Air/Liquid Interfacial Nanoassembly of Molecular Building Blocks into Preferentially Oriented Porous Organic Nanosheet Crystals via Hydrogen BondingClick to copy article linkArticle link copied!
Abstract
Nanosheets with highly regulated nanopores are ultimately thin functional materials for diverse applications including molecular separation and detection, catalysis, and energy conversion and storage. However, their availability has hitherto been restricted to layered parent materials, covalently bonded sheets, which are layered via relatively weak electrostatic interactions. Here, we report a rational bottom-up methodology that enables nanosheet creation beyond the layered systems. We employ the air/liquid interface to assemble a triphenylbenzene derivative into perfectly oriented highly crystalline noncovalent-bonded organic nanosheets under ambient conditions. Each molecular building unit connects laterally by hydrogen bonding, endowing the nanosheets with size- and position-regulated permanent nanoporosity, as established by in situ synchrotron X-ray surface crystallography and gas sorption measurements. Notably, the nanosheets are constructed specifically by interfacial synthesis, which suppresses the intrinsic complex interpenetrated structure of the bulk crystal. Moreover, they possess exceptional long-term and thermal stability and are easily transferrable to numerous substrates without loss of structural integrity. Our work shows the power of interfacial synthesis using a suitably chosen molecular component to create two-dimensional (2D) nanoassemblies not accessible by conventional bulk crystal exfoliation techniques.
Figure 1
Figure 1. Morphological and structural varieties of BTB depending on fabrication technique. (a) Triangular-shaped BTB molecules form hexagonal rings via hydrogen-bonded carboxylic acid dimers. Conventional bulk synthesis results in rodlike crystals with multiply interpenetrated rings. Interfacial synthesis controls the molecular orientation and prevents interpenetration, leading to perfectly oriented nanosheets with long-range molecular columns and size- and position-regulated nanopores. (b) Simple interfacial synthetic process involves spreading BTB solution on pure water subphase, resulting in the creation of crystalline porous nanosheets (LINAS-1) easily transferable to numerous substrates. (c) Contrasting micrometer-scale bulk BTB crystal. Rodlike objects similarly shaped to the bulk crystals are formed by conventional solution-based film fabrication techniques such as dip casting (d) and drop casting (e) on Si substrates. (f) Vacuum deposition on an Si substrate results in the formation of an amorphous film (Figure S9). The morphological images are obtained by AFM, (b, d–f) and optical microscopy (c), respectively.
Results and Discussion
Nanosheet Preparation
Figure 2
Figure 2. Structural characterization of LINAS-1 by in situ GIXRD measurements at the air/liquid interface. (a) Surface-pressure–mean-molecular-area (Π-A) isotherm for LINAS-1 with surface morphological images (inset) obtained by Brewster angle microscopy (BAM) at selected Π. (b, c) Observed in situ in-plane, (b) and out-of-plane, and (c) synchrotron GIXRD (λ = 1.549 Å, Q = 4π sinθ/λ, incident angle, α = 0.12°) profiles at surface pressures, Π = 0, 1, 5, and 20 mN/m together with schematic representation of the scattering geometry. (d) Basal plane projection and (e) stacking motif of the LINAS-1 crystalline structure derived from the GIXRD measurements. (f) Measured in situ (black line, Π = 5 mN/m) and calculated (red line: AA slip-stacking with slip-angle, δ = 5°; blue line: AB stacking model with neighboring honeycomb networks shifted horizontally by half the unit-cell size) in-plane synchrotron XRD profiles. Ticks mark the Bragg reflection positions. The tick marks show the reflection positions.
Structural Characterization of LINAS-1 by in Situ GIXRD Measurements at the Air/Liquid Interface
Integrity and Morphological Characterization of LINAS-1 after Transfer onto Solid Substrates
Figure 3
Figure 3. Integrity and morphological characterization of LINAS-1 after transfer onto solid substrates. (a) Schematic illustration of the horizontal dipping deposition method for nanosheet transfer from the liquid surface to the solid substrate surface. (b) In-plane and (c) out-of-plane synchrotron GIXRD profiles for LINAS-1 transferred on Si substrate (black line) together with those on water surface (red line). The tick marks show the reflection positions. (d) AFM image of LINAS-1 on Si and corresponding height profile along the track marked in red. (e) Height distribution of LINAS-1 evaluated from the AFM images. (f) Ultraviolet–visible (UV–vis) absorption spectra of LINAS-1 on a quartz substrate after successive cycles of sheet deposition. Inset: maximum absorbance versus number of sheet-deposition cycles. (g) Optical microscope image of a holey substrate with micromesh before (left) and after (right) LINAS-1 transfer.
Gas Sorption Characteristics
Figure 4
Figure 4. Gas-sorption properties of LINAS-1. (a) N2-sorption isotherms (77 K) for LINAS-1 (red) and bulk BTB crystals (black). Isotherms show both adsorption (dots) and desorption (open circles) data. Inset: expanded view of the low-pressure region. (b) Pore-size distribution curve for LINAS-1 obtained from Barrett–Joyner–Halenda (BJH) analysis of the N2-sorption isotherm. (c) Water vapor sorption isotherms (298 K). (d) O2-sorption isotherms (77 K).
Conclusions
Methods
Nanosheet Preparation (LINAS-1)
Deposition of LINAS-1 on Solid Substrates
Powdered LINAS-1
In Situ Grazing-Incidence (GI) Synchrotron X-ray Diffraction (GIXRD) Measurements at Air/Liquid Interfaces
Synchrotron XRD Measurements on Solid Substrates
Atomic Force Microscopy
Gas Sorption Isotherm Measurements
Supporting Information
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsnano.7b04447.
Experimental details; bulk single crystal XRD analysis data; UV-vis and IR absorption spectra, PL spectra, powder XRD data, AFM and SEM images (PDF)
Terms & Conditions
Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.
Acknowledgment
We acknowledge financial support from the Japan Science and Technology Agency (JST) on “Precursory Research for Embryonic Science and Technology (PRESTO)” for a project of “Molecular technology and creation of new functions (JPMJPR12K8)”, CREST, the Japan Society for the Promotion of Science (JSPS) on “Grants-in-Aid for Scientific Research, KAKENHI” (JP22108524, JP24108735 “coordination programming”, JP16H05968, JP16K13610, JP17H05139 “π-system figuration”), MEXT “SCF for Promoting Science and Technology”, the Kao Foundation for Arts and Sciences, the INAMORI foundation, the Japan Prize Foundation, Shiseido Female Researcher Science Grant, the Murata Science Foundation, and the Royal Society “International Exchange Scheme”. The synchrotron X-ray radiation experiments were performed at the BL13XU beamline, SPring-8 (2013A1668) and at the ID10B beamline, ESRF. We thank Rigaku for the in situ GIXRD measurements upon heating and Y. Susami, Y. Shibata, and Y. Takabayashi for experimental support.
References
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- 6Mas-Ballesté, R.; Gómez-Navarro, C.; Gómez-Herrero, J.; Zamora, F. 2D Materials: to Graphene and Beyond Nanoscale 2011, 3, 20– 30 DOI: 10.1039/C0NR00323AGoogle Scholar6https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXitVChtr0%253D&md5=b15b6e89bd3a6735ffd861d5be1078e62D materials: to graphene and beyondMas-Balleste, Ruben; Gomez-Navarro, Cristina; Gomez-Herrero, Julio; Zamora, FelixNanoscale (2011), 3 (1), 20-30CODEN: NANOHL; ISSN:2040-3372. (Royal Society of Chemistry)This review is an attempt to illustrate the different alternatives in the field of 2D materials. Graphene seems to be just the tip of the iceberg and we show how the discovery of alternative 2D materials is starting to show the rest of this iceberg. The review comprises the current state-of-the-art of the vast literature in concepts and methods already known for isolation and characterization of graphene, and rationalizes the quite disperse literature in other 2D materials such as metal oxides, hydroxides and chalcogenides, and metal-org. frameworks.
- 7Coleman, J. N.; Lotya, M.; O’Neill, A.; Bergin, S. D.; King, P. J.; Khan, U.; Young, K.; Gaucher, A.; De, S.; Smith, R. J.; Shvets, I. V.; Arora, S. K.; Stanton, G.; Kim, H. Y.; Lee, K.; Kim, G. T.; Duesberg, G. S.; Hallam, T.; Boland, J. J.; Wang, J. J. Two-Dimensional Nanosheets Produced by Liquid Exfoliation of Layered Materials Science 2011, 331, 568– 571 DOI: 10.1126/science.1194975Google Scholar7https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXhtlWisLY%253D&md5=7bd4a9da1b4f81f2caa3d1159dd8a5c7Two-Dimensional Nanosheets Produced by Liquid Exfoliation of Layered MaterialsColeman, Jonathan N.; Lotya, Mustafa; O'Neill, Arlene; Bergin, Shane D.; King, Paul J.; Khan, Umar; Young, Karen; Gaucher, Alexandre; De, Sukanta; Smith, Ronan J.; Shvets, Igor V.; Arora, Sunil K.; Stanton, George; Kim, Hye-Young; Lee, Kangho; Kim, Gyu Tae; Duesberg, Georg S.; Hallam, Toby; Boland, John J.; Wang, Jing Jing; Donegan, John F.; Grunlan, Jaime C.; Moriarty, Gregory; Shmeliov, Aleksey; Nicholls, Rebecca J.; Perkins, James M.; Grieveson, Eleanor M.; Theuwissen, Koenraad; McComb, David W.; Nellist, Peter D.; Nicolosi, ValeriaScience (Washington, DC, United States) (2011), 331 (6017), 568-571CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)If they could be easily exfoliated, layered materials would become a diverse source of two-dimensional crystals whose properties would be useful in applications ranging from electronics to energy storage. Layered compds. such as MoS2, WS2, MoSe2, MoTe2, TaSe2, NbSe2, NiTe2, BN, and Bi2Te3 can be efficiently dispersed in common solvents and can be deposited as individual flakes or formed into films. Electron microscopy strongly suggests that the material is exfoliated into individual layers. By blending this material with suspensions of other nanomaterials or polymer solns., the authors can prep. hybrid dispersions or composites, which can be cast into films. WS2 and MoS2 effectively reinforce polymers, whereas WS2/carbon nanotube hybrid films have high cond., leading to promising thermoelec. properties.
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- 11Varoon, K.; Zhang, X.; Elyassi, B.; Brewer, D. D.; Gettel, M.; Kumar, S.; Lee, J. A.; Maheshwari, S.; Mittal, A.; Sung, C. Y.; Cococcioni, M.; Francis, L. F.; McCormick, A. V.; Mkhoyan, K. A.; Tsapatsis, M. Dispersible Exfoliated Zeolite Nanosheets and their Application as a Selective Membrane Science 2011, 334, 72– 75 DOI: 10.1126/science.1208891Google Scholar11https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXht1Gms7%252FN&md5=93f4e5d1f4d0ce666a7fc837cd29f82aDispersible Exfoliated Zeolite Nanosheets and Their Application as a Selective MembraneVaroon, Kumar; Zhang, Xueyi; Elyassi, Bahman; Brewer, Damien D.; Gettel, Melissa; Kumar, Sandeep; Lee, J. Alex; Maheshwari, Sudeep; Mittal, Anudha; Sung, Chun-Yi; Cococcioni, Matteo; Francis, Lorraine F.; McCormick, Alon V.; Mkhoyan, K. Andre; Tsapatsis, MichaelScience (Washington, DC, United States) (2011), 334 (6052), 72-75CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)Thin zeolite films are attractive for a wide range of applications, including mol. sieve membranes, catalytic membrane reactors, permeation barriers, and low-dielec.-const. materials. Synthesis of thin zeolite films using high-aspect-ratio zeolite nanosheets is desirable because of the packing and processing advantages of the nanosheets over isotropic zeolite nanoparticles. Attempts to obtain a dispersed suspension of zeolite nanosheets via exfoliation of their lamellar precursors have been hampered because of their structure deterioration and morphol. damage (fragmentation, curling, and aggregation). We demonstrated the synthesis and structure detn. of highly cryst. nanosheets of zeolite frameworks MWW and MFI. The purity and morphol. integrity of these nanosheets allow them to pack well on porous supports, facilitating the fabrication of mol. sieve membranes.
- 12Peng, Y.; Li, Y.; Ban, Y.; Jin, H.; Jiao, W.; Liu, X.; Yang, W. Metal-Organic Framework Nanosheets as Building Blocks for Molecular Sieving Membranes Science 2014, 346, 1356– 1359 DOI: 10.1126/science.1254227Google Scholar12https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXitVCgsrjJ&md5=507ed6b5f2ccc54ed1a6aa3cd8f1a4ddMetal-organic framework nanosheets as building blocks for molecular sieving membranesPeng, Yuan; Li, Yanshuo; Ban, Yujie; Jin, Hua; Jiao, Wenmei; Liu, Xinlei; Yang, WeishenScience (Washington, DC, United States) (2014), 346 (6215), 1356-1359CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)Layered metal-org. frameworks would be a diverse source of cryst. sheets with nanometer thickness for mol. sieving if they could be exfoliated, but there is a challenge in retaining the morphol. and structural integrity. The authors report the prepn. of 1-nm-thick sheets with large lateral area and high crystallinity from layered MOFs. They are used as building blocks for ultrathin mol. sieve membranes, which achieve hydrogen gas (H2) permeance of up to several thousand gas permeation units (GPUs) with H2/CO2 selectivity greater than 200. The authors found an unusual proportional relationship between H2 permeance and H2 selectivity for the membranes, and achieved a simultaneous increase in both permeance and selectivity by suppressing lamellar stacking of the nanosheets.
- 13Chandra, S.; Kandambeth, S.; Biswal, B. P.; Lukose, B.; Kunjir, S. M.; Chaudhary, M.; Babarao, R.; Heine, T.; Banerjee, R. Chemically Stable Multilayered Covalent Organic Nanosheets from Covalent Organic Frameworks via Mechanical Delamination J. Am. Chem. Soc. 2013, 135, 17853– 17861 DOI: 10.1021/ja408121pGoogle Scholar13https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXhs1yls7nE&md5=bcf489e02681985891c8273864cbacc3Chemically Stable Multilayered Covalent Organic Nanosheets from Covalent Organic Frameworks via Mechanical DelaminationChandra, Suman; Kandambeth, Sharath; Biswal, Bishnu P.; Lukose, Binit; Kunjir, Shrikant M.; Chaudhary, Minakshi; Babarao, Ravichandar; Heine, Thomas; Banerjee, RahulJournal of the American Chemical Society (2013), 135 (47), 17853-17861CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)A series of five thermally and chem. stable functionalized covalent org. frameworks (COFs), namely, TpPa-NO2, TpPa-F4, TpBD-(NO2)2, TpBD-Me2, and TpBD-(OMe)2 were synthesized by employing the solvothermal aldehyde-amine Schiff base condensation reaction. In order to complete the series, previously reported TpPa-1, TpPa-2, and TpBD have also been synthesized, and altogether, eight COFs were fully characterized through powder X-ray diffraction (PXRD), Fourier transform IR (FT-IR) spectroscopy, 13C solid-state NMR spectroscopy, and thermogravimetric anal. These COFs are cryst., permanently porous, and stable in boiling water, acid (9 N HCl), and base (3 N NaOH). The synthesized COFs (all eight) were successfully delaminated using a simple, safe, and environmentally friendly mech. grinding route to transform into covalent org. nanosheets (CONs) and were well characterized via transmission electron microscopy and at. force microscopy. Further PXRD and FT-IR analyses confirm that these CONs retain their structural integrity throughout the delamination process and also remain stable in aq., acidic, and basic media like the parent COFs. These exfoliated CONs have graphene-like layered morphol. (delaminated layers), unlike the COFs from which they were synthesized.
- 14Makiura, R.; Motoyama, S.; Umemura, Y.; Yamanaka, H.; Sakata, O.; Kitagawa, H. Surface Nano-Architecture of a Metal-Organic Framework Nat. Mater. 2010, 9, 565 DOI: 10.1038/nmat2769Google Scholar14https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXnvVOkt78%253D&md5=b5cd2860dd415d63aead956c0bc973f0Surface nano-architecture of a metal-organic frameworkMakiura, Rie; Motoyama, Soichiro; Umemura, Yasushi; Yamanaka, Hiroaki; Sakata, Osami; Kitagawa, HiroshiNature Materials (2010), 9 (7), 565-571CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)The rational assembly of ultrathin films of metal-org. frameworks (MOFs)-highly ordered microporous materials-with well-controlled growth direction and film thickness is a crit. and as yet unrealized issue for enabling the use of MOFs in nanotechnol. devices, such as sensors, catalysts and electrodes for fuel cells. Here we report the facile bottom-up fabrication at ambient temp. of such a perfect preferentially oriented MOF nanofilm on a solid surface (NAFS-1), consisting of metalloporphyrin building units. The construction of NAFS-1 was achieved by the unconventional integration in a modular fashion of a layer-by-layer growth technique coupled with the Langmuir-Blodgett method. NAFS-1 is endowed with highly cryst. order both in the out-of-plane and in-plane orientations to the substrate, as demonstrated by synchrotron X-ray surface crystallog. The proposed structural model incorporates metal-coordinated mols. projected from the two-dimensional sheets that allow each further layer to dock in a highly ordered interdigitated manner in the growth of NAFS-1. We expect that the versatility of the soln.-based growth strategy presented here will allow the fabrication of various well-ordered MOF nanofilms, opening the way for their use in a range of important applications.
- 15Makiura, R.; Konovalov, O. Interfacial Growth of Large-Area Single-Layer Metal-Organic Framework Nanosheets Sci. Rep. 2013, 3, 2506 DOI: 10.1038/srep02506Google Scholar15https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A280%3ADC%252BC3sbitlGrsA%253D%253D&md5=d15ccc3aa97416a62235795edbe443b2Interfacial growth of large-area single-layer metal-organic framework nanosheetsMakiura Rie; Konovalov OlegScientific reports (2013), 3 (), 2506 ISSN:.The air/liquid interface is an excellent platform to assemble two-dimensional (2D) sheets of materials by enhancing spontaneous organizational features of the building components and encouraging large length scale in-plane growth. We have grown 2D molecularly-thin crystalline metal-organic-framework (MOF) nanosheets composed of porphyrin building units and metal-ion joints (NAFS-13) under operationally simple ambient conditions at the air/liquid interface. In-situ synchrotron X-ray diffraction studies of the formation process performed directly at the interface were employed to optimize the NAFS-13 growth protocol leading to the development of a post-injection method -post-injection of the metal connectors into the water subphase on whose surface the molecular building blocks are pre-oriented- which allowed us to achieve the formation of large-surface area morphologically-uniform preferentially-oriented single-layer nanosheets. The growth of such large-size high-quality sheets is of interest for the understanding of the fundamental physical/chemical properties associated with ultra-thin sheet-shaped materials and the realization of their use in applications.
- 16Makiura, R.; Usui, R.; Sakai, Y.; Nomoto, A.; Ogawa, A.; Sakata, O.; Fujiwara, A. Towards Rational Modulation of In-Plane Molecular Arrangements in Metal-Organic Framework Nanosheets ChemPlusChem 2014, 79, 1352– 1360 DOI: 10.1002/cplu.201402150Google Scholar16https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhsFWjsrrO&md5=72450cc504781eb6694a90124fa35fdfTowards Rational Modulation of In-Plane Molecular Arrangements in Metal-Organic Framework NanosheetsMakiura, Rie; Usui, Ryo; Sakai, Yuta; Nomoto, Akihiro; Ogawa, Akiya; Sakata, Osami; Fujiwara, AkihikoChemPlusChem (2014), 79 (9), 1352-1360CODEN: CHEMM5; ISSN:2192-6506. (Wiley-VCH Verlag GmbH & Co. KGaA)A strategy to modulate the in-plane structural arrangement in preferentially oriented cryst. metal-org. framework (MOF) nanosheets assembled by a two-dimensional interfacial reaction between porphyrin units and metal ion linkers is reported. Starting with a tetratopic porphyrin MOF nanofilm, NAFS-2, the framework size and shape are modified by employing specially designed building units, a trans-ditopic and an expanded tetratopic porphyrin, and Cu2+ linkers. Reducing the no. of binding parts affords a MOF nanosheet, NAFS-31, with a distorted in-plane structure. Extension of the peripheral substituents, while maintaining the tetratopic porphyrin geometry, results in marked unit cell size enlargement in an undistorted square grid in the MOF nanofilm, NAFS-41. The exquisite geometric control that these structural modifications entail is valuable to allow switching of chem./phys. properties of the nanosheets and lead to realization of their use in nanotechnol. applications.
- 17Murray, D. J.; Patterson, D. D.; Payamyar, P.; Bhola, R.; Song, W.; Lackinger, M.; Schlüter, A. D.; King, B. T. Large Area Synthesis of a Nanoporous Two-Dimensional Polymer at the Air/Water Interface J. Am. Chem. Soc. 2015, 137, 3450– 3453 DOI: 10.1021/ja512018jGoogle Scholar17https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXjsVWktr8%253D&md5=d6f7026075684015e452415880470656Large Area Synthesis of a Nanoporous Two-Dimensional Polymer at the Air/Water InterfaceMurray, Daniel J.; Patterson, Dustin D.; Payamyar, Payam; Bhola, Radha; Song, Wentao; Lackinger, Markus; Schluter, A. Dieter; King, Benjamin T.Journal of the American Chemical Society (2015), 137 (10), 3450-3453CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)We present the synthesis of a two-dimensional polymer at the air/water interface and its nm-resoln. imaging. Trigonal star, amphiphilic monomers bearing three anthraceno groups on a central triptycene core are confined at the air/water interface. Compression followed by photopolymn. on the interface provides the two-dimensional polymer. Anal. by scanning tunneling microscopy suggests that the polymer is periodic with ultrahigh pore d.
- 18Rodenas, T.; Luz, I.; Prieto, G.; Seoane, B.; Miro, H.; Corma, A.; Kapteijn, F.; Xamena, F. X. L.; Gascon, J. Metal-Organic Framework Nanosheets in Polymer Composite Materials for Gas Separation Nat. Mater. 2015, 14, 48– 55 DOI: 10.1038/nmat4113Google Scholar18https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhvVGiurnJ&md5=0ed3ba9aa55b42c8597c474cf56355d2Metal-organic framework nanosheets in polymer composite materials for gas separationRodenas, Tania; Luz, Ignacio; Prieto, Gonzalo; Seoane, Beatriz; Miro, Hozanna; Corma, Avelino; Kapteijn, Freek; Llabres i Xamena, Francesc X.; Gascon, JorgeNature Materials (2015), 14 (1), 48-55CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)Composites incorporating two-dimensional nanostructures within polymeric matrixes have potential as functional components for several technologies, including gas sepn. Prospectively, employing metal-org. frameworks (MOFs) as versatile nanofillers would notably broaden the scope of functionalities. However, synthesizing MOFs in the form of freestanding nanosheets has proved challenging. We present a bottom-up synthesis strategy for dispersible copper 1,4-benzenedicarboxylate MOF lamellae of micrometre lateral dimensions and nanometer thickness. Incorporating MOF nanosheets into polymer matrixes endows the resultant composites with outstanding CO2 sepn. performance from CO2/CH4 gas mixts., together with an unusual and highly desired increase in the sepn. selectivity with pressure. As revealed by tomog. focused ion beam SEM, the unique sepn. behavior stems from a superior occupation of the membrane cross-section by the MOF nanosheets as compared with isotropic crystals, which improves the efficiency of mol. discrimination and eliminates unselective permeation pathways. This approach opens the door to ultrathin MOF-polymer composites for various applications.
- 19Theobald, J. A.; Oxtoby, N. S.; Phillips, M. A.; Champness, N. R.; Beton, P. H. Controlling Molecular Deposition and Layer Structure with Supramolecular Surface Assemblies Nature 2003, 424, 1029– 1031 DOI: 10.1038/nature01915Google Scholar19https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3sXmslSjtrk%253D&md5=152beef542cadb27750155493bf6723aControlling molecular deposition and layer structure with supramolecular surface assembliesTheobald, James A.; Oxtoby, Neil S.; Phillips, Michael A.; Champness, Neil R.; Beton, Peter H.Nature (London, United Kingdom) (2003), 424 (6952), 1029-1031CODEN: NATUAS; ISSN:0028-0836. (Nature Publishing Group)Selective non-covalent interactions have been widely exploited in soln.-based chem. to direct the assembly of mols. into nanometer-sized functional structures such as capsules, switches and prototype machines. More recently, the concepts of supramol. organization have also been applied to two-dimensional assemblies on surfaces stabilized by hydrogen bonding, dipolar coupling or metal co-ordination. Structures realized to date include isolated rows, clusters and extended networks, as well as more complex multi-component arrangements. Another approach to controlling surface structures uses adsorbed mol. monolayers to create preferential binding sites that accommodate individual target mols. Here we combine these approaches, by using hydrogen bonding to guide the assembly of two types of mols. into a two-dimensional open honeycomb network that then controls and templates new surface phases formed by subsequently deposited fullerene mols. We find that the open network acts as a two-dimensional array of large pores of sufficient capacity to accommodate several large guest mols., with the network itself also serving as a template for the formation of a fullerene layer.
- 20Elemans, J. A. A. W.; Lei, S.; De Feyter, S. Molecular and Supramolecular Networks on Surfaces: From Two-Dimensional Crystal Engineering to Reactivity Angew. Chem., Int. Ed. 2009, 48, 7298– 7332 DOI: 10.1002/anie.200806339Google Scholar20https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXhtFGrs7zO&md5=2671e78e9c54bcb3830a943327005463Molecular and Supramolecular Networks on Surfaces: From Two-Dimensional Crystal Engineering to ReactivityElemans, Johannes A. A. W.; Lei, Shengbin; De Feyter, StevenAngewandte Chemie, International Edition (2009), 48 (40), 7298-7332CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)A review. The invention of the scanning tunneling microscope has led to the visualization of mols. in real space on atomically flat conductive substrates. This has boosted research into supramol. chem. on surfaces. In this Review, we highlight recent developments in the design and functionality of supramol. surface patterns, with special attention paid to those networks which are chiral or contain a high degree of porosity as well as to the reactivity, which is one of the most important recent developments in supramol. surface chem.
- 21Moulton, B.; Zaworotko, M. J. From Molecules to Crystal Engineering: Supramolecular Isomerism and Polymorphism in Network Solids Chem. Rev. 2001, 101, 1629 DOI: 10.1021/cr9900432Google Scholar21https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3MXjtlyqtrg%253D&md5=00fbfe863055d07d1773be77dc52f023From molecules to crystal engineering. Supramolecular isomerism and polymorphism in network solidsMoulton, Brian; Zaworotko, Michael J.Chemical Reviews (Washington, D. C.) (2001), 101 (6), 1629-1658CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)A review with 299 refs. on how the advances in supramol. chem. have impacted the manner in which chemists view the existence of single crystals and the design of new cryst. phases. Coordination polymers, H-bonded networks, and supramol. isomerism and polymorphism are considered.
- 22Mannige, R. V.; Haxton, T. K.; Proulx, C.; Robertson, E. J.; Battigelli, A.; Butterfoss, G. L.; Zuckermann, R. N.; Whitelam, S. Peptoid Nanosheets Exhibit a New Secondary-Structure Motif Nature 2015, 526, 415– 420 DOI: 10.1038/nature15363Google Scholar22https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhs1KqtLzP&md5=0bd25c531cae096b9b515f15ed52dd56Peptoid nanosheets exhibit a new secondary-structure motifMannige, Ranjan V.; Haxton, Thomas K.; Proulx, Caroline; Robertson, Ellen J.; Battigelli, Alessia; Butterfoss, Glenn L.; Zuckermann, Ronald N.; Whitelam, StephenNature (London, United Kingdom) (2015), 526 (7573), 415-420CODEN: NATUAS; ISSN:0028-0836. (Nature Publishing Group)A promising route to the synthesis of protein-mimetic materials that are capable of complex functions, such as mol. recognition and catalysis, is provided by sequence-defined peptoid polymers-structural relatives of biol. occurring polypeptides. Peptoids, which are relatively non-toxic and resistant to degrdn., can fold into defined structures through a combination of sequence-dependent interactions. However, the range of possible structures that are accessible to peptoids and other biol. mimetics is unknown, and our ability to design protein-like architectures from these polymer classes is limited. Here we use mol.-dynamics simulations, together with scattering and microscopy data, to det. the at.-resoln. structure of the recently discovered peptoid nanosheet, an ordered supramol. assembly that extends macroscopically in only two dimensions. Our simulations show that nanosheets are structurally and dynamically heterogeneous, can be formed only from peptoids of certain lengths, and are potentially porous to water and ions. Moreover, their formation is enabled by the peptoids' adoption of a secondary structure that is not seen in the natural world. This structure, a zigzag pattern that we call a Σ('sigma')-strand, results from the ability of adjacent backbone monomers to adopt opposed rotational states, thereby allowing the backbone to remain linear and untwisted. Linear backbones tiled in a brick-like way form an extended two-dimensional nanostructure, the Σ-sheet. The binary rotational-state motif of the Σ-strand is not seen in regular protein structures, which are usually built from one type of rotational state. We also show that the concept of building regular structures from multiple rotational states can be generalized beyond the peptoid nanosheet system.
- 23Dunitz, J. D.; Gavezzotti, A. How Molecules Stick Together in Organic Crystals: Weak Intermolecular Interactions Chem. Soc. Rev. 2009, 38, 2622– 2633 DOI: 10.1039/b822963pGoogle Scholar23https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXhtVSlsLfI&md5=e017474d43e39e1f1bde0206a2c62e55How molecules stick together in organic crystals: weak intermolecular interactionsDunitz, Jack D.; Gavezzotti, AngeloChemical Society Reviews (2009), 38 (9), 2622-2633CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)This tutorial review introduces the fundamentals of intermol. interactions in terms of the underlying physics and goes on to illustrate the most popular methods for the computer simulation of intermol. interactions, from atom-atom potentials to ab initio methods, including intermediate, hybrid methods, with an appreciation of their relative merits and costs. Typical results are critically presented, culminating in the most difficult exercise of all, the computer prediction of crystal structures. Perspectives on our present and future ability to understand and exploit intermol. interactions are given.
- 24McKeown, N. B. Nanoporous Molecular Crystals J. Mater. Chem. 2010, 20, 10588– 10597 DOI: 10.1039/c0jm01867hGoogle Scholar24https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXhsVOkt77N&md5=1e30750a10ec78dfd8ff03646d755e2fNanoporous molecular crystalsMcKeown, Neil B.Journal of Materials Chemistry (2010), 20 (47), 10588-10597CODEN: JMACEP; ISSN:0959-9428. (Royal Society of Chemistry)A review. Nanoporous Mol. Crystals (NMCs) are nanoporous materials composed of discrete mols. between which there are only non-covalent interactions-i.e. they do not possess an extended framework composed of covalent or coordination bonds. They are formed from removing guest mols. from inclusion compds. (ICs) a process that for most ICs usually results in the collapse of the open structure of the crystals but in the case of NMCs the packing of the host mols. is retained and nanoporosity obtained. In recent years a no. of NMCs have been confirmed by the technique of gas adsorption and these materials are surveyed in this feature article. In addn., the reasons for stability of these crystals are discussed. It is the author's belief that many more ICs, the structures of which are readily obtainable from the Cambridge Structural Database (CSD), may act as precursors to NMCs.
- 25Chen, T.-H.; Popov, I.; Kaveevivitchai, W.; Chuang, Y. C.; Chen, Y. S.; Daugulis, O.; Jacobson, A. J.; Miljanić, O. Š. Thermally Robust and Porous Noncovalent Organic Framework with High Affinity for Fluorocarbons and CFCs Nat. Commun. 2014, 5, 5131 DOI: 10.1038/ncomms6131Google Scholar25https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXitVWgsLnN&md5=72f596c78c5bb02e3d7c61e71bc2a366Thermally robust and porous noncovalent organic framework with high affinity for fluorocarbons and CFCsChen, Teng-Hao; Popov, Ilya; Kaveevivitchai, Watchareeya; Chuang, Yu-Chun; Chen, Yu-Sheng; Daugulis, Olafs; Jacobson, Allan J.; Miljanic, Ognjen S.Nature Communications (2014), 5 (), 5131CODEN: NCAOBW; ISSN:2041-1723. (Nature Publishing Group)Metal-org. and covalent org. frameworks are porous materials characterized by outstanding thermal stability, high porosities and modular synthesis. Their repeating structures offer a great degree of control over pore sizes, dimensions and surface properties. Similarly precise engineering at the nanoscale is difficult to achieve with discrete mols., since they rarely crystallize as porous structures. Here we report a small org. mol. that organizes into a noncovalent org. framework with large empty pores. This structure is held together by a combination of [N-H···N] hydrogen bonds between the terminal pyrazole rings and [π···π] stacking between the electron-rich pyrazoles and electron-poor tetrafluorobenzenes. Such a synergistic arrangement makes this structure stable to at least 250 °C and porous, with an accessible surface area of 1,159 m2 g-1. Crystals of this framework adsorb hydrocarbons, CFCs and fluorocarbons-the latter two being ozone-depleting substances and potent greenhouse species-with wt. capacities of up to 75%.
- 26Chen, B.; Eddaoudi, M.; Hyde, S. T.; O’Keeffe, M.; Yaghi, O. M. Interwoven Metal-Organic Framework on a Periodic Minimal Surface with Extra-Large Pores Science 2001, 291, 1021– 1023 DOI: 10.1126/science.1056598Google Scholar26https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3MXhtFGlu7s%253D&md5=a9c2b80ba2f1b825ee2a55278ef5fe92Interwoven metal-organic framework on a periodic minimal surface with extra-large poresChen, Banglin; Eddaoudi, M.; Hyde, S. T.; O'Keeffe, M.; Yaghi, O. M.Science (Washington, DC, United States) (2001), 291 (5506), 1021-1023CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)A strategy for the design of highly porous and structurally stable networks makes use of metal-org. building blocks that can be assembled on a triply periodic P-minimal geometric surface to produce structures that are interpenetrating-more accurately considered as interwoven. The authors used 4,4',4''-benzene-1,3,5-triyltribenzoic acid (H3BTB), Cu(NO3)2e, and DMF to prep. Cu3(BTB)2(H2O)3·(DMF)9(H2O)2 (MOF-14), whose structure reveals a pair of interwoven metal-org. frameworks that are mutually reinforced. The structure contains remarkably large pores, 16.4 Å in diam., in which voluminous amts. of gases and org. solvents can be reversibly sorbed.
- 27Zentner, C. A.; Lai, H. W. H.; Greenfield, J. T.; Wiscons, R. A.; Zeller, M.; Campana, C. F.; Talu, O.; FitzGerald, S. A.; Rowsell, J. L. C. High Surface Area and Z′ in a Thermally Stable 8-Fold Polycatenated Hydrogen-Bonded Framework Chem. Commun. 2015, 51, 11642– 11645 DOI: 10.1039/C5CC04219DGoogle Scholar27https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhtVCls73O&md5=5c3592ee4b106102ec9b95fe2a1342c0High surface area and Z' in a thermally stable 8-fold polycatenated hydrogen-bonded frameworkZentner, Cassandra A.; Lai, Holden W. H.; Greenfield, Joshua T.; Wiscons, Ren A.; Zeller, Matthias; Campana, Charles F.; Talu, Orhan; FitzGerald, Stephen A.; Rowsell, Jesse L. C.Chemical Communications (Cambridge, United Kingdom) (2015), 51 (58), 11642-11645CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)1,3,5-Tris(4-carboxyphenyl)benzene assembles into an intricate 8-fold polycatenated assembly of (6,3) hexagonal nets formed through hydrogen bonds and π-stacking. One polymorph features 56 independent mols. in the asym. unit, the largest Z' reported to date. The framework is permanently porous, with a BET surface area of 1095 m2 g-1 and readily adsorbs N2, H2 and CO2.
- 28Ciesielski, A.; Samorì, P. Supramolecular Assembly/Reassembly Processes: Molecular Motors and Dynamers Operating at Surfaces Nanoscale 2011, 3, 1397– 1410 DOI: 10.1039/c0nr00914hGoogle Scholar28https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXltF2kurg%253D&md5=e5add9c83bca4a44aef97271b28d7f04Supramolecular assembly/reassembly processes: Molecular motors and dynamers operating at surfacesCiesielski, Artur; Samori, PaoloNanoscale (2011), 3 (4), 1397-1410CODEN: NANOHL; ISSN:2040-3372. (Royal Society of Chemistry)A review. Among the many significant advances within the field of supramol. chem. over the past decades, the development of the so-called "dynamers" features a direct relevance to materials science. Defined as "combinatorial dynamic polymers", dynamers are constitutional dynamic systems and materials resulting from the application of the principles of supramol. chem. to polymer science. Like supramol. materials in general, dynamers are reversible dynamic multifunctional architectures, capable of modifying their constitution by exchanging, recombining, incorporating components. They may exhibit a variety of novel properties and behave as adaptive materials. In this review we focus on the design of responsive switchable monolayers, i.e. monolayers capable to undergo significant changes in their phys. or chem. properties as a result of external stimuli. Scanning tunneling microscopy studies provide direct evidence with a sub-nanometer resoln., on the formation and dynamic response of these self-assembled systems featuring controlled geometries and properties.
- 29Colson, J. W.; Woll, A. R.; Mukherjee, A.; Levendorf, M. P.; Spitler, E. L.; Shields, V. B.; Spencer, M. G.; Park, J.; Dichtel, W. R. Oriented 2D Covalent Organic Framework Thin Films on Single-Layer Graphene Science 2011, 332, 228– 231 DOI: 10.1126/science.1202747Google Scholar29https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXksV2qt7c%253D&md5=0439c797dcb8dbe4bd0af070c29618fbOriented 2D Covalent Organic Framework Thin Films on Single-Layer GrapheneColson, John W.; Woll, Arthur R.; Mukherjee, Arnab; Levendorf, Mark P.; Spitler, Eric L.; Shields, Virgil B.; Spencer, Michael G.; Park, Jiwoong; Dichtel, William R.Science (Washington, DC, United States) (2011), 332 (6026), 228-231CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)Covalent org. frameworks (COFs), in which mol. building blocks form robust microporous networks, are usually synthesized as insol. and unprocessable powders. The authors have grown two-dimensional (2D) COF films on single-layer graphene (SLG) under operationally simple solvothermal conditions. The layered films stack normal to the SLG surface and show improved crystallinity compared with COF powders. The authors used SLG surfaces supported on copper, silicon carbide, and transparent fused silica (SiO2) substrates, enabling optical spectroscopy of COFs in transmission mode. Three chem. distinct COF films grown on SLG exhibit similar vertical alignment and long-range order, and two of these are of interest for org. electronic devices for which thin-film formation is a prerequisite for characterizing their optoelectronic properties.
- 30Ruben, M.; Payer, D.; Landa, A.; Comisso, A.; Gattinoni, C.; Lin, N.; Collin, J.-P.; Sauvage, J.-P.; De Vita, A.; Kern, K. 2D Supramolecular Assemblies of Benzene-1,3,5-triyl-tribenzoic Acid: Temperature-Induced Phase Transformations and Hierarchical Organization with Macrocyclic Molecules J. Am. Chem. Soc. 2006, 128, 15644– 15651 DOI: 10.1021/ja063601kGoogle Scholar30https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD28Xht1WhsLrO&md5=0e795486268a549e58a504886944e6142D Supramolecular Assemblies of Benzene-1,3,5-triyl-tribenzoic Acid: Temperature-Induced Phase Transformations and Hierarchical Organization with Macrocyclic MoleculesRuben, Mario; Payer, Dietmar; Landa, Aitor; Comisso, Alessio; Gattinoni, Chiara; Lin, Nian; Collin, Jean-Paul; Sauvage, Jean-Pierre; De Vita, Alessandro; Kern, KlausJournal of the American Chemical Society (2006), 128 (49), 15644-15651CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Two-dimensional supramol. honeycomb networks with cavities of an internal diam. of 2.95 nm were formed by the self-assembly of 4,4',4''-benzene-1,3,5-triyl-tribenzoic acid (BTA) on a Ag(111) surface at room temp. Annealing to higher temps. resulted in 2 sequential phase transformations into closer-packed supramol. arrangements. The phase transformations are assocd. with stepwise deprotonation of the carboxylic acid groups. The voids of the honeycomb network of BTA have a suitable size for the construction of hierarchical structures with guest mols. Single mols. of the macrocyclic compd. mt-33 were successfully confined inside 2-dimensional nanocavities of the honeycomb networks and released when the phase was transformed to the close-packed structure.
- 31Silly, F. Two-Dimensional 1,3,5-Tris-(4-carboxyphenyl)-benzene Self-Assembly at the 1-Phenyloctane/Graphite Interface Revisited J. Phys. Chem. C 2012, 116, 10029– 10032 DOI: 10.1021/jp300678mGoogle ScholarThere is no corresponding record for this reference.
- 32Lee, S. L.; Fang, Y.; Velpula, G.; Cometto, F. P.; Lingenfelder, M.; Müllen, K.; Mali, K. S.; De Feyter, S. Reversible Local and Global Switching in Multicomponent Supramolecular Networks: Controlled Guest Release and Capture at the Solution/Solid Interface ACS Nano 2015, 9, 11608– 11617 DOI: 10.1021/acsnano.5b06081Google Scholar32https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXitVantbfJ&md5=d9699c077effcae556611470be3a7ea3Reversible Local and Global Switching in Multicomponent Supramolecular Networks: Controlled Guest Release and Capture at the Solution/Solid InterfaceLee, Shern-Long; Fang, Yuan; Velpula, Gangamallaiah; Cometto, Fernando P.; Lingenfelder, Magali; Mullen, Klaus; Mali, Kunal S.; De Feyter, StevenACS Nano (2015), 9 (12), 11608-11617CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)The authors demonstrate an elegant approach where the guest binding ability of a supramol. surface can be controlled by inducing structural transitions in it. A physisorbed self-assembled network of a simple hydrogen bonding building block is used as a switching platform. The authors illustrate that the reversible transition between porous and nonporous networks can be accomplished using an elec. field or applying a thermal stimulus. These transitions are used to achieve controlled guest release or capture at the soln.-solid interface. The elec. field and the temp.-mediated methods of guest release are operative at different length scales. While the former triggers the transition and thus guest release at the nanometer scale, the latter is effective over a much larger scale. The flexibility assocd. with physisorbed self-assembled networks renders this approach an attractive alternative to conventional switchable systems.
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- 34Sing, K. S. W.; Everett, D. H.; Haul, R. A. W.; Moscou, L.; Pierotti, R. A.; Rouquérol, J.; Siemieniewska, T. Reporting Physisorption Data for Gas/Solid Systems with Special Reference to the Determination of Surface Area and Porosity Pure Appl. Chem. 1985, 57, 603– 619 DOI: 10.1351/pac198557040603Google Scholar34https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaL2MXhvFWrtb4%253D&md5=4fbbea83b3a13b5f22e6d26e5d0ab20cReporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity (Recommendations 1984)Sing, K. S. W.; Everett, D. H.; Haul, R. A. W.; Moscou, L.; Pierotti, R. A.; Rouquerol, J.; Siemieniewska, T.Pure and Applied Chemistry (1985), 57 (4), 603-19CODEN: PACHAS; ISSN:0033-4545.Problems and ambiguities in reporting data are discussed. Procedures and terminol. for reporting data re recommended.
- 35Barrett, E. P.; Joyner, L. G.; Halenda, P. P. The Determination of Pore Volume and Area Distributions in Porous Substances. I. Computations from Nitrogen Isotherms J. Am. Chem. Soc. 1951, 73, 373– 380 DOI: 10.1021/ja01145a126Google Scholar35https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaG3MXjsVygsg%253D%253D&md5=5153bbb1018c4eb7aa98fc7e3cd0ea73The determination of pore volume and area distributions in porous substances. I. Computations from nitrogen isothermsBarrett, Elliott P.; Joyner, Leslie G.; Halenda, Paul P.Journal of the American Chemical Society (1951), 73 (), 373-80CODEN: JACSAT; ISSN:0002-7863.An analysis of the N2 desorption isotherms based on the Wheeler theory of combined phys. adsorption and capillary condensation was developed. A method for computing the pore vol. and area distribution directly from the desorption isotherm of porous substances is presented. The method has been successfully applied to adsorbents covering a wide range of pore vol. maxima.
- 36Sakata, O.; Furukawa, Y.; Goto, S.; Mochizuki, T.; Uruga, T.; Takeshita, K.; Ohashi, H.; Ohata, T.; Matsushita, T.; Takahashi, S.; Tajiri, H.; Ishikawa, T.; Nakamura, M.; Ito, M.; Sumitani, K.; Takahashi, T.; Shimura, T.; Saito, A.; Takahasi, M. Beamline for Surface and Interface Structures at SPring-8 Surf. Rev. Lett. 2003, 10, 543– 547 DOI: 10.1021/ja01145a126Google Scholar36https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3sXltFCgtLc%253D&md5=9f1116a3d3ce0bce29d997fc7ef1aca9Beamline for Surface and Interface Structures at SPring-8Sakata, O.; Furukawa, Y.; Goto, S.; Mochizuki, T.; Uruga, T.; Takeshita, K.; Ohashi, H.; Ohata, T.; Matsushita, T.; Takahashi, S.; Tajiri, H.; Ishikawa, T.; Nakamura, M.; Ito, M.; Sumitani, K.; Takahashi, T.; Shimura, T.; Saito, A.; Takahasi, M.Surface Review and Letters (2003), 10 (2 & 3), 543-547CODEN: SRLEFH; ISSN:0218-625X. (World Scientific Publishing Co. Pte. Ltd.)The main components of a new beamline for surface and interface crystal structure detn. at SPring-8 are briefly described. Stages for the beamline monochromator are modified for making an incident X-ray intensity more stable for surface X-ray expts. Abs. photon flux densities were measured with an incident photon energy. A new ultrahigh vacuum system is introduced with preliminary X-ray measurements from an ordered oxygen on Pt (111) surface.
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Abstract
Figure 1
Figure 1. Morphological and structural varieties of BTB depending on fabrication technique. (a) Triangular-shaped BTB molecules form hexagonal rings via hydrogen-bonded carboxylic acid dimers. Conventional bulk synthesis results in rodlike crystals with multiply interpenetrated rings. Interfacial synthesis controls the molecular orientation and prevents interpenetration, leading to perfectly oriented nanosheets with long-range molecular columns and size- and position-regulated nanopores. (b) Simple interfacial synthetic process involves spreading BTB solution on pure water subphase, resulting in the creation of crystalline porous nanosheets (LINAS-1) easily transferable to numerous substrates. (c) Contrasting micrometer-scale bulk BTB crystal. Rodlike objects similarly shaped to the bulk crystals are formed by conventional solution-based film fabrication techniques such as dip casting (d) and drop casting (e) on Si substrates. (f) Vacuum deposition on an Si substrate results in the formation of an amorphous film (Figure S9). The morphological images are obtained by AFM, (b, d–f) and optical microscopy (c), respectively.
Figure 2
Figure 2. Structural characterization of LINAS-1 by in situ GIXRD measurements at the air/liquid interface. (a) Surface-pressure–mean-molecular-area (Π-A) isotherm for LINAS-1 with surface morphological images (inset) obtained by Brewster angle microscopy (BAM) at selected Π. (b, c) Observed in situ in-plane, (b) and out-of-plane, and (c) synchrotron GIXRD (λ = 1.549 Å, Q = 4π sinθ/λ, incident angle, α = 0.12°) profiles at surface pressures, Π = 0, 1, 5, and 20 mN/m together with schematic representation of the scattering geometry. (d) Basal plane projection and (e) stacking motif of the LINAS-1 crystalline structure derived from the GIXRD measurements. (f) Measured in situ (black line, Π = 5 mN/m) and calculated (red line: AA slip-stacking with slip-angle, δ = 5°; blue line: AB stacking model with neighboring honeycomb networks shifted horizontally by half the unit-cell size) in-plane synchrotron XRD profiles. Ticks mark the Bragg reflection positions. The tick marks show the reflection positions.
Figure 3
Figure 3. Integrity and morphological characterization of LINAS-1 after transfer onto solid substrates. (a) Schematic illustration of the horizontal dipping deposition method for nanosheet transfer from the liquid surface to the solid substrate surface. (b) In-plane and (c) out-of-plane synchrotron GIXRD profiles for LINAS-1 transferred on Si substrate (black line) together with those on water surface (red line). The tick marks show the reflection positions. (d) AFM image of LINAS-1 on Si and corresponding height profile along the track marked in red. (e) Height distribution of LINAS-1 evaluated from the AFM images. (f) Ultraviolet–visible (UV–vis) absorption spectra of LINAS-1 on a quartz substrate after successive cycles of sheet deposition. Inset: maximum absorbance versus number of sheet-deposition cycles. (g) Optical microscope image of a holey substrate with micromesh before (left) and after (right) LINAS-1 transfer.
Figure 4
Figure 4. Gas-sorption properties of LINAS-1. (a) N2-sorption isotherms (77 K) for LINAS-1 (red) and bulk BTB crystals (black). Isotherms show both adsorption (dots) and desorption (open circles) data. Inset: expanded view of the low-pressure region. (b) Pore-size distribution curve for LINAS-1 obtained from Barrett–Joyner–Halenda (BJH) analysis of the N2-sorption isotherm. (c) Water vapor sorption isotherms (298 K). (d) O2-sorption isotherms (77 K).
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- 1Bonaccorso, F.; Colombo, L.; Yu, G.; Stoller, M.; Tozzini, V.; Ferrari, A. C.; Ruoff, R. S.; Pellegrini, V. Graphene, Related Two-Dimensional Crystals, and Hybrid Systems for Energy Conversion and Storage Science 2015, 347, 1246501 DOI: 10.1126/science.12465011https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A280%3ADC%252BC2Mvjt1ektQ%253D%253D&md5=f2b976cbe793eb220db317fa6a6717142D materials. Graphene, related two-dimensional crystals, and hybrid systems for energy conversion and storageBonaccorso Francesco; Colombo Luigi; Yu Guihua; Stoller Meryl; Tozzini Valentina; Ferrari Andrea C; Ruoff Rodney S; Pellegrini VittorioScience (New York, N.Y.) (2015), 347 (6217), 1246501 ISSN:.Graphene and related two-dimensional crystals and hybrid systems showcase several key properties that can address emerging energy needs, in particular for the ever growing market of portable and wearable energy conversion and storage devices. Graphene's flexibility, large surface area, and chemical stability, combined with its excellent electrical and thermal conductivity, make it promising as a catalyst in fuel and dye-sensitized solar cells. Chemically functionalized graphene can also improve storage and diffusion of ionic species and electric charge in batteries and supercapacitors. Two-dimensional crystals provide optoelectronic and photocatalytic properties complementing those of graphene, enabling the realization of ultrathin-film photovoltaic devices or systems for hydrogen production. Here, we review the use of graphene and related materials for energy conversion and storage, outlining the roadmap for future applications.
- 2Seiki, N.; Shoji, Y.; Kajitani, T.; Ishiwari, F.; Kosaka, A.; Hikima, T.; Takata, M.; Someya, T.; Fukushima, T. Rational Synthesis of Organic Thin Films with Exceptional Long-Range Structural Integrity Science 2015, 348, 1122– 1126 DOI: 10.1126/science.aab13912https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXpt1Kmu7c%253D&md5=0bc3e73b8e26e20e4008ff3c64d03c55Rational synthesis of organic thin films with exceptional long-range structural integritySeiki, Noriya; Shoji, Yoshiaki; Kajitani, Takashi; Ishiwari, Fumitaka; Kosaka, Atsuko; Hikima, Takaaki; Takata, Masaki; Someya, Takao; Fukushima, TakanoriScience (Washington, DC, United States) (2015), 348 (6239), 1122-1126CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)Highly oriented, domain-boundary-free org. thin films could find use in various high-performance org. materials and devices. However, even with state-of-the-art supramol. chem., it is difficult to construct org. thin films with structural integrity in a size regime beyond the micrometer length scale. We show that a space-filling design, relying on the two-dimensional (2D) nested hexagonal packing of a particular type of triptycene, enables the formation of large-area mol. films with long-range 2D structural integrity up to the centimeter length scale by vacuum evapn., spin-coating, and cooling from the isotropic liq. of the triptycene. X-ray diffraction anal. and microscopic observations reveal that triptycene mols. form a completely oriented 2D (hexagonal triptycene array) + 1D (layer stacking) structure, which is key for the long-range propagation of structural order.
- 3Corma, A.; Fornes, V.; Pergher, S. B.; Maesen, T. L. M.; Buglass, J. G. Delaminated Zeolite Precursors as Selective Acidic Catalysts Nature 1998, 396, 353– 356 DOI: 10.1038/245923https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK1cXnvVaku7s%253D&md5=005b038fc4d2310811901fae85973dc4Delaminated zeolite precursors as selective acidic catalystsCorma, A.; Fornes, V.; Pergher, S. B.; Maesen, Th. L. M.; Buglass, J. G.Nature (London) (1998), 396 (6709), 353-356CODEN: NATUAS; ISSN:0028-0836. (Macmillan Magazines)Providing access for larger mols. to the catalytic sites would expand the range of reactions that zeolites can catalyze. This paper describes an approach in which a layered zeolite precursor is delaminated. The result is an aluminosilicate whose zeolite-type catalytic sites are contained within thin, readily accessible sheets. Performance tests show that the delamination process improves the accessibility of the catalytic sites without affecting their activity. The authors expect that their approach could be adapted to other layered zeolite precursors.
- 4Zhang, J.; Yu, J.; Zhang, Y.; Li, Q.; Gong, J. R. Visible Light Photocatalytic H2-Production Activity of CuS/ZnS Porous Nanosheets Based on Photoinduced Interfacial Charge Transfer Nano Lett. 2011, 11, 4774– 4779 DOI: 10.1021/nl202587b4https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXht1Ort77L&md5=20527f32ae36d86a52b55539b63780fcVisible Light Photocatalytic H2-Production Activity of CuS-ZnS Porous Nanosheets Based on Photoinduced Interfacial Charge TransferZhang, Jun; Yu, Jiaguo; Zhang, Yimin; Li, Qin; Gong, Jian RuNano Letters (2011), 11 (11), 4774-4779CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)Visible light photocatalytic H2 prodn. through H2O splitting is of great importance for its potential application in converting solar energy into chem. energy. A novel visible-light-driven photocatalyst was designed based on photoinduced interfacial charge transfer (IFCT) through surface modification of ZnS porous nanosheets by CuS. CuS/ZnS porous nanosheet photocatalysts were prepd. by a simple hydrothermal and cation exchange reaction between preformed ZnS(en)0.5 nanosheets and Cu(NO3)2. Even without a Pt cocatalyst, the as-prepd. CuS/ZnS porous nanosheets reach a high H2-prodn. rate of 4147 μmol h-1 g-1 at CuS loading content of 2 mol % and an apparent quantum efficiency of 20% at 420 nm. This high visible light photocatalytic H2-prodn. activity is due to the IFCT from the valence band of ZnS to CuS, which causes the redn. of partial CuS to Cu2S and thus enhances H2-prodn. activity. This work not only shows a possibility for substituting low-cost CuS for noble metals in the photocatalytic H2 prodn. but also for the 1st time exhibits a facile method for enhancing H2-prodn. activity by photoinduced IFCT.
- 5Hatton, B.; Mishchenko, L.; Davis, S.; Sandhage, K. H.; Aizenberg, J. Assembly of Large-Area, Highly Ordered, Crack-Free Inverse Opal Films Proc. Natl. Acad. Sci. U. S. A. 2010, 107, 10354– 10359 DOI: 10.1073/pnas.10009541075https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXnvV2is78%253D&md5=e534e0e2d782084402dc44edce3d4488Assembly of large-area, highly ordered, crack-free inverse opal filmsHatton, Benjamin; Mishchenko, Lidiya; Davis, Stan; Sandhage, Kenneth H.; Aizenberg, JoannaProceedings of the National Academy of Sciences of the United States of America (2010), 107 (23), 10354-10359, S10354/1-S10354/4CODEN: PNASA6; ISSN:0027-8424. (National Academy of Sciences)Whereas considerable interest exists in self-assembly of well-ordered, porous "inverse opal" structures for optical, electronic, and (bio)chem. applications, uncontrolled defect formation has limited the scale-up and practicality of such approaches. Here we demonstrate a new method for assembling highly ordered, crack-free inverse opal films over a centimeter scale. Multilayered composite colloidal crystal films have been generated via evaporative deposition of polymeric colloidal spheres suspended within a hydrolyzed silicate sol-gel precursor soln. The coassembly of a sacrificial colloidal template with a matrix material avoids the need for liq. infiltration into the preassembled colloidal crystal and minimizes the assocd. cracking and inhomogeneities of the resulting inverse opal films. We discuss the underlying mechanisms that may account for the formation of large-area defect-free films, their unique preferential growth along the (110) direction and unusual fracture behavior. We demonstrate that this coassembly approach allows the fabrication of hierarchical structures not achievable by conventional methods, such as multilayered films and deposition onto patterned or curved surfaces. These robust SiO2 inverse opals can be transformed into various materials that retain the morphol. and order of the original films, as exemplified by the reactive conversion into Si or TiO2 replicas. We show that colloidal coassembly is available for a range of organometallic sol-gel and polymer matrix precursors, and represents a simple, low-cost, scalable method for generating high-quality, chem. tailorable inverse opal films for a variety of applications.
- 6Mas-Ballesté, R.; Gómez-Navarro, C.; Gómez-Herrero, J.; Zamora, F. 2D Materials: to Graphene and Beyond Nanoscale 2011, 3, 20– 30 DOI: 10.1039/C0NR00323A6https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXitVChtr0%253D&md5=b15b6e89bd3a6735ffd861d5be1078e62D materials: to graphene and beyondMas-Balleste, Ruben; Gomez-Navarro, Cristina; Gomez-Herrero, Julio; Zamora, FelixNanoscale (2011), 3 (1), 20-30CODEN: NANOHL; ISSN:2040-3372. (Royal Society of Chemistry)This review is an attempt to illustrate the different alternatives in the field of 2D materials. Graphene seems to be just the tip of the iceberg and we show how the discovery of alternative 2D materials is starting to show the rest of this iceberg. The review comprises the current state-of-the-art of the vast literature in concepts and methods already known for isolation and characterization of graphene, and rationalizes the quite disperse literature in other 2D materials such as metal oxides, hydroxides and chalcogenides, and metal-org. frameworks.
- 7Coleman, J. N.; Lotya, M.; O’Neill, A.; Bergin, S. D.; King, P. J.; Khan, U.; Young, K.; Gaucher, A.; De, S.; Smith, R. J.; Shvets, I. V.; Arora, S. K.; Stanton, G.; Kim, H. Y.; Lee, K.; Kim, G. T.; Duesberg, G. S.; Hallam, T.; Boland, J. J.; Wang, J. J. Two-Dimensional Nanosheets Produced by Liquid Exfoliation of Layered Materials Science 2011, 331, 568– 571 DOI: 10.1126/science.11949757https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXhtlWisLY%253D&md5=7bd4a9da1b4f81f2caa3d1159dd8a5c7Two-Dimensional Nanosheets Produced by Liquid Exfoliation of Layered MaterialsColeman, Jonathan N.; Lotya, Mustafa; O'Neill, Arlene; Bergin, Shane D.; King, Paul J.; Khan, Umar; Young, Karen; Gaucher, Alexandre; De, Sukanta; Smith, Ronan J.; Shvets, Igor V.; Arora, Sunil K.; Stanton, George; Kim, Hye-Young; Lee, Kangho; Kim, Gyu Tae; Duesberg, Georg S.; Hallam, Toby; Boland, John J.; Wang, Jing Jing; Donegan, John F.; Grunlan, Jaime C.; Moriarty, Gregory; Shmeliov, Aleksey; Nicholls, Rebecca J.; Perkins, James M.; Grieveson, Eleanor M.; Theuwissen, Koenraad; McComb, David W.; Nellist, Peter D.; Nicolosi, ValeriaScience (Washington, DC, United States) (2011), 331 (6017), 568-571CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)If they could be easily exfoliated, layered materials would become a diverse source of two-dimensional crystals whose properties would be useful in applications ranging from electronics to energy storage. Layered compds. such as MoS2, WS2, MoSe2, MoTe2, TaSe2, NbSe2, NiTe2, BN, and Bi2Te3 can be efficiently dispersed in common solvents and can be deposited as individual flakes or formed into films. Electron microscopy strongly suggests that the material is exfoliated into individual layers. By blending this material with suspensions of other nanomaterials or polymer solns., the authors can prep. hybrid dispersions or composites, which can be cast into films. WS2 and MoS2 effectively reinforce polymers, whereas WS2/carbon nanotube hybrid films have high cond., leading to promising thermoelec. properties.
- 8Kory, M. J.; Wörle, M.; Weber, T.; Payamyar, P.; van de Poll, S. W.; Dshemuchadse, J.; Trapp, N.; Schlüter, A. D. Gram-Scale Synthesis of Two-Dimensional Polymer Crystals and their Structure Analysis by X-Ray Diffraction Nat. Chem. 2014, 6, 779– 784 DOI: 10.1038/nchem.20078https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXht1ait73P&md5=b893c31a56512800669b727f4fe9e405Gram-scale synthesis of two-dimensional polymer crystals and their structure analysis by X-ray diffractionKory, Max J.; Worle, Michael; Weber, Thomas; Payamyar, Payam; van de Poll, Stan W.; Dshemuchadse, Julia; Trapp, Nils; Schluter, A. DieterNature Chemistry (2014), 6 (9), 779-784CODEN: NCAHBB; ISSN:1755-4330. (Nature Publishing Group)The rise of graphene, a natural two-dimensional polymer (2DP) with topol. planar repeat units, has challenged synthetic chem., and has highlighted that accessing equiv. covalently bonded sheet-like macromols. has, until recently, not been achieved. Here we show that non-centrosym., enantiomorphic single crystals of a simple-to-make monomer can be photochem. converted into chiral 2DP crystals and cleanly reversed back to the monomer. X-ray diffraction established unequivocal structural proof for this synthetic 2DP, which has an all-carbon scaffold and can be synthesized on the gram scale. The monomer crystals are highly robust, can be easily grown to sizes greater than 1 mm and the resulting 2DP crystals exfoliated into nanometer-thin sheets. This unique combination of features suggests that these 2DPs could find use in membranes and nonlinear optics.
- 9Kissel, P.; Murray, D. J.; Wulftange, W. J.; Catalano, V. J.; King, B. T. A Nanoporous Two-Dimensional Polymer by Single-Crystal-to-Single-Crystal Photopolymerization Nat. Chem. 2014, 6, 774– 778 DOI: 10.1038/nchem.20089https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXht1ait7zF&md5=ed65f0ade8a7eb0c4c5ada2cff1aef90A nanoporous two-dimensional polymer by single-crystal-to-single-crystal photopolymerizationKissel, Patrick; Murray, Daniel J.; Wulftange, William J.; Catalano, Vincent J.; King, Benjamin T.Nature Chemistry (2014), 6 (9), 774-778CODEN: NCAHBB; ISSN:1755-4330. (Nature Publishing Group)In contrast to the wide no. and variety of available synthetic routes to conventional linear polymers, the synthesis of two-dimensional polymers and unambiguous proof of their structure remains a challenge. Two-dimensional polymers-single-layered polymers that form a tiling network in exactly two dimensions-have potential for use in nanoporous membranes and other applications. Here, we report the prepn. of a fluorinated hydrocarbon two-dimensional polymer that can be exfoliated into single sheets, and its characterization by high-resoln. single-crystal X-ray diffraction anal. The procedure involves three steps: preorganization in a lamellar crystal of a rigid monomer bearing three photoreactive arms, photopolymn. of the cryst. monomers by [4 + 4] cycloaddn., and isolation of individual two-dimensional polymer sheets. This polymer is a molecularly thin (∼1 nm) material that combines precisely defined monodisperse pores of ∼9 Å with a high pore d. of 3.3 × 1013 pores cm-2. Atomic-resoln. single-crystal X-ray structures of the monomer, an intermediate dimer and the final cryst. two-dimensional polymer were obtained and prove the single-crystal-to-single-crystal nature and mol. precision of the two-dimensional photopolymn.
- 10Lai, Z.; Bonilla, G.; Diaz, L.; Nery, J. G.; Sujaoti, K.; Amat, M. A.; Kokkoli, E.; Terasaki, O.; Thompson, R. W.; Tsapatsis, M.; Vlachos, D. G. Microstructural Optimization of a Zeolite Membrane for Organic Vapor Separation Science 2003, 300, 456– 460 DOI: 10.1126/science.108216910https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3sXivFymsrk%253D&md5=a9291818e17048b0246c697d88b18647Microstructural optimization of a zeolite membrane for organic vapor separationLai, Zhiping; Bonilla, Griselda; Diaz, Isabel; Nery, Jose Geraldo; Sujaoti, Khristina; Amat, Miguel A.; Kokkoli, Efrosini; Terasaki, Osamu; Thompson, Robert W.; Tsapatsis, Michael; Vlachos, Dionisios G.Science (Washington, DC, United States) (2003), 300 (5618), 456-460CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)A seeded growth method for the fabrication of high-permeance, high-sepn.-factor zeolite (siliceous ZSM-5, [Si96O192]-MFI) membranes is reported. The method consists of growing the crystals of an oriented seed layer to a well-intergrown film by avoiding events that lead to a loss of preferred orientation, such as twin overgrowths and random nucleation. Org. polycations were used as zeolite crystal shape modifiers to enhance relative growth rates along the desirable out-of-plane direction. The polycryst. films are thin (∼1 μm) with single grains extending along the film thickness and with large in-plane grain size (∼1 μm). The preferred orientation is such that straight channels with an open diam. of ∼5.5 Å run down the membrane thickness. Comparison with previously reported membranes shows that these microstructurally optimized films have superior performance for the sepn. of org. mixts. with components that have small differences in size and shape, such as xylene isomers.
- 11Varoon, K.; Zhang, X.; Elyassi, B.; Brewer, D. D.; Gettel, M.; Kumar, S.; Lee, J. A.; Maheshwari, S.; Mittal, A.; Sung, C. Y.; Cococcioni, M.; Francis, L. F.; McCormick, A. V.; Mkhoyan, K. A.; Tsapatsis, M. Dispersible Exfoliated Zeolite Nanosheets and their Application as a Selective Membrane Science 2011, 334, 72– 75 DOI: 10.1126/science.120889111https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXht1Gms7%252FN&md5=93f4e5d1f4d0ce666a7fc837cd29f82aDispersible Exfoliated Zeolite Nanosheets and Their Application as a Selective MembraneVaroon, Kumar; Zhang, Xueyi; Elyassi, Bahman; Brewer, Damien D.; Gettel, Melissa; Kumar, Sandeep; Lee, J. Alex; Maheshwari, Sudeep; Mittal, Anudha; Sung, Chun-Yi; Cococcioni, Matteo; Francis, Lorraine F.; McCormick, Alon V.; Mkhoyan, K. Andre; Tsapatsis, MichaelScience (Washington, DC, United States) (2011), 334 (6052), 72-75CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)Thin zeolite films are attractive for a wide range of applications, including mol. sieve membranes, catalytic membrane reactors, permeation barriers, and low-dielec.-const. materials. Synthesis of thin zeolite films using high-aspect-ratio zeolite nanosheets is desirable because of the packing and processing advantages of the nanosheets over isotropic zeolite nanoparticles. Attempts to obtain a dispersed suspension of zeolite nanosheets via exfoliation of their lamellar precursors have been hampered because of their structure deterioration and morphol. damage (fragmentation, curling, and aggregation). We demonstrated the synthesis and structure detn. of highly cryst. nanosheets of zeolite frameworks MWW and MFI. The purity and morphol. integrity of these nanosheets allow them to pack well on porous supports, facilitating the fabrication of mol. sieve membranes.
- 12Peng, Y.; Li, Y.; Ban, Y.; Jin, H.; Jiao, W.; Liu, X.; Yang, W. Metal-Organic Framework Nanosheets as Building Blocks for Molecular Sieving Membranes Science 2014, 346, 1356– 1359 DOI: 10.1126/science.125422712https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXitVCgsrjJ&md5=507ed6b5f2ccc54ed1a6aa3cd8f1a4ddMetal-organic framework nanosheets as building blocks for molecular sieving membranesPeng, Yuan; Li, Yanshuo; Ban, Yujie; Jin, Hua; Jiao, Wenmei; Liu, Xinlei; Yang, WeishenScience (Washington, DC, United States) (2014), 346 (6215), 1356-1359CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)Layered metal-org. frameworks would be a diverse source of cryst. sheets with nanometer thickness for mol. sieving if they could be exfoliated, but there is a challenge in retaining the morphol. and structural integrity. The authors report the prepn. of 1-nm-thick sheets with large lateral area and high crystallinity from layered MOFs. They are used as building blocks for ultrathin mol. sieve membranes, which achieve hydrogen gas (H2) permeance of up to several thousand gas permeation units (GPUs) with H2/CO2 selectivity greater than 200. The authors found an unusual proportional relationship between H2 permeance and H2 selectivity for the membranes, and achieved a simultaneous increase in both permeance and selectivity by suppressing lamellar stacking of the nanosheets.
- 13Chandra, S.; Kandambeth, S.; Biswal, B. P.; Lukose, B.; Kunjir, S. M.; Chaudhary, M.; Babarao, R.; Heine, T.; Banerjee, R. Chemically Stable Multilayered Covalent Organic Nanosheets from Covalent Organic Frameworks via Mechanical Delamination J. Am. Chem. Soc. 2013, 135, 17853– 17861 DOI: 10.1021/ja408121p13https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXhs1yls7nE&md5=bcf489e02681985891c8273864cbacc3Chemically Stable Multilayered Covalent Organic Nanosheets from Covalent Organic Frameworks via Mechanical DelaminationChandra, Suman; Kandambeth, Sharath; Biswal, Bishnu P.; Lukose, Binit; Kunjir, Shrikant M.; Chaudhary, Minakshi; Babarao, Ravichandar; Heine, Thomas; Banerjee, RahulJournal of the American Chemical Society (2013), 135 (47), 17853-17861CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)A series of five thermally and chem. stable functionalized covalent org. frameworks (COFs), namely, TpPa-NO2, TpPa-F4, TpBD-(NO2)2, TpBD-Me2, and TpBD-(OMe)2 were synthesized by employing the solvothermal aldehyde-amine Schiff base condensation reaction. In order to complete the series, previously reported TpPa-1, TpPa-2, and TpBD have also been synthesized, and altogether, eight COFs were fully characterized through powder X-ray diffraction (PXRD), Fourier transform IR (FT-IR) spectroscopy, 13C solid-state NMR spectroscopy, and thermogravimetric anal. These COFs are cryst., permanently porous, and stable in boiling water, acid (9 N HCl), and base (3 N NaOH). The synthesized COFs (all eight) were successfully delaminated using a simple, safe, and environmentally friendly mech. grinding route to transform into covalent org. nanosheets (CONs) and were well characterized via transmission electron microscopy and at. force microscopy. Further PXRD and FT-IR analyses confirm that these CONs retain their structural integrity throughout the delamination process and also remain stable in aq., acidic, and basic media like the parent COFs. These exfoliated CONs have graphene-like layered morphol. (delaminated layers), unlike the COFs from which they were synthesized.
- 14Makiura, R.; Motoyama, S.; Umemura, Y.; Yamanaka, H.; Sakata, O.; Kitagawa, H. Surface Nano-Architecture of a Metal-Organic Framework Nat. Mater. 2010, 9, 565 DOI: 10.1038/nmat276914https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXnvVOkt78%253D&md5=b5cd2860dd415d63aead956c0bc973f0Surface nano-architecture of a metal-organic frameworkMakiura, Rie; Motoyama, Soichiro; Umemura, Yasushi; Yamanaka, Hiroaki; Sakata, Osami; Kitagawa, HiroshiNature Materials (2010), 9 (7), 565-571CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)The rational assembly of ultrathin films of metal-org. frameworks (MOFs)-highly ordered microporous materials-with well-controlled growth direction and film thickness is a crit. and as yet unrealized issue for enabling the use of MOFs in nanotechnol. devices, such as sensors, catalysts and electrodes for fuel cells. Here we report the facile bottom-up fabrication at ambient temp. of such a perfect preferentially oriented MOF nanofilm on a solid surface (NAFS-1), consisting of metalloporphyrin building units. The construction of NAFS-1 was achieved by the unconventional integration in a modular fashion of a layer-by-layer growth technique coupled with the Langmuir-Blodgett method. NAFS-1 is endowed with highly cryst. order both in the out-of-plane and in-plane orientations to the substrate, as demonstrated by synchrotron X-ray surface crystallog. The proposed structural model incorporates metal-coordinated mols. projected from the two-dimensional sheets that allow each further layer to dock in a highly ordered interdigitated manner in the growth of NAFS-1. We expect that the versatility of the soln.-based growth strategy presented here will allow the fabrication of various well-ordered MOF nanofilms, opening the way for their use in a range of important applications.
- 15Makiura, R.; Konovalov, O. Interfacial Growth of Large-Area Single-Layer Metal-Organic Framework Nanosheets Sci. Rep. 2013, 3, 2506 DOI: 10.1038/srep0250615https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A280%3ADC%252BC3sbitlGrsA%253D%253D&md5=d15ccc3aa97416a62235795edbe443b2Interfacial growth of large-area single-layer metal-organic framework nanosheetsMakiura Rie; Konovalov OlegScientific reports (2013), 3 (), 2506 ISSN:.The air/liquid interface is an excellent platform to assemble two-dimensional (2D) sheets of materials by enhancing spontaneous organizational features of the building components and encouraging large length scale in-plane growth. We have grown 2D molecularly-thin crystalline metal-organic-framework (MOF) nanosheets composed of porphyrin building units and metal-ion joints (NAFS-13) under operationally simple ambient conditions at the air/liquid interface. In-situ synchrotron X-ray diffraction studies of the formation process performed directly at the interface were employed to optimize the NAFS-13 growth protocol leading to the development of a post-injection method -post-injection of the metal connectors into the water subphase on whose surface the molecular building blocks are pre-oriented- which allowed us to achieve the formation of large-surface area morphologically-uniform preferentially-oriented single-layer nanosheets. The growth of such large-size high-quality sheets is of interest for the understanding of the fundamental physical/chemical properties associated with ultra-thin sheet-shaped materials and the realization of their use in applications.
- 16Makiura, R.; Usui, R.; Sakai, Y.; Nomoto, A.; Ogawa, A.; Sakata, O.; Fujiwara, A. Towards Rational Modulation of In-Plane Molecular Arrangements in Metal-Organic Framework Nanosheets ChemPlusChem 2014, 79, 1352– 1360 DOI: 10.1002/cplu.20140215016https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhsFWjsrrO&md5=72450cc504781eb6694a90124fa35fdfTowards Rational Modulation of In-Plane Molecular Arrangements in Metal-Organic Framework NanosheetsMakiura, Rie; Usui, Ryo; Sakai, Yuta; Nomoto, Akihiro; Ogawa, Akiya; Sakata, Osami; Fujiwara, AkihikoChemPlusChem (2014), 79 (9), 1352-1360CODEN: CHEMM5; ISSN:2192-6506. (Wiley-VCH Verlag GmbH & Co. KGaA)A strategy to modulate the in-plane structural arrangement in preferentially oriented cryst. metal-org. framework (MOF) nanosheets assembled by a two-dimensional interfacial reaction between porphyrin units and metal ion linkers is reported. Starting with a tetratopic porphyrin MOF nanofilm, NAFS-2, the framework size and shape are modified by employing specially designed building units, a trans-ditopic and an expanded tetratopic porphyrin, and Cu2+ linkers. Reducing the no. of binding parts affords a MOF nanosheet, NAFS-31, with a distorted in-plane structure. Extension of the peripheral substituents, while maintaining the tetratopic porphyrin geometry, results in marked unit cell size enlargement in an undistorted square grid in the MOF nanofilm, NAFS-41. The exquisite geometric control that these structural modifications entail is valuable to allow switching of chem./phys. properties of the nanosheets and lead to realization of their use in nanotechnol. applications.
- 17Murray, D. J.; Patterson, D. D.; Payamyar, P.; Bhola, R.; Song, W.; Lackinger, M.; Schlüter, A. D.; King, B. T. Large Area Synthesis of a Nanoporous Two-Dimensional Polymer at the Air/Water Interface J. Am. Chem. Soc. 2015, 137, 3450– 3453 DOI: 10.1021/ja512018j17https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXjsVWktr8%253D&md5=d6f7026075684015e452415880470656Large Area Synthesis of a Nanoporous Two-Dimensional Polymer at the Air/Water InterfaceMurray, Daniel J.; Patterson, Dustin D.; Payamyar, Payam; Bhola, Radha; Song, Wentao; Lackinger, Markus; Schluter, A. Dieter; King, Benjamin T.Journal of the American Chemical Society (2015), 137 (10), 3450-3453CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)We present the synthesis of a two-dimensional polymer at the air/water interface and its nm-resoln. imaging. Trigonal star, amphiphilic monomers bearing three anthraceno groups on a central triptycene core are confined at the air/water interface. Compression followed by photopolymn. on the interface provides the two-dimensional polymer. Anal. by scanning tunneling microscopy suggests that the polymer is periodic with ultrahigh pore d.
- 18Rodenas, T.; Luz, I.; Prieto, G.; Seoane, B.; Miro, H.; Corma, A.; Kapteijn, F.; Xamena, F. X. L.; Gascon, J. Metal-Organic Framework Nanosheets in Polymer Composite Materials for Gas Separation Nat. Mater. 2015, 14, 48– 55 DOI: 10.1038/nmat411318https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhvVGiurnJ&md5=0ed3ba9aa55b42c8597c474cf56355d2Metal-organic framework nanosheets in polymer composite materials for gas separationRodenas, Tania; Luz, Ignacio; Prieto, Gonzalo; Seoane, Beatriz; Miro, Hozanna; Corma, Avelino; Kapteijn, Freek; Llabres i Xamena, Francesc X.; Gascon, JorgeNature Materials (2015), 14 (1), 48-55CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)Composites incorporating two-dimensional nanostructures within polymeric matrixes have potential as functional components for several technologies, including gas sepn. Prospectively, employing metal-org. frameworks (MOFs) as versatile nanofillers would notably broaden the scope of functionalities. However, synthesizing MOFs in the form of freestanding nanosheets has proved challenging. We present a bottom-up synthesis strategy for dispersible copper 1,4-benzenedicarboxylate MOF lamellae of micrometre lateral dimensions and nanometer thickness. Incorporating MOF nanosheets into polymer matrixes endows the resultant composites with outstanding CO2 sepn. performance from CO2/CH4 gas mixts., together with an unusual and highly desired increase in the sepn. selectivity with pressure. As revealed by tomog. focused ion beam SEM, the unique sepn. behavior stems from a superior occupation of the membrane cross-section by the MOF nanosheets as compared with isotropic crystals, which improves the efficiency of mol. discrimination and eliminates unselective permeation pathways. This approach opens the door to ultrathin MOF-polymer composites for various applications.
- 19Theobald, J. A.; Oxtoby, N. S.; Phillips, M. A.; Champness, N. R.; Beton, P. H. Controlling Molecular Deposition and Layer Structure with Supramolecular Surface Assemblies Nature 2003, 424, 1029– 1031 DOI: 10.1038/nature0191519https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3sXmslSjtrk%253D&md5=152beef542cadb27750155493bf6723aControlling molecular deposition and layer structure with supramolecular surface assembliesTheobald, James A.; Oxtoby, Neil S.; Phillips, Michael A.; Champness, Neil R.; Beton, Peter H.Nature (London, United Kingdom) (2003), 424 (6952), 1029-1031CODEN: NATUAS; ISSN:0028-0836. (Nature Publishing Group)Selective non-covalent interactions have been widely exploited in soln.-based chem. to direct the assembly of mols. into nanometer-sized functional structures such as capsules, switches and prototype machines. More recently, the concepts of supramol. organization have also been applied to two-dimensional assemblies on surfaces stabilized by hydrogen bonding, dipolar coupling or metal co-ordination. Structures realized to date include isolated rows, clusters and extended networks, as well as more complex multi-component arrangements. Another approach to controlling surface structures uses adsorbed mol. monolayers to create preferential binding sites that accommodate individual target mols. Here we combine these approaches, by using hydrogen bonding to guide the assembly of two types of mols. into a two-dimensional open honeycomb network that then controls and templates new surface phases formed by subsequently deposited fullerene mols. We find that the open network acts as a two-dimensional array of large pores of sufficient capacity to accommodate several large guest mols., with the network itself also serving as a template for the formation of a fullerene layer.
- 20Elemans, J. A. A. W.; Lei, S.; De Feyter, S. Molecular and Supramolecular Networks on Surfaces: From Two-Dimensional Crystal Engineering to Reactivity Angew. Chem., Int. Ed. 2009, 48, 7298– 7332 DOI: 10.1002/anie.20080633920https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXhtFGrs7zO&md5=2671e78e9c54bcb3830a943327005463Molecular and Supramolecular Networks on Surfaces: From Two-Dimensional Crystal Engineering to ReactivityElemans, Johannes A. A. W.; Lei, Shengbin; De Feyter, StevenAngewandte Chemie, International Edition (2009), 48 (40), 7298-7332CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)A review. The invention of the scanning tunneling microscope has led to the visualization of mols. in real space on atomically flat conductive substrates. This has boosted research into supramol. chem. on surfaces. In this Review, we highlight recent developments in the design and functionality of supramol. surface patterns, with special attention paid to those networks which are chiral or contain a high degree of porosity as well as to the reactivity, which is one of the most important recent developments in supramol. surface chem.
- 21Moulton, B.; Zaworotko, M. J. From Molecules to Crystal Engineering: Supramolecular Isomerism and Polymorphism in Network Solids Chem. Rev. 2001, 101, 1629 DOI: 10.1021/cr990043221https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3MXjtlyqtrg%253D&md5=00fbfe863055d07d1773be77dc52f023From molecules to crystal engineering. Supramolecular isomerism and polymorphism in network solidsMoulton, Brian; Zaworotko, Michael J.Chemical Reviews (Washington, D. C.) (2001), 101 (6), 1629-1658CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)A review with 299 refs. on how the advances in supramol. chem. have impacted the manner in which chemists view the existence of single crystals and the design of new cryst. phases. Coordination polymers, H-bonded networks, and supramol. isomerism and polymorphism are considered.
- 22Mannige, R. V.; Haxton, T. K.; Proulx, C.; Robertson, E. J.; Battigelli, A.; Butterfoss, G. L.; Zuckermann, R. N.; Whitelam, S. Peptoid Nanosheets Exhibit a New Secondary-Structure Motif Nature 2015, 526, 415– 420 DOI: 10.1038/nature1536322https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhs1KqtLzP&md5=0bd25c531cae096b9b515f15ed52dd56Peptoid nanosheets exhibit a new secondary-structure motifMannige, Ranjan V.; Haxton, Thomas K.; Proulx, Caroline; Robertson, Ellen J.; Battigelli, Alessia; Butterfoss, Glenn L.; Zuckermann, Ronald N.; Whitelam, StephenNature (London, United Kingdom) (2015), 526 (7573), 415-420CODEN: NATUAS; ISSN:0028-0836. (Nature Publishing Group)A promising route to the synthesis of protein-mimetic materials that are capable of complex functions, such as mol. recognition and catalysis, is provided by sequence-defined peptoid polymers-structural relatives of biol. occurring polypeptides. Peptoids, which are relatively non-toxic and resistant to degrdn., can fold into defined structures through a combination of sequence-dependent interactions. However, the range of possible structures that are accessible to peptoids and other biol. mimetics is unknown, and our ability to design protein-like architectures from these polymer classes is limited. Here we use mol.-dynamics simulations, together with scattering and microscopy data, to det. the at.-resoln. structure of the recently discovered peptoid nanosheet, an ordered supramol. assembly that extends macroscopically in only two dimensions. Our simulations show that nanosheets are structurally and dynamically heterogeneous, can be formed only from peptoids of certain lengths, and are potentially porous to water and ions. Moreover, their formation is enabled by the peptoids' adoption of a secondary structure that is not seen in the natural world. This structure, a zigzag pattern that we call a Σ('sigma')-strand, results from the ability of adjacent backbone monomers to adopt opposed rotational states, thereby allowing the backbone to remain linear and untwisted. Linear backbones tiled in a brick-like way form an extended two-dimensional nanostructure, the Σ-sheet. The binary rotational-state motif of the Σ-strand is not seen in regular protein structures, which are usually built from one type of rotational state. We also show that the concept of building regular structures from multiple rotational states can be generalized beyond the peptoid nanosheet system.
- 23Dunitz, J. D.; Gavezzotti, A. How Molecules Stick Together in Organic Crystals: Weak Intermolecular Interactions Chem. Soc. Rev. 2009, 38, 2622– 2633 DOI: 10.1039/b822963p23https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXhtVSlsLfI&md5=e017474d43e39e1f1bde0206a2c62e55How molecules stick together in organic crystals: weak intermolecular interactionsDunitz, Jack D.; Gavezzotti, AngeloChemical Society Reviews (2009), 38 (9), 2622-2633CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)This tutorial review introduces the fundamentals of intermol. interactions in terms of the underlying physics and goes on to illustrate the most popular methods for the computer simulation of intermol. interactions, from atom-atom potentials to ab initio methods, including intermediate, hybrid methods, with an appreciation of their relative merits and costs. Typical results are critically presented, culminating in the most difficult exercise of all, the computer prediction of crystal structures. Perspectives on our present and future ability to understand and exploit intermol. interactions are given.
- 24McKeown, N. B. Nanoporous Molecular Crystals J. Mater. Chem. 2010, 20, 10588– 10597 DOI: 10.1039/c0jm01867h24https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXhsVOkt77N&md5=1e30750a10ec78dfd8ff03646d755e2fNanoporous molecular crystalsMcKeown, Neil B.Journal of Materials Chemistry (2010), 20 (47), 10588-10597CODEN: JMACEP; ISSN:0959-9428. (Royal Society of Chemistry)A review. Nanoporous Mol. Crystals (NMCs) are nanoporous materials composed of discrete mols. between which there are only non-covalent interactions-i.e. they do not possess an extended framework composed of covalent or coordination bonds. They are formed from removing guest mols. from inclusion compds. (ICs) a process that for most ICs usually results in the collapse of the open structure of the crystals but in the case of NMCs the packing of the host mols. is retained and nanoporosity obtained. In recent years a no. of NMCs have been confirmed by the technique of gas adsorption and these materials are surveyed in this feature article. In addn., the reasons for stability of these crystals are discussed. It is the author's belief that many more ICs, the structures of which are readily obtainable from the Cambridge Structural Database (CSD), may act as precursors to NMCs.
- 25Chen, T.-H.; Popov, I.; Kaveevivitchai, W.; Chuang, Y. C.; Chen, Y. S.; Daugulis, O.; Jacobson, A. J.; Miljanić, O. Š. Thermally Robust and Porous Noncovalent Organic Framework with High Affinity for Fluorocarbons and CFCs Nat. Commun. 2014, 5, 5131 DOI: 10.1038/ncomms613125https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXitVWgsLnN&md5=72f596c78c5bb02e3d7c61e71bc2a366Thermally robust and porous noncovalent organic framework with high affinity for fluorocarbons and CFCsChen, Teng-Hao; Popov, Ilya; Kaveevivitchai, Watchareeya; Chuang, Yu-Chun; Chen, Yu-Sheng; Daugulis, Olafs; Jacobson, Allan J.; Miljanic, Ognjen S.Nature Communications (2014), 5 (), 5131CODEN: NCAOBW; ISSN:2041-1723. (Nature Publishing Group)Metal-org. and covalent org. frameworks are porous materials characterized by outstanding thermal stability, high porosities and modular synthesis. Their repeating structures offer a great degree of control over pore sizes, dimensions and surface properties. Similarly precise engineering at the nanoscale is difficult to achieve with discrete mols., since they rarely crystallize as porous structures. Here we report a small org. mol. that organizes into a noncovalent org. framework with large empty pores. This structure is held together by a combination of [N-H···N] hydrogen bonds between the terminal pyrazole rings and [π···π] stacking between the electron-rich pyrazoles and electron-poor tetrafluorobenzenes. Such a synergistic arrangement makes this structure stable to at least 250 °C and porous, with an accessible surface area of 1,159 m2 g-1. Crystals of this framework adsorb hydrocarbons, CFCs and fluorocarbons-the latter two being ozone-depleting substances and potent greenhouse species-with wt. capacities of up to 75%.
- 26Chen, B.; Eddaoudi, M.; Hyde, S. T.; O’Keeffe, M.; Yaghi, O. M. Interwoven Metal-Organic Framework on a Periodic Minimal Surface with Extra-Large Pores Science 2001, 291, 1021– 1023 DOI: 10.1126/science.105659826https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3MXhtFGlu7s%253D&md5=a9c2b80ba2f1b825ee2a55278ef5fe92Interwoven metal-organic framework on a periodic minimal surface with extra-large poresChen, Banglin; Eddaoudi, M.; Hyde, S. T.; O'Keeffe, M.; Yaghi, O. M.Science (Washington, DC, United States) (2001), 291 (5506), 1021-1023CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)A strategy for the design of highly porous and structurally stable networks makes use of metal-org. building blocks that can be assembled on a triply periodic P-minimal geometric surface to produce structures that are interpenetrating-more accurately considered as interwoven. The authors used 4,4',4''-benzene-1,3,5-triyltribenzoic acid (H3BTB), Cu(NO3)2e, and DMF to prep. Cu3(BTB)2(H2O)3·(DMF)9(H2O)2 (MOF-14), whose structure reveals a pair of interwoven metal-org. frameworks that are mutually reinforced. The structure contains remarkably large pores, 16.4 Å in diam., in which voluminous amts. of gases and org. solvents can be reversibly sorbed.
- 27Zentner, C. A.; Lai, H. W. H.; Greenfield, J. T.; Wiscons, R. A.; Zeller, M.; Campana, C. F.; Talu, O.; FitzGerald, S. A.; Rowsell, J. L. C. High Surface Area and Z′ in a Thermally Stable 8-Fold Polycatenated Hydrogen-Bonded Framework Chem. Commun. 2015, 51, 11642– 11645 DOI: 10.1039/C5CC04219D27https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhtVCls73O&md5=5c3592ee4b106102ec9b95fe2a1342c0High surface area and Z' in a thermally stable 8-fold polycatenated hydrogen-bonded frameworkZentner, Cassandra A.; Lai, Holden W. H.; Greenfield, Joshua T.; Wiscons, Ren A.; Zeller, Matthias; Campana, Charles F.; Talu, Orhan; FitzGerald, Stephen A.; Rowsell, Jesse L. C.Chemical Communications (Cambridge, United Kingdom) (2015), 51 (58), 11642-11645CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)1,3,5-Tris(4-carboxyphenyl)benzene assembles into an intricate 8-fold polycatenated assembly of (6,3) hexagonal nets formed through hydrogen bonds and π-stacking. One polymorph features 56 independent mols. in the asym. unit, the largest Z' reported to date. The framework is permanently porous, with a BET surface area of 1095 m2 g-1 and readily adsorbs N2, H2 and CO2.
- 28Ciesielski, A.; Samorì, P. Supramolecular Assembly/Reassembly Processes: Molecular Motors and Dynamers Operating at Surfaces Nanoscale 2011, 3, 1397– 1410 DOI: 10.1039/c0nr00914h28https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXltF2kurg%253D&md5=e5add9c83bca4a44aef97271b28d7f04Supramolecular assembly/reassembly processes: Molecular motors and dynamers operating at surfacesCiesielski, Artur; Samori, PaoloNanoscale (2011), 3 (4), 1397-1410CODEN: NANOHL; ISSN:2040-3372. (Royal Society of Chemistry)A review. Among the many significant advances within the field of supramol. chem. over the past decades, the development of the so-called "dynamers" features a direct relevance to materials science. Defined as "combinatorial dynamic polymers", dynamers are constitutional dynamic systems and materials resulting from the application of the principles of supramol. chem. to polymer science. Like supramol. materials in general, dynamers are reversible dynamic multifunctional architectures, capable of modifying their constitution by exchanging, recombining, incorporating components. They may exhibit a variety of novel properties and behave as adaptive materials. In this review we focus on the design of responsive switchable monolayers, i.e. monolayers capable to undergo significant changes in their phys. or chem. properties as a result of external stimuli. Scanning tunneling microscopy studies provide direct evidence with a sub-nanometer resoln., on the formation and dynamic response of these self-assembled systems featuring controlled geometries and properties.
- 29Colson, J. W.; Woll, A. R.; Mukherjee, A.; Levendorf, M. P.; Spitler, E. L.; Shields, V. B.; Spencer, M. G.; Park, J.; Dichtel, W. R. Oriented 2D Covalent Organic Framework Thin Films on Single-Layer Graphene Science 2011, 332, 228– 231 DOI: 10.1126/science.120274729https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXksV2qt7c%253D&md5=0439c797dcb8dbe4bd0af070c29618fbOriented 2D Covalent Organic Framework Thin Films on Single-Layer GrapheneColson, John W.; Woll, Arthur R.; Mukherjee, Arnab; Levendorf, Mark P.; Spitler, Eric L.; Shields, Virgil B.; Spencer, Michael G.; Park, Jiwoong; Dichtel, William R.Science (Washington, DC, United States) (2011), 332 (6026), 228-231CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)Covalent org. frameworks (COFs), in which mol. building blocks form robust microporous networks, are usually synthesized as insol. and unprocessable powders. The authors have grown two-dimensional (2D) COF films on single-layer graphene (SLG) under operationally simple solvothermal conditions. The layered films stack normal to the SLG surface and show improved crystallinity compared with COF powders. The authors used SLG surfaces supported on copper, silicon carbide, and transparent fused silica (SiO2) substrates, enabling optical spectroscopy of COFs in transmission mode. Three chem. distinct COF films grown on SLG exhibit similar vertical alignment and long-range order, and two of these are of interest for org. electronic devices for which thin-film formation is a prerequisite for characterizing their optoelectronic properties.
- 30Ruben, M.; Payer, D.; Landa, A.; Comisso, A.; Gattinoni, C.; Lin, N.; Collin, J.-P.; Sauvage, J.-P.; De Vita, A.; Kern, K. 2D Supramolecular Assemblies of Benzene-1,3,5-triyl-tribenzoic Acid: Temperature-Induced Phase Transformations and Hierarchical Organization with Macrocyclic Molecules J. Am. Chem. Soc. 2006, 128, 15644– 15651 DOI: 10.1021/ja063601k30https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD28Xht1WhsLrO&md5=0e795486268a549e58a504886944e6142D Supramolecular Assemblies of Benzene-1,3,5-triyl-tribenzoic Acid: Temperature-Induced Phase Transformations and Hierarchical Organization with Macrocyclic MoleculesRuben, Mario; Payer, Dietmar; Landa, Aitor; Comisso, Alessio; Gattinoni, Chiara; Lin, Nian; Collin, Jean-Paul; Sauvage, Jean-Pierre; De Vita, Alessandro; Kern, KlausJournal of the American Chemical Society (2006), 128 (49), 15644-15651CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Two-dimensional supramol. honeycomb networks with cavities of an internal diam. of 2.95 nm were formed by the self-assembly of 4,4',4''-benzene-1,3,5-triyl-tribenzoic acid (BTA) on a Ag(111) surface at room temp. Annealing to higher temps. resulted in 2 sequential phase transformations into closer-packed supramol. arrangements. The phase transformations are assocd. with stepwise deprotonation of the carboxylic acid groups. The voids of the honeycomb network of BTA have a suitable size for the construction of hierarchical structures with guest mols. Single mols. of the macrocyclic compd. mt-33 were successfully confined inside 2-dimensional nanocavities of the honeycomb networks and released when the phase was transformed to the close-packed structure.
- 31Silly, F. Two-Dimensional 1,3,5-Tris-(4-carboxyphenyl)-benzene Self-Assembly at the 1-Phenyloctane/Graphite Interface Revisited J. Phys. Chem. C 2012, 116, 10029– 10032 DOI: 10.1021/jp300678mThere is no corresponding record for this reference.
- 32Lee, S. L.; Fang, Y.; Velpula, G.; Cometto, F. P.; Lingenfelder, M.; Müllen, K.; Mali, K. S.; De Feyter, S. Reversible Local and Global Switching in Multicomponent Supramolecular Networks: Controlled Guest Release and Capture at the Solution/Solid Interface ACS Nano 2015, 9, 11608– 11617 DOI: 10.1021/acsnano.5b0608132https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXitVantbfJ&md5=d9699c077effcae556611470be3a7ea3Reversible Local and Global Switching in Multicomponent Supramolecular Networks: Controlled Guest Release and Capture at the Solution/Solid InterfaceLee, Shern-Long; Fang, Yuan; Velpula, Gangamallaiah; Cometto, Fernando P.; Lingenfelder, Magali; Mullen, Klaus; Mali, Kunal S.; De Feyter, StevenACS Nano (2015), 9 (12), 11608-11617CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)The authors demonstrate an elegant approach where the guest binding ability of a supramol. surface can be controlled by inducing structural transitions in it. A physisorbed self-assembled network of a simple hydrogen bonding building block is used as a switching platform. The authors illustrate that the reversible transition between porous and nonporous networks can be accomplished using an elec. field or applying a thermal stimulus. These transitions are used to achieve controlled guest release or capture at the soln.-solid interface. The elec. field and the temp.-mediated methods of guest release are operative at different length scales. While the former triggers the transition and thus guest release at the nanometer scale, the latter is effective over a much larger scale. The flexibility assocd. with physisorbed self-assembled networks renders this approach an attractive alternative to conventional switchable systems.
- 33Li, J.; Gottardi, S.; Solianyk, L.; López, J. C. M.; Stöhr, M. 1,3,5-Benzenetribenzoic Acid on Cu(111) and Graphene/Cu(111): A Comparative STM Study J. Phys. Chem. C 2016, 120, 18093– 18098 DOI: 10.1021/acs.jpcc.6b0554133https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhtF2iu77M&md5=86270d9edd16737394b54e5721326f5c1,3,5-Benzenetribenzoic Acid on Cu(111) and Graphene/Cu(111): A Comparative STM StudyLi, Jun; Gottardi, Stefano; Solianyk, Leonid; Moreno-Lopez, Juan Carlos; Stoehr, MeikeJournal of Physical Chemistry C (2016), 120 (32), 18093-18098CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)The self-assembly of 1,3,5-benzenetribenzoic acid (BTB) mols. on both Cu(111) and epitaxial graphene grown on Cu(111) were studied by scanning tunneling microscopy (STM) and LEED under ultrahigh vacuum conditions. On Cu(111), the BTB mols. were found to mainly arrange in close-packed structures through H-bonding between the (partially) deprotonated carboxylic acid groups. In addn., porous structures formed by intact BTB mols.-and also based on H-bonding-were obsd. On graphene grown on Cu(111) the BTB mols. mainly form porous structures accompanied by small patches of disordered close-packed structures. Upon annealing, BTB adsorbed on Cu(111) is fully deprotonated and arranges in the close-packed structure while in contrast on graphene/Cu(111) the porous network is exclusively formed. This shows that the mol. self-assembly behavior is highly dependent on the first substrate layer: one graphene layer is sufficient to considerably alter the interplay of mol. substrate and intermol. interactions in favor of the latter interactions.
- 34Sing, K. S. W.; Everett, D. H.; Haul, R. A. W.; Moscou, L.; Pierotti, R. A.; Rouquérol, J.; Siemieniewska, T. Reporting Physisorption Data for Gas/Solid Systems with Special Reference to the Determination of Surface Area and Porosity Pure Appl. Chem. 1985, 57, 603– 619 DOI: 10.1351/pac19855704060334https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaL2MXhvFWrtb4%253D&md5=4fbbea83b3a13b5f22e6d26e5d0ab20cReporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity (Recommendations 1984)Sing, K. S. W.; Everett, D. H.; Haul, R. A. W.; Moscou, L.; Pierotti, R. A.; Rouquerol, J.; Siemieniewska, T.Pure and Applied Chemistry (1985), 57 (4), 603-19CODEN: PACHAS; ISSN:0033-4545.Problems and ambiguities in reporting data are discussed. Procedures and terminol. for reporting data re recommended.
- 35Barrett, E. P.; Joyner, L. G.; Halenda, P. P. The Determination of Pore Volume and Area Distributions in Porous Substances. I. Computations from Nitrogen Isotherms J. Am. Chem. Soc. 1951, 73, 373– 380 DOI: 10.1021/ja01145a12635https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaG3MXjsVygsg%253D%253D&md5=5153bbb1018c4eb7aa98fc7e3cd0ea73The determination of pore volume and area distributions in porous substances. I. Computations from nitrogen isothermsBarrett, Elliott P.; Joyner, Leslie G.; Halenda, Paul P.Journal of the American Chemical Society (1951), 73 (), 373-80CODEN: JACSAT; ISSN:0002-7863.An analysis of the N2 desorption isotherms based on the Wheeler theory of combined phys. adsorption and capillary condensation was developed. A method for computing the pore vol. and area distribution directly from the desorption isotherm of porous substances is presented. The method has been successfully applied to adsorbents covering a wide range of pore vol. maxima.
- 36Sakata, O.; Furukawa, Y.; Goto, S.; Mochizuki, T.; Uruga, T.; Takeshita, K.; Ohashi, H.; Ohata, T.; Matsushita, T.; Takahashi, S.; Tajiri, H.; Ishikawa, T.; Nakamura, M.; Ito, M.; Sumitani, K.; Takahashi, T.; Shimura, T.; Saito, A.; Takahasi, M. Beamline for Surface and Interface Structures at SPring-8 Surf. Rev. Lett. 2003, 10, 543– 547 DOI: 10.1021/ja01145a12636https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3sXltFCgtLc%253D&md5=9f1116a3d3ce0bce29d997fc7ef1aca9Beamline for Surface and Interface Structures at SPring-8Sakata, O.; Furukawa, Y.; Goto, S.; Mochizuki, T.; Uruga, T.; Takeshita, K.; Ohashi, H.; Ohata, T.; Matsushita, T.; Takahashi, S.; Tajiri, H.; Ishikawa, T.; Nakamura, M.; Ito, M.; Sumitani, K.; Takahashi, T.; Shimura, T.; Saito, A.; Takahasi, M.Surface Review and Letters (2003), 10 (2 & 3), 543-547CODEN: SRLEFH; ISSN:0218-625X. (World Scientific Publishing Co. Pte. Ltd.)The main components of a new beamline for surface and interface crystal structure detn. at SPring-8 are briefly described. Stages for the beamline monochromator are modified for making an incident X-ray intensity more stable for surface X-ray expts. Abs. photon flux densities were measured with an incident photon energy. A new ultrahigh vacuum system is introduced with preliminary X-ray measurements from an ordered oxygen on Pt (111) surface.
Supporting Information
Supporting Information
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsnano.7b04447.
Experimental details; bulk single crystal XRD analysis data; UV-vis and IR absorption spectra, PL spectra, powder XRD data, AFM and SEM images (PDF)
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