (SCSC) upon desorption/adsorption of water spirals and coordinated water mols., resp.
    28. 28
      Markey, K.; Putzeys, T.; Horcajada, P.; Devic, T.; Guillou, N.; Wübbenhorst, M.; Van Cleuvenbergen, S.; Verbiest, T.; De Vos, D. E.; van der Veen, M. A. Second Harmonic Generation Microscopy Reveals Hidden Polar Organization in Fluoride Doped MIL-53(Fe) Dalt. Trans. 2016, 45, 4401– 4406 DOI: 10.1039/C5DT04632G
      28
      Second harmonic generation microscopy reveals hidden polar organization in fluoride doped MIL-53(Fe)
      Markey, Karen; Putzeys, Tristan; Horcajada, Patricia; Devic, Thomas; Guillou, Nathalie; Wubbenhorst, Michael; Cleuvenbergen, Stijn Van; Verbiest, Thierry; De Vos, Dirk E.; van der Veen, Monique A.
      Dalton Transactions (2016), 45 (10), 4401-4406CODEN: DTARAF; ISSN:1477-9226. (Royal Society of Chemistry)
      Polar metal-org. frameworks have potential applications as functional nonlinear optical, piezoelec., pyroelec. and ferroelec. materials. Using 2nd harmonic generation microscopy fluoride doping of the microporous Fe(III) terephthalate MOF MIL-53(Fe) induces a polar organization in its structure, which was not previously detected with XRD. The polar order is only obsd. when both fluoride and guest mols. are present, and may be related to a complex interplay between the adsorbates and the framework, leading to a modification of the positioning of fluoride in the inorg. Fe-chains. Combined polarized 2nd harmonic generation microscopy and scanning pyroelec. microscopy show that the polar axis is unidirectional and of the same sense over the whole crystal, extending up to 100 μm. This finding shows how MOF materials can be endowed with useful properties by doping MOFs with fluoride.
    29. 29
      Abrahams, S. C.; Robertson, J. M. The Crystal Structure of P-Nitroaniline, NO2.C6H4.NH2 Acta Crystallogr. 1948, 1, 252– 259 DOI: 10.1107/S0365110X48000673
      29
      The crystal structure of p-nitroaniline
      Abrahams, S. C.; Robertson, J. Monteath
      Acta Crystallographica (1948), 1 (), 252-9CODEN: ACCRA9; ISSN:0365-110X.
      cf. C.A. 42, 1779e. p-Nitroaniline forms monoclinic crystals, space group C52h - P21/n, a = 12.34 ± 0.02, b = 6.02 ± 0.02, c = 8.63 ± 0.02 A., β = 91°40', with 4 asymmetric mols. in the unit cell. Fourier methods using 250 reflections from the axial zones yielded the coordinates of the atoms, the mol. dimensions, and intermol. distances. The nitro group is sym. and lies in the plane of the benzene ring. Hydrogen bridges connect the O atoms of the NO2 to the NH2 of adjoining mols. There is a very close approach (2.7-3.0 A.) between one of the NO2 oxygen atoms and three of the aromatic C atoms of an adjoining mol. This new intermol. attraction may be responsible for the formation of many mol. compds. between aromatic nitro compds. and polycyclic hydrocarbons.
    30. 30
      Donohue, J.; Trueblood, K. The Crystal Structure of P-Nitroaniline Acta Crystallogr. 1956, 9, 960– 965 DOI: 10.1107/S0365110X56002680
      There is no corresponding record for this reference.
    31. 31
      Wübbenhorst, M.; Klap, G. J.; Jansen, J. C.; van Bekkum, H.; van Turnhout, J. Glass Transition of One-Dimensional Molecular Chains of P-Nitroaniline Confined in AlPO4–5 Nanopores Revealed by Dielectric Spectroscopy J. Chem. Phys. 1999, 111, 5637– 5640 DOI: 10.1063/1.479864
      There is no corresponding record for this reference.
    32. 32
      van der Veen, M. A.; Van Noyen, J.; Sels, B. F.; Jacobs, P. A.; Verbiest, T.; De Vos, D. E. Mapping of the Organization of P-Nitroaniline in SAPO-5 by Second-Harmonic Generation Microscopy Phys. Chem. Chem. Phys. 2010, 12, 10688 DOI: 10.1039/c0cp00257g
      There is no corresponding record for this reference.
    33. 33
      van der Veen, M. A.; Sels, B. F.; De Vos, D. E.; Verbiest, T. Localization of P-Nitroaniline Chains Inside Zeolite ZSM-5 with Second-Harmonic Generation Microscopy J. Am. Chem. Soc. 2010, 132, 6630– 6631 DOI: 10.1021/ja101614w
      33
      Localization of p-Nitroaniline Chains Inside Zeolite ZSM-5 with Second-Harmonic Generation Microscopy
      van der Veen, Monique A.; Sels, Bert F.; De Vos, Dirk E.; Verbiest, Thierry
      Journal of the American Chemical Society (2010), 132 (19), 6630-6631CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      For the 1st time, 2nd-harmonic generation microscopy (SHGM) was employed to study zeolites. Large ZSM-5 crystals filled with p-nitroaniline (PNA) dipoles were visualized. SHGM can discriminate between the straight b-pores and the sinusoidal a-pores of this zeolite, thus revealing the intergrown structure of these crystals. Also, dipole chains are formed not only in the b-pores but also in the a-pores. PNA only assembles into dipole chains of parallel orientation in those pores that are directly accessible from the outer surface. The area in which this PNA ordering prevails is limited to a strip near the outer surface of the zeolite crystal. A rationalization for these two observations is offered.
    34. 34
      Marlow, F.; Wübbenhorst, M.; Caro, J. Pyroelectric Effects on Molecular Sieve Crystals Loaded with Dipole Molecules J. Phys. Chem. 1994, 98, 12315– 12319 DOI: 10.1021/j100098a029
      There is no corresponding record for this reference.
    35. 35
      Klap, G. J.; van Klooster, S. M.; Wübbenhorst, M.; Jansen, J. C.; van Bekkum, H.; van Turnhout, J. Polarization Reversal in AlPO4-5 Crystals Containing Polar or Nonpolar Organic Molecules: A Scanning Pyroelectric Microscopy Study J. Phys. Chem. B 1998, 102, 9518– 9524 DOI: 10.1021/jp982816g
      There is no corresponding record for this reference.
    36. 36
      Klap, G. J.; Wübbenhorst, M.; Jansen, J. C.; van Koningsveld, H.; van Bekkum, H.; van Turnhout, J. Polar Growth and Directional Adsorption of Large AlPO4-5 Crystals Determined by Scanning Pyroelectric Microscopy Chem. Mater. 1999, 11, 3497– 3503 DOI: 10.1021/cm991043l
      There is no corresponding record for this reference.
    37. 37
      Skibo, E. B.; Gilchrist, J. H. Synthesis and Electrochemistry of Pyrimidoquinazoline-5,10-Diones. Design of Hydrolytically Stable High Potential Quinones and New Reductive Alkylation Systems J. Org. Chem. 1988, 53, 4209– 4218 DOI: 10.1021/jo00253a010
      There is no corresponding record for this reference.
    38. 38
      Stock, N. Hochdurchsatzmethoden Zur Entdeckung Und Optimierung Kristalliner Poröser Materialien Chem. Ing. Tech. 2010, 82, 1039– 1047 DOI: 10.1002/cite.201000029
      38
      High-throughput methods for discovery and optimization of crystalline porous materials
      Stock, N.
      Chemie Ingenieur Technik (2010), 82 (7), 1039-1047CODEN: CITEAH; ISSN:0009-286X. (Wiley-VCH Verlag GmbH & Co. KGaA)
      High throughput (HD) methods allow a systematic and efficient anal. of complex parameter areas such as obsd. in solvothermal synthesis. Their application is used to find new compds. to optimize synthesis conditions and reaction trends. Some HD methods were developed with a different degree of parallelism, miniaturization and automation of individual steps within the last decade to obtain the use of new outstanding microporous compds. in the field of zeolites, ZIFs (zeolitic imidazolate frameworks) and MOFs (metal-org. frameworks).
    39. 39
      Stock, N. High-Throughput Investigations Employing Solvothermal Syntheses Microporous Mesoporous Mater. 2010, 129, 287– 295 DOI: 10.1016/j.micromeso.2009.06.007
      39
      High-throughput investigations employing solvothermal syntheses
      Stock, Norbert
      Microporous and Mesoporous Materials (2009), 129 (3), 287-295CODEN: MIMMFJ; ISSN:1387-1811. (Elsevier Inc.)
      High-throughput (HT) methods applied to solvothermal reaction systems are a powerful technique for the rapid systematic investigation of large parameter spaces in a short time, giving rise to the accelerated discovery of new compds. and optimization of synthesis parameters. Large amts. of data can be generated in a short period of time, which provides the opportunity to ext. relevant reaction trends and contribute to a better understanding of the role of reaction parameters. While the primary driving forces in the development of high-throughput methods were com. considerations to cut down the time to market for new or improved products, the methodol. is also well suited for investigations in academia. The fields of application range from the discovery of new compds., the optimization of syntheses conditions to the extn. of synthesis trends. Examples demonstrating the power of HT methods will be based on different classes of compds. such as zeolites, inorg.-org. hybrid compds. such as ZIFs, MOFs, and MILs and will range from the investigation of two-dimensional to multi-dimensional parameter spaces.
    40. 40
      Stock, N.; Biswas, S. Synthesis of Metal-Organic Frameworks (MOFs): Routes to Various MOF Topologies, Morphologies, and Composites Chem. Rev. 2012, 112, 933– 969 DOI: 10.1021/cr200304e
      40
      Synthesis of Metal-Organic Frameworks (MOFs): Routes to Various MOF Topologies, Morphologies, and Composites
      Stock, Norbert; Biswas, Shyam
      Chemical Reviews (Washington, DC, United States) (2012), 112 (2), 933-969CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
      A review. The synthesis of metal-org. frameworks (MOFs) has attracted immense attention during the last 2 decades due to the possibility to obtain a large variety of aesthetically interesting structures that could also be of great interest for applications in a no. of fields related to porous materials. This includes the more traditional areas of storage, sepn., and catalysis, which are based on the pore size and shape as well as the host guest interactions involved. In addn., biomedical applications or the use as sensor materials are currently intensively investigated. Although MOF synthesis was originally set out for making new compds. and structures with interesting properties, the field has matured and is broadening its scope. This holds for the synthesis methods applied as well as the areas of application. While conventional syntheses methods have been widely used, the fields of mechano-, sono-, and electrochem. synthesis as well as microwave-assisted syntheses are just emerging. They have demonstrated to be applicable for some compds., often under milder reaction conditions, yielding materials with different particle sizes and properties. This could be of interest for up-scaling of syntheses and the application of MOFs.
    41. 41
      Bauer, S.; Stock, N. Hochdurchsatz-Methoden in Der Festkörperchemie. Schneller Zum Ziel. Chem Chem. Unserer Zeit 2007, 41, 390– 398 DOI: 10.1002/ciuz.200700404
      41
      Quicker to achieve the goal. High through-put method in solid state chemistry
      Bauer, Sebastian; Stock, Norbert
      Chemie in Unserer Zeit (2007), 41 (5), 390-398CODEN: CUNZAW; ISSN:0009-2851. (Wiley-VCH Verlag GmbH & Co. KGaA)
      A review. High-throughput (HT) methods applied to materials discovery have attracted much attention over the last few years because they permit a fast and efficient investigation of parameter space while consuming only small amts. of starting materials. Nowadays, many different HT techniques in solid state science are employed to accelerate the discovery and optimization of materials. The degree of parallelization, automation, and miniaturization dets. the efficiency of a HT methodol. Systematic investigation of parameter space and careful data anal. allow the identification of reaction trends and may give important guidance in better understanding of reaction systems. The described HT methodol. for solvothermal reactions allows the systematic investigation of 48 different hydrothermal reactions at a time. The methodol. includes automatic dispensing of solids and liqs., followed by homogenization, pH measurement, synthesis, isolation, washing as well as automated phase anal. by x-ray diffraction without the manipulation of individual samples. The focus of this article is on the application of HT methods in the investigation of the parameter space in solid state sciences. Based on selected examples, the power of HT methods in the discovery of new compds., the optimization of reactions, the identification of reaction trends, as well as the investigation of the influence of process parameters is described. The large amt. of data obtained in a short time leads to an improvement towards the understanding of the role that synthesis and process parameters play in the formation of compds. and materials.
    42. 42
      Topas Academic 4.2; Coelho Software: Brisbane, Australia, 2007.
      There is no corresponding record for this reference.
    43. 43
      Loiseau, T.; Serre, C.; Huguenard, C.; Fink, G.; Taulelle, F.; Henry, M.; Bataille, T.; Férey, G. A Rationale for the Large Breathing of the Porous Aluminum Terephthalate (MIL-53) Upon Hydration Chem. - Eur. J. 2004, 10, 1373– 1382 DOI: 10.1002/chem.200305413
      43
      A rationale for the large breathing of the porous aluminum terephthalate (MIL-53) upon hydration
      Loiseau, Thierry; Serre, Christian; Huguenard, Clarisse; Fink, Gerhard; Taulelle, Francis; Henry, Marc; Bataille, Thierry; Ferey, Gerard
      Chemistry - A European Journal (2004), 10 (6), 1373-1382CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)
      Al 1,4-benzenedicarboxylate Al(OH)[O2CC6H4CO2][HO2C-C6H4-CO2H]0.70 or MIL-53as (Al) was hydrothermally synthesized by heating a mixt. of Al nitrate, 1,4-benzenedicarboxylic acid, and H2O, for three days at 220°. Its 3 D framework is built up of infinite trans chains of corner-sharing AlO4(OH)2 octahedra. The chains are interconnected by the 1,4-benzenedicarboxylate groups, creating 1 D rhombic-shaped tunnels. Disordered 1,4-benzenedicarboxylic acid mols. are trapped inside these tunnels. Their evacuation upon heating, between 275 and 420°, leads to a nanoporous open-framework (MIL-53ht (Al) or Al(OH)[O2CC6H4CO2]) with empty pores of diam. 8.5 Å. This solid exhibits a Langmuir surface area. of 1590(1) m2g-1 together with a remarkable thermal stability, since it starts to decomp. only at 500°. At room temp., the solid reversibly absorbs H2O in its tunnels, causing a very large breathing effect and shrinkage of the pores. Anal. of the hydration process by solid-state NMR (1H, 13C, 27Al) has clearly indicated that the trapped H2O mols. interact with the carboxylate groups through H bonds, but do not affect the hydroxyl species bridging the Al atoms. The H bonds between H2O and the O atoms of the framework are responsible for the contraction of the rhombic channels. The structures of the three forms were detd. by powder x-ray diffraction anal. Crystal data for MIL-53as (Al) are as follows: orthorhombic system, Pnma (no. 62), a 17.129(2), b 6.628(1), c 12.182(1) Å; for MIL-53ht (Al), orthorhombic system, Imma (no. 74), a 6.608(1), b 16.675(3), c 12.813(2) Å; for MIL-53lt (Al), monoclinic system, Cc (no. 9), a 19.513(2), b 7.612(1), c 6.576(1) Å, β 104.24(1)°.
    44. 44
      Materials Studio, version 5.0; Accelrys Software, Inc., 2009.
      There is no corresponding record for this reference.
    45. 45
      Dovesi, R.; Orlando, R.; Erba, A.; Zicovich-Wilson, C. M.; Civalleri, B.; Casassa, S.; Maschio, L.; Ferrabone, M.; De La Pierre, M.; D’Arco, P. CRYSTAL14: A Program for the Ab Initio Investigation of Crystalline Solids Int. J. Quantum Chem. 2014, 114, 1287– 1317 DOI: 10.1002/qua.24658
      45
      CRYSTAL14: A program for the ab initio investigation of crystalline solids
      Dovesi, Roberto; Orlando, Roberto; Erba, Alessandro; Zicovich-Wilson, Claudio M.; Civalleri, Bartolomeo; Casassa, Silvia; Maschio, Lorenzo; Ferrabone, Matteo; De La Pierre, Marco; D'Arco, Philippe; Noel, Yves; Causa, Mauro; Rerat, Michel; Kirtman, Bernard
      International Journal of Quantum Chemistry (2014), 114 (19), 1287-1317CODEN: IJQCB2; ISSN:0020-7608. (John Wiley & Sons, Inc.)
      The capabilities of the CRYSTAL14 program are presented, and the improvements made with respect to the previous CRYSTAL09 version discussed. CRYSTAL14 is an ab initio code that uses a Gaussian-type basis set: both pseudopotential and all-electron strategies are permitted; the latter is not much more expensive than the former up to the first-second transition metal rows of the periodic table. A variety of d. functionals is available, including as an extreme case Hartree-Fock; hybrids of various nature (global, range-sepd., double) can be used. In particular, a very efficient implementation of global hybrids, such as popular B3LYP and PBE0 prescriptions, allows for such calcns. to be performed at relatively low computational cost. The program can treat on the same grounds zero-dimensional (mols.), one-dimensional (polymers), two-dimensional (slabs), as well as three-dimensional (3D; crystals) systems. No spurious 3D periodicity is required for low-dimensional systems as happens when plane-waves are used as a basis set. Symmetry is fully exploited at all steps of the calcn.; this permits, for example, to investigate nanotubes of increasing radius at a nearly const. cost (better than linear scaling!) or to perform self-consistent-field (SCF) calcns. on fullerenes as large as (10,10), with 6000 atoms, 84,000 AOs, and 20 SCF cycles, on a single core in one day. Three versions of the code exist, serial, parallel, and massive-parallel. In the second one, the most relevant matrixes are duplicated, whereas in the third one the matrixes in reciprocal space are distributed for diagonalization. All the relevant vectors are now dynamically allocated and deallocated after use, making CRYSTAL14 much more agile than the previous version, in which they were statically allocated. The program now fits more easily in low-memory machines (as many supercomputers nowadays are). CRYSTAL14 can be used on parallel machines up to a high no. of cores (benchmarks up to 10,240 cores are documented) with good scalability, the main limitation remaining the diagonalization step. Many tensorial properties can be evaluated in a fully automated way by using a single input keyword: elastic, piezoelec., photoelastic, dielec., as well as first and second hyperpolarizabilies, elec. field gradients, Born tensors and so forth. Many tools permit a complete anal. of the vibrational properties of cryst. compds. The IR and Raman intensities are now computed anal. and related spectra can be generated. Isotopic shifts are easily evaluated, frequencies of only a fragment of a large system computed and nuclear contribution to the dielec. tensor detd. New algorithms have been devised for the investigation of solid solns. and disordered systems. The topol. anal. of the electron charge d., according to the Quantum Theory of Atoms in Mols., is now incorporated in the code via the integrated merge of the TOPOND package. Electron correlation can be evaluated at the Moeller-Plesset second-order level (namely MP2) and a set of double-hybrids are presently available via the integrated merge with the CRYSCOR program.
    46. 46
      Dovesi, R.; Saunders, V. R.; Roetti, C.; Orlando, R.; Zicovich-Wilson, C. M.; Pascale, F.; Civalleri, B.; Doll, K.; Harrison, N. M.; Bush, I. J.; . CRYSTAL14 User’s Manual; University of Torino: Torino, Italy, 2014.
      There is no corresponding record for this reference.
    47. 47
      Seidler, T.; Champagne, B. Which Charge Definition for Describing the Crystal Polarizing Field and the χ (1) and χ (2) of Organic Crystals? Phys. Chem. Chem. Phys. 2015, 17, 19546– 19556 DOI: 10.1039/C5CP03248B
      There is no corresponding record for this reference.
    48. 48
      Seidler, T.; Champagne, B. Second-Order Nonlinear Optical Susceptibilities of Metal–Organic Frameworks Using a Combined Local Field Theory/Charge Embedding Electrostatic Scheme J. Phys. Chem. C 2016, 120, 6741– 6749 DOI: 10.1021/acs.jpcc.6b00217
      48
      Second-Order Nonlinear Optical Susceptibilities of Metal-Organic Frameworks Using a Combined Local Field Theory/Charge Embedding Electrostatic Scheme
      Seidler, Tomasz; Champagne, Benoit
      Journal of Physical Chemistry C (2016), 120 (12), 6741-6749CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)
      The linear (χ(1)) and second-order nonlinear (χ(2)) optical properties of metal-org. frameworks (MOFs) have been evaluated and interpreted by employing the combined local field theory/charge embedding approach. Three MOFs have been selected, the isostructural bis{4-[2-(4-pyridyl)ethenyl]benzoato}-zinc(II) (PEB-Zn) and bis{4-[2-(4-pyridyl)ethenyl]benzoato}-cadmium(II) (PEB-Cd) and bis{4-[3-(4-pyridyl)ethenyl]benzoato}-cadmium(II) (PEB'-Cd). The simulations, employing the Moller-Plesset second-order perturbation theory level to describe the ion properties, conclude that (i) χ(2) of PEB-Zn (∼60 pm/V at 1064 nm) is about 10% larger than that of PEB-Cd, (ii) χ(2) of PEB'-Cd attains 100 pm/V at 1064 nm [i.e., twice more than that of PEB-Cd or an amplitude similar to that of the 4-(N,N-dimethylamino)-3-acetamidonitrobenzene (DAN) mol. crystal] and (iii) the change of crystal structure accompanying an increase of temp. from 173 to 298 K leads to a decrease of χ(2) by ca. 10%. For the isostructural PEB-Zn and PEB-Cd, the outcome of Kurtz-Perry SHG powder method has been simulated as a function of the grain size, demonstrating that differences between the two MOFs only show up for room temp. structures. A value of 1.29 was estd. for the PEB-Zn/PEB-Cd contrast ratio, in qual. agreement with expt. (1.16). This work opens the way toward a theor. based design of MOFs with outstanding second-order nonlinear optical responses.
    49. 49
      Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Gaussian 09, revision B.01; Gaussian, Inc.: Wallingford, CT, 2009.
      There is no corresponding record for this reference.
    50. 50
      MUNN, R. W. A. General Microscopic Theory of Bulk Second-Harmonic Generation from Molecular Crystals Mol. Phys. 1996, 89, 555– 569 DOI: 10.1080/002689796173903
      There is no corresponding record for this reference.
    51. 51
      Kirtman, B.; Dykstra, C. E.; Champagne, B. Major Intermolecular Effects on Nonlinear Electrical Response in a Hexatriene Model of Solid State Polyacetylene Chem. Phys. Lett. 1999, 305, 132– 138 DOI: 10.1016/S0009-2614(99)00375-9
      51
      Major intermolecular effects on nonlinear electrical response in a hexatriene model of solid state polyacetylene
      Kirtman, Bernard; Dykstra, Clifford E.; Champagne, Benoit
      Chemical Physics Letters (1999), 305 (1,2), 132-138CODEN: CHPLBC; ISSN:0009-2614. (Elsevier Science B.V.)
      Through detailed model studies, benchmarked by extensive ab initio calcns., we show (1) how sizable medium effects on mol. elec. response of polymeric solids can arise; (2) that classical electrostatics accurately reproduces a full quantum treatment; and (3) that for a large bundle of hexatriene mols. taken as a model of polyacetylene, the medium effect will lead to as much as a 95% redn. in the second hyperpolarizability and a 50% redn. in the polarizability. For designing org. materials with enhanced nonlinear optical (NLO) properties, the results reveal features that might be optimized and point to a sound model for selecting other features.
    52. 52
      Reis, H.; Papadopoulos, M. G.; Calaminici, P.; Jug, K.; Köster, A. M. Calculation of Macroscopic Linear and Nonlinear Optical Susceptibilities for the Naphthalene, Anthracene and Meta-Nitroaniline Crystals Chem. Phys. 2000, 261, 359– 371 DOI: 10.1016/S0301-0104(00)00305-0
      52
      Calculation of macroscopic linear and nonlinear optical susceptibilities for the naphthalene, anthracene and meta-nitroaniline crystals
      Reis, H.; Papadopoulos, M. G.; Calaminici, P.; Jug, K.; Koster, A. M.
      Chemical Physics (2000), 261 (3), 359-371CODEN: CMPHC2; ISSN:0301-0104. (Elsevier Science B.V.)
      The macroscopic first- to third-order susceptibilities of naphthalene, anthracene and meta-nitroaniline (mNA) are calcd. using a rigorous local field approach. Mol. (hyper)polarizabilities used as input are detd. by d. functional theory calcns. with specially designed basis sets and for mNA also by MP2 calcns. with the 6-31++G** basis set. In the case of mNA, the permanent elec. local field due to the surrounding dipoles in the crystal is taken into account for the first- and second-order susceptibility by a self-consistent approach. The mol. dipole moment and first hyperpolarizability of mNA are drastically changed by the permanent local field. In all cases the calcd. first-order susceptibility compares very favorably with exptl. data, if the mol. response is distributed over all heavy atoms in the mols. Similarly, the calcd. second-order susceptibility for mNA is in good agreement with available exptl. data, if the same distribution scheme is used and the permanent local field is taken into account properly. This implies that accurate values for the mol. second-order hyperpolarizability γ have to be available. The anisotropic Lorentz field factor approxn. yields results that are only slightly worse than the best ones of the rigorous local field theory for the first-order susceptibilities, but fails for the second-order susceptibility of mNA, due to its incapability to describe the large effect of the permanent local field on the first-order hyperpolarizability β.
    53. 53
      Seidler, T.; Stadnicka, K.; Champagne, B. Investigation of the Linear and Second-Order Nonlinear Optical Properties of Molecular Crystals within the Local Field Theory J. Chem. Phys. 2013, 139, 114105 DOI: 10.1063/1.4819769
      53
      Investigation of the linear and second-order nonlinear optical properties of molecular crystals within the local field theory
      Seidler, Tomasz; Stadnicka, Katarzyna; Champagne, Benoit
      Journal of Chemical Physics (2013), 139 (11), 114105/1-114105/15CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)
      Modest calcns. combining 1st principles evaluations of the mol. properties with electrostatic interaction schemes to account for the crystal environment effects are reliable for predicting and interpreting the exptl. measured elec. linear and 2nd-order nonlinear optical susceptibilities of mol. crystals within the exptl. error bars. This is illustrated by considering 2 mol crystals, namely: 2-Me-4-nitroaniline and 4-(N,N-dimethylamino)-3-acetamidonitrobenzene. Three types of surrounding effects should be accounted for (i) the polarization due to the surrounding mols., described here by static elec. fields originating from their elec. dipoles or charge distributions, (ii) the intermol. interactions, which affect the geometry and particularly the mol. conformation, and (iii) the screening of the external elec. field by the constitutive mols. This study further highlights the role of electron correlation on the linear and nonlinear responses of mol. crystals and the challenge of describing frequency dispersion. (c) 2013 American Institute of Physics.
    54. 54
      Seidler, T.; Stadnicka, K.; Champagne, B. Second-Order Nonlinear Optical Susceptibilities and Refractive Indices of Organic Crystals from a Multiscale Numerical Simulation Approach Adv. Opt. Mater. 2014, 2, 1000– 1006 DOI: 10.1002/adom.201400245
      54
      Second-order Nonlinear Optical Susceptibilities and Refractive Indices of Organic Crystals from a Multiscale Numerical Simulation Approach
      Seidler, Tomasz; Stadnicka, Katarzyna; Champagne, Benoit
      Advanced Optical Materials (2014), 2 (10), 1000-1006CODEN: AOMDAX; ISSN:2195-1071. (Wiley-VCH Verlag GmbH & Co. KGaA)
      The performance of a simple multiscale approach to rapidly screen the second-order nonlinear optical (NLO) susceptibilities [χ(2)] as well as the refractive indexes of org. crystals solely from the knowledge of their crystal structure is demonstrated. The method combines first principles calcns. of the mol. properties with a classical electrostatic interactions scheme to account for the crystal environment effects. The calcd. values reproduce closely the measured χ(2) response for 10 org. crystals, including ionic cryst. salts, covering a χ(2) range from 10 to 600 pm V-1. The agreement between calcns. and measurements is also excellent in the case of the refractive indexes. Moreover, the method allows to analyze the relationship between the macroscopic responses [χ(2)] and the mol. first hyperpolarizabilities, highlighting the effects of crystal packing and chromophore d. as well as the role played by the crystal dressing field.
    55. 55
      Seidler, T.; Stadnicka, K.; Champagne, B. Evaluation of the Linear and Second-Order NLO Properties of Molecular Crystals within the Local Field Theory: Electron Correlation Effects, Choice of XC Functional, ZPVA Contributions, and Impact of the Geometry in the Case of 2-Methyl-4-Nitroaniline J. Chem. Theory Comput. 2014, 10, 2114– 2124 DOI: 10.1021/ct5001654
      55
      Evaluation of the Linear and Second-Order NLO Properties of Molecular Crystals within the Local Field Theory: Electron Correlation Effects, Choice of XC Functional, ZPVA Contributions, and Impact of the Geometry in the Case of 2-Methyl-4-nitroaniline
      Seidler, Tomasz; Stadnicka, Katarzyna; Champagne, Benoit
      Journal of Chemical Theory and Computation (2014), 10 (5), 2114-2124CODEN: JCTCCE; ISSN:1549-9618. (American Chemical Society)
      The linear [χ(1)] and 2nd-order nonlinear [χ(2)] optical susceptibilities of the 2-Me-4-nitroaniline (MNA) crystal are calcd. within the local field theory, which consists of 1st computing the mol. properties, accounting for the dressing effects of the surroundings, and then taking into account the local field effects. Several aspects of these calcns. are tackled with the aim of monitoring the convergence of the χ(1) and χ(2) predictions with respect to expt. by accounting for the effects of (i) the dressing field within successive approxns., of (ii) the 1st-order ZPVA corrections, and of (iii) the geometry. With respect to the ref. CCSD-based results, besides double hybrid functionals, the most reliable exchange-correlation functionals are LC-BLYP for the static χ(1) and CAM-B3LYP (and M05-2X, to a lesser extent) for the dynamic χ(1) but they strongly underest. χ(2). Double hybrids perform better for χ(2) but not necessarily for χ(1), and, also, their performances are much similar to MP2, which is known to slightly overestimate β, with respect to high-level coupled-clusters calcns. and, therefore, χ(2). Other XC functionals with less HF exchange perform poorly with overestns./underestns. of χ(1)/χ(2), whereas the HF method leads to underestns. of both. The 1st-order ZPVA corrections, estd. at the B3LYP level, are usually small but not negligible. After ZPVA corrections, the mol. polarizabilities and 1st hyperpolarizabilities increase by 2% and 5%, resp., whereas their impact is magnified on the macroscopic responses with enhancements of χ(1) by up to 5% and of χ(2) by ≤10%-12% at λ = 1064 nm. The geometry plays also a key role in view of predicting accurate susceptibilities, particularly for push-pull π-conjugated compds. such as MNA. The geometry optimized using periodic boundary conditions is characterized by an overestd. bond length alternation, which gives larger mol. properties and even larger macroscopic responses, because of the local field factor amplification effects. The best ests. based on exptl. geometries, charge dressing field, ZPVA correction, and CCSD mol. properties lead to an overestn. of χ(1) by 12% in the static limit and 7% at λ = 1064 nm. For χ(2), the difference, with respect to the expt., is satisfactory and of the order of 1 std. deviation.
    56. 56
      Seidler, T.; Stadnicka, K.; Champagne, B. Linear and Second-Order Nonlinear Optical Properties of Ionic Organic Crystals J. Chem. Phys. 2014, 141, 104109 DOI: 10.1063/1.4894483
      56
      Linear and second-order nonlinear optical properties of ionic organic crystals
      Seidler, Tomasz; Stadnicka, Katarzyna; Champagne, Benoit
      Journal of Chemical Physics (2014), 141 (10), 104109/1-104109/10CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)
      The linear and second-order nonlinear optical susceptibilities of three ionic org. crystals, 4-N,N-dimethylamino-4'-N'-methyl-stilbazolium tosylate (DAST), 4-N,N-dimethylamino-4'-N'-methyl-stilbazolium 2,4,6-trimethylbenzenesulfonate (DSTMS), and 4-N,N-dimethylamino-4'-N'-phenyl-stilbazolium hexafluorophosphate (DAPSH), were calcd. by adopting a two-step multi-scale procedure, which consists in calcg.: (i) the ion properties using ab initio or d. functional theory methods and then (ii) in accounting for the crystal environment effects using classical electrostatic models. Provided that the ionic properties are evaluated at the second-order Moller-Plesset level and that the dressing field effects using point charges are accounted for, the agreement with expt. is excellent and enables to explain the origin of the larger χ(2) response of DAPSH with respect to DAST and DSTMS. Also including the dressing field decreases the χ(2) response of ionic crystals whereas its effect is opposite for mol. crystals. Also, also this multi-scale approach can be used to interpret the impact of the nature and position of the counterion on the linear and nonlinear optical susceptibilities of ionic crystals. Finally, the use of a conventional exchange-correlation functional like B3LYP leads to severe overestimations of χ(1) but large underestimations of χ(2) whereas the use of homogeneous dipole field is not recommended because it usually leads to overestimations of the linear and nonlinear optical susceptibilities. (c) 2014 American Institute of Physics.
    57. 57
      Wittmann, T.; Siegel, R.; Reimer, N.; Milius, W.; Stock, N.; Senker, J. Enhancing the Water Stability of Al-MIL-101-NH2 via Postsynthetic Modification Chem. - Eur. J. 2015, 21, 314– 323 DOI: 10.1002/chem.201404654
      57
      Enhancing the Water Stability of Al-MIL-101-NH2 via Postsynthetic Modification
      Wittmann, Thomas; Siegel, Renee; Reimer, Nele; Milius, Wolfgang; Stock, Norbert; Senker, Juergen
      Chemistry - A European Journal (2015), 21 (1), 314-323CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)
      Stabilization of the mesoporous MOF Al-MIL-101-NH2 via postsynthetic modification with Ph isocyanate is reported. In this process 86% of the amino groups were converted into phenylurea units. As a consequence, the long-term stability of Al-MIL-101-URPh in liq. water could be extended beyond a week. In water satd. atms. Al-MIL-101-URPh decompd. at least 12-times slower than the unfunctionalized analog. To study the underlying processes both materials were characterized by Ar, N2 and H2O sorption measurements, powder X-ray diffraction, thermogravimetric and chem. anal. as well as solid-state NMR and IR spectroscopy. Postsynthetic modification decreased the BET equiv. surface area from 3363 to 1555 m2 g-1 for Al-MIL-101-URPh and reduced the mean diams. of the mesopores by 0.6 nm without degrading the structure significantly and reducing thermal stability. In spite of similar water uptake capacities, the relative humidity-dependent uptake of Al-MIL-101-URPh is slowed and occurs at higher relative humidity values. In combination with 1H-27Al D-HMQC NMR spectroscopy expts. this favors a shielding mechanism of the Al clusters by the pendant Ph groups and rules out pore blocking.
    58. 58
      Ahnfeldt, T.; Gunzelmann, D.; Loiseau, T.; Hirsemann, D.; Senker, J.; Férey, G.; Stock, N. Synthesis and Modification of a Functionalized 3D Open-Framework Structure with MIL-53 Topology Inorg. Chem. 2009, 48, 3057– 3064 DOI: 10.1021/ic8023265
      58
      Synthesis and Modification of a Functionalized 3D Open-Framework Structure with MIL-53 Topology
      Ahnfeldt, Tim; Gunzelmann, Daniel; Loiseau, Thierry; Hirsemann, Dunja; Senker, Jurgen; Ferey, Gerard; Stock, Norbert
      Inorganic Chemistry (2009), 48 (7), 3057-3064CODEN: INOCAJ; ISSN:0020-1669. (American Chemical Society)
      Al aminoterephthalate Al(OH)[H2N-BDC]·0.3(H2N-H2BDC) (denoted MIL-53-NH2(as)) was synthesized under hydrothermal conditions. The activation of the compd. can be achieved in two steps. The treatment with DMF at 150° leads to Al(OH)[H2N-BDC]·0.95DMF (MIL-53-NH2(DMF)). In the 2nd step, DMF is thermally removed at 130°. Upon cooling in air, the hydrated form Al(OH)[H2N-BDC]·0.9H2O (MIL-53-NH2(lt)) was obtained. The dehydration leads to a porous compd. that exhibits hysteresis behavior in the N2 sorption expts. The MIL-53-NH2(lt) can be modified by postsynthetic functionalization using formic acid, and the corresponding amide Al(OH)[HC(O)N(H)-BDC]·H2O (MIL-53-NHCHO) is formed. All four phases were thoroughly characterized by x-ray powder diffraction, solid-state NMR and IR spectroscopy, and sorption measurements, as well as thermogravimetric and elemental anal. Based on the refined lattice parameter similar breathing behavior of the framework as found in the unfunctionalized MIL-53 can be deduced. Solid-state NMR spectra unequivocally demonstrate the guest species, as well as the successful postsynthetic functionalization.
    59. 59
      Sumida, K.; Rogow, D. L.; Mason, J. A.; McDonald, T. M.; Bloch, E. D.; Herm, Z. R.; Bae, T.; Long, J. R. Carbon Dioxide Capture in Metal–Organic Frameworks Chem. Rev. 2012, 112, 724– 781 DOI: 10.1021/cr2003272
      59
      Carbon Dioxide Capture in Metal-Organic Frameworks
      Sumida, Kenji; Rogow, David L.; Mason, Jarad A.; McDonald, Thomas M.; Bloch, Eric D.; Herm, Zoey R.; Bae, Tae-Hyun; Long, Jeffrey R.
      Chemical Reviews (Washington, DC, United States) (2012), 112 (2), 724-781CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
      An extensive review is given on progress made in the capture of CO2 from power plant emissions, briefly considering also the CO2 storage (sequestration) of the enormous quantities of CO2 that would be obtained as a result of a successful capture framework. The main existing CO2 capture technologies are discussed in the context of capture performance considerations of aq. alkanolamine solns. and porous solids such as zeolites and activated carbons. Schematic diagrams are presented of idealized temp. swing adsorption, pressure swing adsorption, and vacuum swing adsorption processes for regenerating solid adsorbent in a fixed-bed column. The structural features and CO2 adsorption characteristics of isoreticular metal-org. frameworks (MOF) are discussed in detail. The high-pressure adsorption capacities of 36 MOF and the lower-pressure adsorption capacities of many more MOF, at 293-319 K, are tabulated. The various types of functionalities that have been explored to date for prepg. materials with enhanced CO2 capture performance are outlined, including amines, strongly polarizing org. functionalities, and exposed metal cation sites. The synthesis of continuous films of MOF and their use in membranes for gas sepn. are examd., with the tabulation of the CO2 sepn. performance of MOF mixed-matrix membranes. A final section outlines main issues that need to be addressed to achieve next-generation materials capable of fulfilling the criteria required for the gas sepns. relevant to post-combustion CO2 capture, pre-combustion CO2 capture, and oxy-fuel combustion.
    60. 60
      Serra-Crespo, P.; Gobechiya, E.; Ramos-Fernandez, E. V.; Juan-Alcañiz, J.; Martinez-Joaristi, A.; Stavitski, E.; Kirschhock, C. E. a.; Martens, J. a.; Kapteijn, F.; Gascon, J. Interplay of Metal Node and Amine Functionality in NH2-MIL-53: Modulating Breathing Behavior through Intra-Framework Interactions Langmuir 2012, 28, 12916– 12922 DOI: 10.1021/la302824j
      60
      Interplay of Metal Node and Amine Functionality in NH2-MIL-53: Modulating Breathing Behavior through Intra-framework Interactions
      Serra-Crespo, Pablo; Gobechiya, Elena; Ramos-Fernandez, Enrique V.; Juan-Alcaniz, Jana; Martinez-Joaristi, Alberto; Stavitski, Eli; Kirschhock, Christine E. A.; Martens, Johan A.; Kapteijn, Freek; Gascon, Jorge
      Langmuir (2012), 28 (35), 12916-12922CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)
      Amino-functionalized MIL-53 with different metals as nodes were synthesized, NH2-MIL-53(Al, Ga, and In) derived with 2-aminoterephthalic acid. By detg. adsorption properties and spectroscopic characterization, the authors unequivocally show that the interaction between the amines of the org. linker and bridging μ2-OH of the inorg. scaffold modulates metal org. framework (MOF) flexibility. The strength of the interaction was found to correlate with the electropositivity of the metal.
    61. 61
      Boyd, R. W. Nonlinear Optics; Elsevier, 2008.
      There is no corresponding record for this reference.
    62. 62
      Le Floc’h, V.; Brasselet, S.; Roch, J.-F.; Zyss, J. Monitoring of Orientation in Molecular Ensembles by Polarization Sensitive Nonlinear Microscopy J. Phys. Chem. B 2003, 107, 12403– 12410 DOI: 10.1021/jp034950t
      62
      Monitoring of Orientation in Molecular Ensembles by Polarization Sensitive Nonlinear Microscopy
      Le Floc'h, Veronique; Brasselet, Sophie; Roch, Jean-Francois; Zyss, Joseph
      Journal of Physical Chemistry B (2003), 107 (45), 12403-12410CODEN: JPCBFK; ISSN:1520-6106. (American Chemical Society)
      The authors present high resoln. 2-photon excitation microscopy studies combining 2-photon fluorescence (TPF) and 2nd harmonic generation (SHG) to probe orientational distributions of mol. ensembles at room temp. A detailed polarization anal. of TPF and SHG signals is used to unravel the parameters of the mol. orientational statistical distribution, using a technique which can be extended and generalized to a broad variety of mol. arrangements. A polymer film contg. mols. active for TPF and/or SHG emission is studied as a model system. Polarized TPF provides information on specific properties pertaining to incoherent emission in mol. media, such as excitation transfer. SHG, being highly sensitive to a slight departure from centrosymmetry such as induced by an external elec. field in the medium, complements TPF. The response of each signal to a variable excitation polarization allows study of mol. behavior in complex environments which affect their orientations and interactions.
    63. 63
      Loiseau, T.; Muguerra, H.; Haouas, M.; Taulelle, F.; Férey, G. Hydrothermal Synthesis and Structural Characterization of a Gallium Pyromellitate Ga(OH)(btec)·0.5H2O, with Infinite Ga-(μ2-OH)-Ga Chains (MIL-61) Solid State Sci. 2005, 7, 603– 609 DOI: 10.1016/j.solidstatesciences.2005.01.014
      63
      Hydrothermal synthesis and structural characterization of a gallium pyromellitate Ga(OH)(btec).0.5H2O, with infinite Ga-(μ2-OH)-Ga chains (MIL-61)
      Loiseau, Thierry; Muguerra, Herve; Haouas, Mohamed; Taulelle, Francis; Ferey, Gerard
      Solid State Sciences (2005), 7 (5), 603-609CODEN: SSSCFJ; ISSN:1293-2558. (Elsevier B.V.)
      A new Ga carboxylate Ga(OH)(btec).0.5H2O (MIL-61) was synthesized under mild hydrothermal conditions (200°, 24 h) in the presence of 1,2,4,5-benzenetetracarboxylic (btec) acid and H2O. The crystal structure, characterized by Rietevelt refinement of powder XRD data, consists of trans chains of GaO4(OH)2 octahedra, connected to each other through a μ 2 -OH group. The three-dimensional framework is built up from these chains linked together via the org. mols. thus delimiting the cavities where the H2O mols. are encapsulated. Anal. by solid state NMR (1H and 13C) confirmed the presence within the structure of both H2O mols. and carboxylate moieties partially deprotonated. The structure of Ga(OH)(btec).0.5H2O corresponds to that of MIL-61 obtained with V replacing Ga. Crystal data for Ga4(OH)4((HO2C)2-C6H4-(CO2)2)4·2H2O: a 14.8325(10), b 6.7792(10), c 10.6726(10) Å, V = 1073.2(2) Å3, Pnma (n°62).
    64. 64
      Gándara, F.; Gomez-Lor, B.; Gutiérrez-Puebla, E.; Iglesias, M.; Monge, M. A.; Proserpio, D. M.; Snejko, N. An Indium Layered MOF as Recyclable Lewis Acid Catalyst Chem. Mater. 2008, 20, 72– 76 DOI: 10.1021/cm071079a
      64
      An Indium Layered MOF as Recyclable Lewis Acid Catalyst
      Gandara, F.; Gomez-Lor, B.; Gutierrez-Puebla, E.; Iglesias, M.; Monge, M. A.; Proserpio, D. M.; Snejko, N.
      Chemistry of Materials (2008), 20 (1), 72-76CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
      By using the bent linker 4,4'-(hexafluoroisopropylidene)bis(benzoic acid) (H2hippb), whose central atom is an sp3 carbon, a new In(III) MOF (metal-org. framework) was obtained. The structure is described as thick layers with the bent geometry of the ligand leading to the formation of square-shaped channels, which run inside the framework layers. This microporous, thermally stable compd. is an efficient heterogeneous catalyst for acetalization of aldehydes. Differences in the catalytic activity when a compd. with empty or filled channels is used demonstrate that the catalytic reactions take place inside the pores.
    65. 65
      Van Der Veen, M. A.; Verbiest, T.; De Vos, D. E. Probing Microporous Materials with Second-Harmonic Generation Microporous Mesoporous Mater. 2013, 166, 102– 108 DOI: 10.1016/j.micromeso.2012.04.051
      There is no corresponding record for this reference.
    66. 66
      Falaise, C.; Volkringer, C.; Facqueur, J.; Bousquet, T.; Gasnot, L.; Loiseau, T. Capture of Iodine in Highly Stable Metal–Organic Frameworks: A Systematic Study Chem. Commun. 2013, 49, 10320 DOI: 10.1039/c3cc43728k
      66
      Capture of iodine in highly stable metal-organic frameworks: a systematic study
      Falaise, Clement; Volkringer, Christophe; Facqueur, Jacques; Bousquet, Till; Gasnot, Laurent; Loiseau, Thierry
      Chemical Communications (Cambridge, United Kingdom) (2013), 49 (87), 10320-10322CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)
      Aluminum-based metal-org. frameworks were studied for sorption of iodine (I2) in cyclohexane. The best sorption uptake was obtained with solids decorated by electro-donor groups attached either to the org. ligand (-NH2) or the inorg. sub-network (-OH).
    67. 67
      Armstrong, D. J.; Alford, W. J.; Raymond, T. D.; Smith, A. V. Absolute Measurement of the Effective Nonlinearities of KTP and BBO Crystals by Optical Parametric Amplification Appl. Opt. 1996, 35, 2032– 2040 DOI: 10.1364/AO.35.002032
      67
      Absolute measurement of the effective nonlinearities of KTP and BBO crystals by optical parametric amplification
      Armstrong, D. J.; Alford, W. J.; Raymond, T. D.; Smith, A. V.
      Applied Optics (1996), 35 (12), 2032-2040CODEN: APOPAI; ISSN:0003-6935. (Optical Society of America)
      Abs. magnitudes of the effective nonlinearity, deff, were measured for 7 KTP and 6 BBO crystals. The deff's were derived from the parametric gain of an 800-nm signal wave in the sample crystals when they were pumped by the frequency-doubled, spatially filtered light from an injection-seeded, Q-switched Nd:YAG laser. The KTP crystals, all type II phase matched with propagation in the X-Z plane, had deff values ranging from 1.97 to 3.50 pm/V. Measurements of gain as a function of phase velocity mismatch indicate that 2 of the KTP crystals clearly contain multiple ferroelec. domains. For 5 type I phase-matched BBO crystals, deff ranged from 1.76 to 1.83 pm/V, and a single type II phase-matched BBO crystal had a deff of 1.56 pm/V. The uncertainty in the measurements of deff values is ±5% for KTP and ±10% for BBO.

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