Pyrene-Containing ortho-Oligo(phenylene)ethynylene Foldamer as a Ratiometric Probe Based on Circularly Polarized Luminescence
- Pablo ReinéPablo ReinéDepartment of Organic Chemistry, University of Granada, Avenida de la Fuente Nueva, 18071 Granada, SpainMore by Pablo Reiné
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- Jose JusticiaJose JusticiaDepartment of Organic Chemistry, University of Granada, Avenida de la Fuente Nueva, 18071 Granada, SpainMore by Jose Justicia
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- Sara P. MorcilloSara P. MorcilloDepartment of Organic Chemistry, University of Granada, Avenida de la Fuente Nueva, 18071 Granada, SpainMore by Sara P. Morcillo
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- Sergio AbbateSergio AbbateDipartimento di Medicina Molecolare e Traslazionale, Universitá di Brescia, Viale Europa 11, 25123 Brescia, ItalyMore by Sergio Abbate
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- Belen VazBelen VazDepartment of Organic Chemistry, Biomedical Research Center (CINBIO), and Southern Galicia Institute of Health Research (IISSG), Universidade de Vigo, 36310 Vigo, SpainMore by Belen Vaz
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- María RibagordaMaría RibagordaDepartment of Organic Chemistry, Universidad Autónoma de Madrid, Ciudad Universitaria de Cantoblanco, 28049 Madrid, SpainMore by María Ribagorda
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- Ángel OrteÁngel OrteDepartment of Physical Chemistry, University of Granada, Avenida de la Fuente Nueva, 18071 Granada, SpainMore by Ángel Orte
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- Luis Álvarez de CienfuegosLuis Álvarez de CienfuegosDepartment of Organic Chemistry, University of Granada, Avenida de la Fuente Nueva, 18071 Granada, SpainMore by Luis Álvarez de Cienfuegos
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- Giovanna LonghiGiovanna LonghiDipartimento di Medicina Molecolare e Traslazionale, Universitá di Brescia, Viale Europa 11, 25123 Brescia, ItalyMore by Giovanna Longhi
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- Araceli G. CampañaAraceli G. CampañaDepartment of Organic Chemistry, University of Granada, Avenida de la Fuente Nueva, 18071 Granada, SpainMore by Araceli G. Campaña
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- Delia Miguel*Delia Miguel*E-mail: [email protected]Department of Physical Chemistry, University of Granada, Avenida de la Fuente Nueva, 18071 Granada, SpainMore by Delia Miguel
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- Juan M. Cuerva*Juan M. Cuerva*E-mail: [email protected]Department of Organic Chemistry, University of Granada, Avenida de la Fuente Nueva, 18071 Granada, SpainMore by Juan M. Cuerva
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Abstract
In this manuscript, we report the first synthesis of an organic monomolecular emitter, which behaves as a circularly polarized luminescence (CPL)-based ratiometric probe. The enantiopure helical ortho-oligo(phenylene)ethynylene (o-OPE) core has been prepared by a new and efficient macrocyclization reaction. The combination of such o-OPE helical skeleton and a pyrene couple leads to two different CPL emission features in a single structure whose ratio linearly responds to silver(I) concentration.
Introduction
ARTICLE SECTIONS
Fluorescence spectroscopy is nowadays one of the most versatile techniques for the detection of analytes thanks to its high sensitivity and noninvasiveness. Nevertheless, fluorescence is quite limited when quantitative information is required, since molecular emission intensity can be altered by multiple factors, such as photobleaching, phototransformation, and/or diffusive processes, which may modify the local probe concentration. As a result of this, there has been an effort to develop fluorescence probes that do not depend on the intrinsic intensity of the signal. One approach is the use of ratiometric probes, (1) which are based on a self-calibration process: the ratio of two excitation or emission signals is used for quantitative detection. The relationship between the two emission responses is maintained and is independent of the probe concentration, minimizing the above-mentioned interferences. The difficulty relies on the selection of suitable fluorophores that work together in a proper manner.
Fluorescence spectroscopy in complex mixtures, as living systems, is particularly challenging owing to the fluorescence background. To avoid this, many researchers have been recently focused on the study of circularly polarized luminescence (CPL)-active organic molecules, (2,3) which can potentially behave as more selective fluorescent probes. CPL response depends on the preferential emission of circularly polarized light of one handedness and is usually represented as using (IL – IR), ΔI, as a function of the wavelength, with IL and IR being the intensities of the left and right circularly polarized light. The dimensionless value glum, defined as 2(IL – IR)/(IL + IR), serves to characterized the dissymmetry of the transition. Although many interesting CPL active systems have been described, the use of the CPL emission as quantitative signal in a ratiometric probe has never been demonstrated.
Therefore, we wondered if the ratiometric probe concept could be extended to CPL-active molecules. First, a hypothetical CPL probe should present two different CPL emitters in a single structure, with at least one of them being able to interact with an external stimulus and respond to it. Second, a (usually linear) relationship between the ratio of their chiroptical responses and the analyte concentration is also required. The combination of both requirements in a single structure is highly challenging since the very limited ability of CPL emitters to interact with different species. (4) Noteworthy, CPL spectroscopy provides another level of resolution compared with the unpolarized emission spectrum. Thus, for example, two peaks may overlap in the total emission spectrum, but the electronic transitions involved may have opposite rotational strengths and, therefore, could be clearly distinguished in the CPL spectrum.
Within this context, we have recently described a new family of easy-to-tune CPL emitters based on stapled ortho-oligo(phenylene)ethynylenes (o-OPEs), presenting C2 symmetry ((P,1S,2S)-1, Figure 1), which showed glum values up to 10–2, one of the highest values described for an organic molecule. (5) Besides, they act as a CPL switch based on carbophilic interactions with Ag(I) cations. (5) Interestingly, the pyrene functionalization of the C1 and C2 stereogenic carbons might result in a second CPL emitter unit in the same structure, and therefore a ratio between both chiroptical responses is expected (Figure 1). Moreover, this CPL ratio could be related to the concentration of Ag(I) cations due to their interaction with the o-OPE moiety. Considering this hypothesis, we have synthesized enantiopure (P,1S,2S)-2 and (P,1S,2S)-3 (Figure 1) giving rise to the first ratiometric probe based on CPL, a step beyond a simple switch between two structures. A new enantioespecific synthetic strategy to obtain these helical structures with an intense CPL emission has also been developed, widening the possibility of future exploration of the chemical space of these enantiopure helical compounds by incorporating new functionalities.
Figure 1
Figure 1. Working hypothesis of a CPL-based ratiometric probe based on (P,1S,2S)-1.
Results and Discussion
ARTICLE SECTIONS
Although our previously reported approach toward enantiopure stapled o-OPEs was straightforward, the key stereochemical control was completed by a final chiral HPLC resolution, which is not possible in all cases. On route to (P,1S,2S)-2 and (P,1S,2S)-3, we then decided to develop a more versatile convergent approach using a macrocyclization reaction of known bisphenol 4 and a commercially available chiral ditosylate 5 (Scheme 1). (6) With this strategy, both enantiomers (P,1S,2S)-1 and (M,1R,2R)-1 are now easily available at a large scale from the corresponding (1S,2S)/(1R,2R)-5. In this work, we focused our attention in (P,1S,2S)-1, which was further functionalized using 1-chloromethylpyrene and 1-pyrenecarboxylic acid to yield enantiopure (P,1S,2S)-2 and (P,1S,2S)-3 in good yields.
Scheme 1
Scheme 1. Enantioespecific Synthesis of (P,1S,2S)-2 and (P,1S,2S)-3a
aReaction conditions: (a) (1S,2S)-5, Cs2CO3, MeCN, 80 °C, 22 h, 77%; (b) p-TsOH, EtOH/H2O, reflux, 85%; (c) 1-chloromethylpyrene, NaH, DMF, rt, 12 h, 58%; (d) 1-pyrenecarboxylic acid, DCC, DMAP, rt, 24 h, 85%.
In these systems, the P/M helical chirality is controlled by the chirality of the oxygenated tether. Therefore, the flexibility of the macrocyclic backbone allows a “biased” equilibrium between P and M configurations. In the case of a (S,S)-diol, the observed helicity is P. A total bias of such equilibrium is desired in order to maximize the chiroptical responses as they mainly depend on the helix. An exploration of this effect in simple derivatives led us to conclude that the very robust glum value around 10–2 of (P,1S,2S)-1 was retained and was independent of any substitution in the diol. (7) This observed relationship between the helix and the tether suggests that they were stereochemically coupled. That is, strong variations of the OPE helicity could, in principle, affect the spatial arrangement of a pyrene-functionalized tether and vice versa. The controlled translation of this dynamism into chiroptical properties could result in a ratiometric probe. In this case, the anticipated interaction of Ag(I) cation with the OPE will probably be the driving force for the change in the spatial arrangement of the whole molecule.
To this end, we prepared the alkyl-(P,1S,2S)-2 and acyl-(P,1S,2S)-3 derivatives (Scheme 1). In this case, the pyrene moieties included in the oxygenated tether can interact with each other, resulting in interesting photophysical properties. (8) Remarkably, such optical responses are transported to chiroptical properties (CD and CPL signals) once the environment is chiral. (9)
Compounds (P,1S,2S)-2 and (P,1S,2S)-3 are fluorescent with solvent dependent quantum yields (QY) going from 0.14 to 0.55 and from 0.18 to 0.44, respectively (Table S1). When exciting at 350 nm, the emission is controlled by two main contributions: one broad emission band around 410 nm, where the emission from both the helix and monomer pyrene appears overlapped, and other one corresponding to the pyrene excimer (a broad unstructured band centered around 520–540 nm) (Figure S4). The relative contribution of these bands is highly dependent on the solvent. (See Figures S5 and S6.) The presence of a pyrene excimer band confirmed the close proximity of the two pyrene units, for an intramolecular excited-state interaction. Time-resolved emission spectroscopy (TRES) allowed following the time evolution of the spectral profiles. For (P,1S,2S)-2, a red shift of the emission maximum in the first 15 ns of decay indicates a slow solvent reorganization upon excitation (Figure 2a and Figure S7). This is consistent with the slow dynamics of the helix and the large size of the molecule. The species-associated emission spectra (SAEMS) allowed differentiating three species with lifetimes of 1, 8.1, and 21.3 ns, showing the solvent relaxation-mediated red shift in the emission maximum, and the latter exhibiting the pyrene excimer emission between 510 and 650 nm. A fourth species, with a lifetime of 24.4 ns exhibited a maximum at 450 nm with a typical structure of the helix emission (Figure 2b). This lifetime was longer than the one previously described for this kind of helices due to the pyrenes excimer contribution to the main transitions.
Figure 2
Figure 2. (a) TRES spectra of (P,1S,2S)-2 after a δ-pulse excitation as a function of time and emission wavelength in CH2Cl2 as a solvent. (b) SAEMS spectra of compound (P,1S,2S)-2 in CH2Cl2 as a solvent.
More interesting results were obtained for (P,1S,2S)-3, which presents features of excited-state dynamics as the emission of the pyrene excimer is formed from other species (Figures 3a and S5). The spectral decomposition (SAEMS, Figure 3b) showed three species with the typical emission of pyrenes and lifetimes of 1.0, 6.1, and 22.1 ns. These species exhibited negative contributions in the pyrene excimer region, clearly supporting that the excimer emission (fourth species with a lifetime of 43.9 ns) builds up from the others through an excited-state reaction. The o-OPE emission appears as a shoulder overlapping the pyrene excimer species of a 22.1 ns lifetime.
Figure 3
Figure 3. (a) TRES spectra of (P,1S,2S)-3 after a δ-pulse excitation as a function of time and emission wavelength in CH2Cl2 as a solvent. (b) SAEMS spectra of compound (P,1S,2S)-3 in CH2Cl2 as a solvent.
Circular dichroism (CD) spectra of (P,1S,2S)-2 and (P,1S,2S)-3 were also recorded (Figure 4). For (P,1S,2S)-2, overlapped absorption signals corresponding to the absorption of the o-OPE (at 345 nm) and pyrene subunits (at 365 nm) could be clearly observed. Remarkably, the opposite signs allowed us to discern between the contributions of each substructure throughout the entire spectra, which might be very relevant for a potential chiroptical ratiometric probe, as we commented before. In the case of (P,1S,2S)-3, the presence of the carbonyl group red shifts the absorption of the pyrenes and their CD signals were partially resolved (λ = 387 nm).
Figure 4
Figure 4. (a) Left: experimental (solid line) and average of the main calculated (dash-dotted line) CD spectra of compound (P,1S,2S)-2 in the absence (black) and presence (red) of Ag(I). Experimental intensity of the silver complex has been multiplied by 5. Right: calculated main conformer of (P,1S,2S)-2 in the absence (light blue) and presence (blue) of Ag(I). (b) Left: experimental (solid line) and average of the main calculated (dash-dotted line) CD spectra of compound (P,1S,2S)-3 in the absence (green) and presence (violet) of Ag(I). Right: CD titration of compound (P,1S,2S)-3. Offsets of 15 nm have been applied to theoretical data.
The CD spectra of (P,1S,2S)-2 in the presence of Ag(I) showed a decrease in the CD intensity as Ag(I) concentration increased (Figure 4a and Figures S9 and S10). This phenomenon, already described by us, (5a) is due to the planar arrangement of the OPE alkynes to accommodate the cation in nonpolar solvents. (10,11)
The same behavior is observed for (P,1S,2S)-3 silver coordination, causing again the disappearance of the OPE helicity due to the planarization of the structure and the corresponding CD signal disappearance (345 nm) (Figure 4b and Figures S11–S13). However, such a strong structural change affected to a much lesser extent the chiral environment of the pyrenes, remaining the corresponding CD signal (387 nm) (Figure 4b, right). This result supports the idea that the geometry of the two subunits may be independent in the ground state, and therefore, (P,1S,2S)-3 could be used as a Ag(I) ratiometric probe based on CD. In fact, a good linear relationship (R2 = 0.96) was obtained between the ratio of Δε intensities at 345 and 387 nm and Ag(I) concentration. (See the inset in Figures 4b and S12 for more details.) Fitting of Δε value at 345 nm at different silver concentrations gives a binding constant of K(P,S,S)-3 = 6360 ± 5% M–1. (12)
To gain some insights into these different behaviors, we performed theoretical calculations at the DFT level. In all of the cases, the calculated CD spectra reproduced the experimental sign taking into account the chiral synthon used. For (P,1S,2S)-2, several conformers were analyzed, and a majority of P conformations of the OPE moiety was obtained (a total of 77% of population). Moreover, among the conformers with the same helicity, differences were only found in the pyrene orientation and not in the shape of the OPE backbone. (See the Supporting Information for details.) In all of the cases, the interaction with Ag(I) changes the shape of the OPE, which lost the helicoidal shape as was previously described for analogous p,p-substituted compounds (Figure 5). (10)
Figure 5
Figure 5. (a) Calculated first two conformers of (P,1S,2S)-2 in the absence (light blue) and presence (blue) of Ag(I).
Considering the orbitals involved in the first principal transition for major conformers in the absence of Ag(I), a main difference can be observed between compounds (P,1S,2S)-2 and 3. Alkyl derivative (P,1S,2S)-2 presents orbitals localized just on the pyrene rings, just on the OPE backbone, and some delocalized on the whole molecule. However, for compound (P,1S,2S)-3, there is a clear separation between pyrene and OPE moieties (Figure 6).
Figure 6
Figure 6. Examples of different orbitals of the main conformer of (P,1S,2S)-2 (left) and (P,1S,2S)-3 (right) in the absence of Ag(I).
The rotational strengths of different conformers and the orbitals involved in the first main transitions were also analyzed to assign the observed features to either the OPE or the pyrene chromophore. (See the Supporting Information for details.) In this sense, a good agreement between experimental and theory both in absorption and CD spectra was observed. As it can be seen in Figure 4a, the calculated CD response reproduces quite satisfactorily the observed spectra and also their variations upon silver addition; only the intensity of the narrow bands attributed to pyrene are overestimated by calculations. The same kind of calculations were carried out for compound (P,1S,2S)-3. As was previously mentioned, the main observed difference is related with the orbitals responsible for the main transitions in the absence of Ag(I), which are localized either in the pyrene subunit or in the OPE moiety, whereas for the ether derivative 2 there was not a clear separation between the two moieties. (See Figures S19 and S24). Again, we obtained a good fitting between calculated and experimental CD spectra (Figure 4b).
CPL responses of both compounds were recorded in the absence and presence of Ag(I). (P,1S,2S)-2 presented a differential emission with two different signals, which can be attributed to the two decoupled subunits (Figure 7a). The first one, corresponding to the OPE subunit, presented glum values of 1.2 × 10–2 at around 390 nm (Figure S14), as it was previously observed for diol (P,1S,2S)-1. The second signal, with a negative sign derived from the pyrenes, presented a glum value around −5 × 10–3 (around 515 nm). These two values can be reasonably detected by CPL equipment. Unexpectedly, (P,1S,2S)-3 presented a very different behavior (Figure 7b). In this case, the fluorescent o-OPE subunit showed no CPL emission, being only detectable by the response of the pyrenes excimer with a glum value around −3 × 10–2 at 540 nm and +0.7 × 10–2 at about 480 nm (Figure S14) to prevent the use of (P,1S,2S)-3 as a ratiometric probe based on CPL measurements. (9c,f) This signal observed in the emissive region of the pyrene groups is a couplet. The interpretation of such couplet is not an easy task, although some explanations of the bisignated signals in CPL have been described: (5a,13,14) one may invoke the presence of different conformers, with different geometries in their ground state and also different S1 excited states, (5a) or one may find that the dominant conformer in the ground state presents a S1 state with two minima (like in camphor). (13a) Considering the TRES results and the OPE emissive bands observed in the other studied compounds containing the same moiety, both CPL features may be assigned to pyrene fluorophore with different arrangements. In any case, it seems that once the pyrene unit is excited, the excimer with the second pyrene unit, in close proximity, is formed within 1 ns, as evidenced by the negative pre-exponential factor of the shortest lifetime in the fluorescence decay traces. This fast formation of the excimer and the subsequent change in geometry forced a planarization of the OPE.
Figure 7
Figure 7. Fluorescence spectra (dashed line) and left–right (ΔI) intensities (solid line) of compounds (a) (P,1S,2S)-2 and (b) (P,1S,2S)-3. (ΔI intensities of the Ag(I) complex are referred to as right axis.) (c) CPL titration of compound (P,1S,2S)-2 with AgBF4. Inset: linear fitting of the ratio between left–right fluorescence intensity (ΔI) at 400 and 500 nm versus Ag(I) concentration.
Thus, we proceeded with the study of the CPL response of compound (P,1S,2S)-2 in the presence of Ag(I). The CPL response in terms of ΔI diminishes in the presence of increasing amounts of Ag(I) for both signals (Figure 7c). Moreover, the different sign of the two CPL responses was ideal for the quantification. In fact, the ratio between absolute values of ΔI (400 nm)/ΔI (500 nm) showed a linear response with the Ag(I) content as required for a ratiometric probe (Figure 7c, inset). (15)
Conclusion
ARTICLE SECTIONS
In summary, we have synthesized two compounds, each one bearing two moieties with a characteristic chiroptical and fluorescent activity. The OPE moiety structure is sensitive to Ag; on the contrary, the pyrene reciprocal orientation appears to be preserved also in the Ag complex. We developed and demonstrated that compound (P,1S,2S)-2 with two CPL emissions can behave as the first example reported of a ratiometric probe based on CPL emission. Although the described example presents limitations, the expected superiority in terms of sensitivity and selectivity of CPL probes for future applications in CPL-based microscopes relies in the assumption that the translation of the usual fluorescent-based analytic techniques is possible. (16) In this sense, the synthesis of novel CPL probes able to carry different functions is a prerequisite for the full development of this technique into a standard analytical technique. Development of ratiometric probes with more balanced CPL emissions and better signal-to-noise ratios is underway.
Experimental Section
ARTICLE SECTIONS
General Section
All reagents were used as purchased from standard chemical suppliers and used without further purification. TLC was performed on aluminum-backed plates coated with silica gel 60 (230–240 mesh) with the F254 indicator. The spots were visualized with UV light (254 nm). All chromatography purifications were performed with silica gel 60 (40–60 μm). NMR spectra were measured at room temperature. 1H NMR spectra were recorded at 400 and 500 MHz. Chemical shifts are reported in ppm using the residual solvent peak as a reference (CHCl3 δ = 7.26 ppm, CH2Cl2 δ = 5.32 ppm). Data are reported as follows: chemical shift, multiplicity (s = singlet, d = doublet, t = triplet, q = quartet, quint = quintuplet, m = multiplet, dd = doublet of doublets, dt = doublet of triplets, dq = doublet of quartets, td = triplet of doublets, bs = broad singlet), coupling constant (J in Hz), and integration. 13C NMR spectra were recorded at 100 and 125 MHz using broad-band proton decoupling, and chemical shifts are reported in ppm using residual solvent peaks as a reference (CHCl3 δ = 77.16 ppm, CH2Cl2 δ = 54.0 ppm). Carbon multiplicities were assigned by DEPT techniques. High resolution mass spectra (HRMS) were recorded on a mass spectrometer using atmospheric-pressure chemical ionization (APCI+) or electrospray ionization (ESI). Known compound 4 was isolated as a pure sample and showed NMR spectra matching those of previously reported data. (5a)
Synthesis of Compound (P,1S,2S)-1
A solution of 4 (943 mg, 2.3 mmol) in CH3CN (15 mL) was added to a mixture of 1,4-di-O-tosyl-2,3-O-isopropyl-indene-l-threitol (S,S)-5 (1.1 g, 2.3 mmol) (6) and Cs2CO3 (1.8 g, 5.52 mmol) in CH3CN (135 mL). The mixture was heated under reflux for 22 h. Then, the solvent was removed. The residue was purified by flash chromatography (EtOAc/hexane 3:7) to give the corresponding ketal (P,1S,2S)-6 (950 mg, 77%). Yellow solid, mp 165–174 °C. 1H NMR (400 MHz, CDCl3): δ 7.66–7.61 (m, 2H), 7.60–7.56 (m, 2H), 7.35–7.28 (m, 4H), 7.24 (d, J = 8.7 Hz, 4H), 6.42 (d, J = 8.7 Hz, 4H), 4.39–4.22 (m, 6H), 1.50 (s, 6H). 13C NMR (100 MHz, CDCl3): δ 158.2 (C), 133.8 (CH), 133.4 (CH), 133.1 (CH), 130.1 (C), 128.2 (CH), 127.7 (CH), 125.3 (C), 124.9 (C), 115.9 (C), 114.4 (CH), 109.5 (C), 93.8 (C), 92.6 (C), 87.5 (C), 75.2 (CH), 67.0 (CH2), 27.0 (CH3). HRMS (ESI-TOF) m/z: [M + Na]+ calcd for C37H28O4Na, 559.1879; found, 559.1864.
To a solution of previously described ketal (P,1S,2S)-6 (295 mg, 0.55 mmol) in MeOH (25 mL), pTsOH (10 mg, 0.055 mmol) and water (40 mg, 2.2 mmol) were added. The reaction was heated under reflux for 2.5 h. Then, the mixture was diluted with abundant CH2Cl2, washed with water, and dried over anhydrous Na2SO4, and the solvent was removed. The residue was purified by flash chromatography (EtOAc/hexane 4:6) to give diol (P,1S,2S)-1 (232 mg, 85%). Its 1H and 13C NMR data matched with previously described data. (5a)
Synthesis of Pyrene Derivative (P,1S,2S)-2
A mixture of diol (P,1S,2S)-1 (50 mg, 0.1 mmol) and NaH (32 mg, 0.8 mmol, 60% purity) in DMF (1 mL) was stirred under an Ar atmosphere for 1 h. Then, a solution of 1-chloromethylpyrene (100 mg, 0.4 mmol) in DMF (2 mL) was added, and the new mixture was stirred at room temperature and under an Ar atmosphere for 12 h. Then, CH2Cl2 was added. The mixture was washed with HCl2N and dried over anhydrous Na2SO4, and the solvent was removed. The residue was purified by flash chromatography (EtOAc/hexane 1:9) to give compound (P,1S,2S)-2 (54 mg, 58%). White solid, mp 180–193 °C. 1H NMR (500 MHz, CDCl3): δ 8.56 (d, J = 9.2 Hz, 1H), 8.27–8.21 (m, 3H), 8.18–8.13 (m, 3H), 8.08–7.96 (m, 2H), 7.62 (d, J = 7.5 Hz, 2H), 7.37 (td, J = 7.6, 1.5 Hz, 1H), 7.31 (td, J = 7.6, 1.4 Hz, 1H), 6.80 (d, J = 7.5 Hz, 2H), 5.67 (d, J = 12.4 Hz, 1H), 5.56–5.46 (m, 2H), 5.32–5.21 (m, 1H), 4.13–3.98 (m, 1H), 3.93–3.78 (m, 1H), 3.63 (dd, J = 11.6, 3.9 Hz, 1H). 13C NMR (125 MHz, CDCl3): δ 156.3 (C), 133.5 (CH), 133.1 (CH), 132.7 (CH), 132.0 (CH), 131.4 (C), 131.0 (C), 130.8 (C), 130.3 (C), 128.8 (CH), 128.3 (CH), 128.21 (CH), 128.19 (CH), 127.6 (CH), 127.4 (CH), 126.3 (CH), 125.7 (CH), 125.5 (C), 125.2 (C), 125.0 (C), 124.8 (C), 124.4 (CH), 124.0 (CH), 115.4 (C), 114.3 (CH), 93.9 (C), 92.3 (C), 87.3 (C), 72.5 (CH2), 70.9 (CH), 63.6 (CH2). HRMS (APCI-TOF) m/z: [M]+ calcd for C68H45O4, 925.3312; found, 925.3313.
Synthesis of Pyrene Derivative (P,1S,2S)-3
To a solution of (P,1S,2S)-1 (25 mg, 0.05 mmol) in CH2Cl2 (5 mL) were added DMAP (12 mg, 0.1 mmol), dicyclohexylcabodiimide (DCC) (37 mg, 0.18 mmol), and 1-pyrenecarboxylic acid (44 mg). The mixture was stirred at room temperature for 24 h. Then, the solvent was removed. The residue was purified by flash chromatography (EtOAc/hexane 1:9) to give compound (P,1S,2S)-3 (41 mg, 87%). Yellow solid, mp 235–246 °C. 1H NMR (400 MHz, CD2Cl2): δ 9.26 (d, J = 9.5 Hz, 2H), 8.77 (d, J = 8.2 Hz, 2H), 8.26–8.19 (m, 3H), 8.16 (d, J = 5.2 Hz, 2H), 8.12 (dd, J = 6.4, 1.9 Hz, 4H), 8.07 (d, J = 5.1 Hz, 2H), 8.03 (d, J = 1.5 Hz, 2H), 8.01 (d, J = 2.9 Hz, 2H), 7.76–7.60 (m, 4H), 7.44–7.35 (m, 8H), 6.78 (d, J = 8.6 Hz, 4H), 6.19 (d, J = 6.9 Hz, 2H), 4.80 (dd, J = 11.8, 2.9 Hz, 2H), 4.52 (dd, J = 11.4, 7.8 Hz, 2H). 13C NMR (100 MHz, CD2Cl2): δ 167.5 (C), 157.8 (C), 135.3 (C), 134.1 (CH), 134.0 (CH), 133.3 (CH), 131.9 (C), 131.5 (C), 130.7 (C), 130.4 (CH), 130.2 (CH), 129.2 (CH), 128.9 (CH), 128.2 (CH), 127.6 (CH), 127.1 (CH), 127.0 (CH), 126.9 (CH), 125.8 (C), 125.3 (C), 125.2 (C), 125.0 (CH), 124.7 (CH), 124.4 (C), 122.8 (C), 116.4 (C), 115.1 (CH), 94.4 (C), 92.8 (C), 87.8 (C), 69.1 (CH), 64.8 (CH2). HRMS (APCI-TOF) m/z: [M]+ calcd for C68H41O6, 953.2898; found, 953.2893.
Steady-State and Time-Resolved Emission Spectroscopy
Steady-State Fluorescence Spectra Were Recorded Using a JASCO FP-8300 Spectrofluorometer in 10 × 10 mm Cuvettes
Time-resolved fluorescence decay traces were collected via the time-correlated single photon counting (TCSPC) method using a FluoTime 200 fluoromoter (PicoQuant, GmbH). The excitation source was a 375 nm pulsed diode laser (LDH-P-C-375B PicoQuant, GmbH) using a 20 MHz excitation frequency for measurements at 400 nm and 5 MHz frequency for excimer measurements at 540 nm. The full width at half-maximum (fwhm) of the laser pulses was around 40 ps. The fluorescence emission was collected at a 90° geometry, focused at the detector after crossing through a polarizer (set at the magic angle), 2 mm slits, and a 2 nm bandwidth monochromator. TCSPC was achieved by a TimeHarp200 board, set at 36 ps/channel. Fluorescence decay traces were collected for the necessary time to reach 20 000 counts at the peak channel. For both compounds (P,1S,2S)-2 and (P,1S,2S)-3 decay traces were collected at 398, 400, and 402 nm, where the maximum of emission was observed (corresponding to OPE and pyrene structures) and at 536, 538, and 540 nm, where excimer emission is observed.
Time-resolved emission spectroscopy (TRES) of compounds (P,1S,2S)-2 and (P,1S,2S)-3 dissolved in CH2Cl2 was performed by collecting 66 fluorescence decay traces in the 390–650 nm emission range (Δλem = 4 nm) at 5 MHz excitation frequency during a fixed amount of time (500 s), to maintain the overall intensity information.
Circular Dichroism and Circularly Polarized Luminiscence Measurements
CD titrations were performed in an Olis DSM172 spectrophotometer with a xenon lamp of 150 W with a 1.0 cm path-length quartz cell. In all of the cases, a fixed slit width of 1 mm and integration time of 0.2 s were selected. Titrations of compounds (P,1S,2S)-2 and (P,1S,2S)-3 were carried out by the addition of progressive quantities of a 2.5 × 10–4 M solution of AgBF4 salt, which was commercially available, to a 2.5 × 10–5 M solution of the corresponding compound in a 95:5 mixture of CH2Cl2/acetone. To make the fitting of the kinetic constant easier, the concentration of ligands (P,1S,2S)-2 and (P,1S,2S)-3 was kept constant during the titration. To ensure this, a 2.5 × 10–5 M solution of these compounds was used as a solvent to prepare the AgBF4 solution.
Circularly polarized luminiscence (CPL) measurements were recorded in an Olis DSM172 spectrophotometer. The spectra were recorded at 1 × 10–5 M concentrations in HPLC grade solvents. A fixed wavelength LED (372 nm) as the excitation source was used.
Supporting Information
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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.joc.8b00162.
Experimental details on optical measurements, further details on theoretical calculations of computed structures, and spectral data (PDF)
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Author Information
ARTICLE SECTIONS
- Juan M. Cuerva - Department of Organic Chemistry, University of Granada, Avenida de la Fuente Nueva, 18071 Granada, Spain;
http://orcid.org/0000-0001-6896-9617;
- Sergio Abbate - Dipartimento di Medicina Molecolare e Traslazionale, Universitá di Brescia, Viale Europa 11, 25123 Brescia, Italy;http://orcid.org/0000-0001-9359-1214
- María Ribagorda - Department of Organic Chemistry, Universidad Autónoma de Madrid, Ciudad Universitaria de Cantoblanco, 28049 Madrid, Spain;http://orcid.org/0000-0001-7185-4095
- Ángel Orte - Department of Physical Chemistry, University of Granada, Avenida de la Fuente Nueva, 18071 Granada, Spain;http://orcid.org/0000-0003-1905-4183
- Giovanna Longhi - Dipartimento di Medicina Molecolare e Traslazionale, Universitá di Brescia, Viale Europa 11, 25123 Brescia, Italy;http://orcid.org/0000-0002-0011-5946
- Araceli G. Campaña - Department of Organic Chemistry, University of Granada, Avenida de la Fuente Nueva, 18071 Granada, Spain;http://orcid.org/0000-0001-5483-5642
Acknowledgments
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We thank the Ministerio de Economía y Competitividad (MINECO, Spain) (CTQ2017-85454-C2-1-P, CTQ2017-85454-C2-2-P, CTQ2015-70283-P, CTQ2014-53598-R), the European Research Council (ERC) (ERC-2015-STG-677023), and the “Unidad de Excelencia Química Aplicada a Biomedicina y Medioambiente” (UGR) for funding. A.G.C. and P.R also acknowledge funding from MINECO and MECD (Spain) for RyC-2013-12943 and FPU contracts, respectively. The Computing Center CINECA Via Magnanelli 6/3 40033, Casalecchio di Reno (Bologna) Italy, is also acknowledged for access to computational facilities.
References
ARTICLE SECTIONS
This article references 16 other publications.
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For recent examples, see:
(a) Gobo, Y.; Yamamura, M.; Nakamura, T.; Nabeshima, T. Org. Lett. 2016, 18, 2719– 2721, DOI: 10.1021/acs.orglett.6b01237[ACS Full Text.], [CAS], Google Scholar3ahttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28Xot12ksbY%253D&md5=70e3e188bc9e215ed7786fb3a55ede37Synthesis and Chiroptical Properties of a Ring-Fused BODIPY with a Skewed Chiral π SkeletonGobo, Yuki; Yamamura, Masaki; Nakamura, Takashi; Nabeshima, TatsuyaOrganic Letters (2016), 18 (11), 2719-2721CODEN: ORLEF7; ISSN:1523-7052. (American Chemical Society)A twisted chiral boron-dipyrrin complex (BODIPY) was synthesized by oxidative annulation of the biphenyl units at the β positions. The chiral BODIPY has two asym. carbons in the large planar skeleton, which were generated upon the ring-fused reaction. Its π-elongated and twisted structure resulted in the Cotton effect in the red region (λmax = 614 nm, Δε = 60 M-1·cm-1) as well as the strong fluorescence (ΦF = 0.73) and circularly polarized luminescence (CPL). [Bis(trifluoroacetoxy)iodo]benzene (808 mg, 1.88 mmol) and BF3≥OEt2.(b) Nishimura, H.; Tanaka, K.; Morisaki, Y.; Chujo, Y.; Wakamiya, A.; Murata, Y. J. Org. Chem. 2017, 82, 5242– 5249, DOI: 10.1021/acs.joc.7b00511[ACS Full Text.], [CAS], Google Scholar3bhttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXmsFajsb4%253D&md5=7bc0e85a51e5bb0ad1ef144e580d91f4Oxygen-Bridged Diphenylnaphthylamine as a Scaffold for Full-Color Circularly Polarized Luminescent MaterialsNishimura, Hidetaka; Tanaka, Kazuo; Morisaki, Yasuhiro; Chujo, Yoshiki; Wakamiya, Atsushi; Murata, YasujiroJournal of Organic Chemistry (2017), 82 (10), 5242-5249CODEN: JOCEAH; ISSN:0022-3263. (American Chemical Society)An O-bridged diphenylnaphthylamine with a helical shape was designed and synthesized as a key scaffold for circularly polarized luminescent (CPL) materials. The introduction of electron-withdrawing groups, such as formyl and 2,2-dicyanovinyl substituents at the naphthyl moiety in this skeleton effectively decreases the LUMO level and allows a tuning of the band gap. The prepd. model compds. exhibit intense CPL signals with a dissymmetry factor (g value) of 10-3 both in CH2Cl2 solns. and in the solid states. The emission colors of these derivs. are influenced both by the substituents as well as by solvent effects, covering the whole visible region from blue to deep red. Crystallog. data are given.(c) Takase, K.; Noguchi, K.; Nakano, K. Org. Lett. 2017, 19, 5082– 5085, DOI: 10.1021/acs.orglett.7b02337 .(c1) Kögel, J. 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The completely fixed conformers are resolved into M- and P-enantiomer, which showed mirror imaged CD and almost quant. fluorescence quantum yield. Also, it also showed a mirror and large circularly polarized luminescence dissym. factor, depending on the helicity of the enantiomer. The result provides the most direct and persuasive evidence for AIE via the restriction of intramol. rotation and finds the new insight of the compds. in chiroptical property.(f) Hellou, N.; Srebro-Hooper, M.; Favereau, L.; Zinna, F.; Caytan, E.; Toupet, L.; Dorcet, V.; Jean, M.; Vanthuyne, N.; Williams, J. A. G.; Di Bari, L.; Autschbach, J.; Crassous, J. Angew. Chem., Int. Ed. 2017, 56, 8236– 8239, DOI: 10.1002/anie.201704263 .(g) Schulte, T. R.; Holstein, J. J.; Krause, L.; Michel, R.; Stalke, D.; Sakuda, E.; Umakoshi, K.; Longhi, G.; Abbate, S.; Clever, G. H. J. Am. Chem. Soc. 2017, 139, 6863– 6866, DOI: 10.1021/jacs.7b03963 .(h) Gon, M.; Morisaki, Y.; Chujo, Y. Chem. 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Carmen; Ribagorda, Maria; Longhi, Giovanna; Mota, Antonio J.; Alvarez de Cienfuegos, Luis; Cuerva, Juan M.Chemistry - A European Journal (2018), 24 (11), 2653-2662CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)A new family of homochiral silver complexes based on carbophilic interactions with ortho-phenylene ethynylene (o-OPE) scaffolds contg. up to two silver atoms are described. These compds. represent a unique class of complexes with chirality at the metal. Chiral induction is based on the inclusion of chiral sulfoxides, which allow efficient transfer of chirality to the helically folded o-OPE, leading to circularly polarized luminescence (CPL)- and vibrational CD (VCD)-active compds. In the presence of silver(I) cations, carbophilic interactions dominate, which promote helical structures with a defined helicity. This is one of the very scarce examples of the use of such interactions in the attractive field of abiotic foldamers. The switching event has been extensively studied by using different chiroptical techniques, including CD, CPL, and VCD, and represents one of the few CPL switches described in the literature. - 4
For example, see:
(a) Maeda, H.; Bando, Y.; Shimomura, K.; Yamada, I.; Naito, M.; Nobusawa, K.; Tsumatori, H.; Kawai, T. J. Am. Chem. Soc. 2011, 133, 9266– 9269, DOI: 10.1021/ja203206g .(b) Maeda, H.; Shirai, T.; Bando, Y.; Takaishi, K.; Uchiyama, M.; Muranaka, A.; Kawai, T.; Naito, M. Org. Lett. 2013, 15, 6006– 6009, DOI: 10.1021/ol402895r .(c) Saleh, N.; Moore, B.; Srebro, M.; Vanthuyne, N.; Toupet, L.; Williams, J. A. G.; Roussel, C.; Deol, K. K.; Muller, G.; Autschbach, J.; Crassous, J. Chem. - Eur. J. 2015, 21, 1673– 1681, DOI: 10.1002/chem.201405176[Crossref], [PubMed], [CAS], Google Scholar.4chttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhvFKmtb7L&md5=076f30defb61cc784b70a3c1f58bafcdAcid/Base-Triggered Switching of Circularly Polarized Luminescence and Electronic Circular Dichroism in Organic and Organometallic HelicenesSaleh, Nidal; Moore, Barry II; Srebro, Monika; Vanthuyne, Nicolas; Toupet, Loic; Williams, J. A. Gareth; Roussel, Christian; Deol, Kirandeep K.; Muller, Gilles; Autschbach, Jochen; Crassous, JeanneChemistry - A European Journal (2015), 21 (4), 1673-1681CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)Electronic CD and circularly polarized luminescence acid/base switching activity has been demonstrated in helicene-bipyridine proligand 1a and in its "rollover" cycloplatinated deriv. 2a. Whereas proligand 1a displays a strong bathochromic shift (>160 nm) of the nonpolarized and circularly polarized luminescence upon protonation, complex 2a displays slightly stronger emission. This strikingly different behavior between singlet emission in the org. helicene and triplet emission in the organometallic deriv. has been rationalized by using quantum-chem. calcns. The very large bathochromic shift of the emission obsd. upon protonation of azahelicene-bipyridine 1a has been attributed to the decrease in aromaticity (promoting a charge-transfer-type transition rather than a π-π* transition) as well as an increase in the HOMO-LUMO character of the transition and stabilization of the LUMO level upon protonation.(d) Hashimoto, Y.; Nakashima, T.; Shimizu, D.; Kawai, T. Chem. Commun. 2016, 52, 5171– 5174, DOI: 10.1039/C6CC01277A .(e) Isla, H.; Srbo-Hooper, M.; Jean, M.; Vanthuyne, N.; Roisnel, T.; Lunkley, J. L.; Muller, G.; Willians, J. A. G.; Autschbach, J.; Crassous, J. Chem. Commun. 2016, 52, 5932– 5935 - 5(a) Morcillo, S. P.; Miguel, D.; Álvarez de Cienfuegos, L.; Justicia, J.; Abbate, S.; Castiglioni, E.; Bour, C.; Ribagorda, M.; Cárdenas, D. J.; Paredes, J. M.; Crovetto, L.; Choquesillo-Lazarte, D.; Mota, A. J.; Carreño, M. C.; Longhi, G.; Cuerva, J. M. Chem. Sci. 2016, 7, 5663– 5670, DOI: 10.1039/C6SC01808D[Crossref], [PubMed], [CAS], Google Scholar.5ahttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XotVWlsrY%253D&md5=d9a83ef62dc2df47f742e07a630dae59Stapled helical o-OPE foldamers as new circularly polarized luminescence emitters based on carbophilic interactions with Ag(I)-sensitivityMorcillo, Sara P.; Miguel, Delia; Alvarez de Cienfuegos, Luis; Justicia, Jose; Abbate, Sergio; Castiglioni, Ettore; Bour, Christophe; Ribagorda, Maria; Cardenas, Diego J.; Paredes, Jose Manuel; Crovetto, Luis; Choquesillo-Lazarte, Duane; Mota, Antonio J.; Carreno, M. Carmen; Longhi, Giovanna; Cuerva, Juan M.Chemical Science (2016), 7 (9), 5663-5670CODEN: CSHCCN; ISSN:2041-6520. (Royal Society of Chemistry)Ortho-Oligo(phenylene)ethynylenes (o-OPEs) stapled with enantiopure 2,3-dihydroxybutane diethers have highly intense CD (CD) spectra and excellent circular polarized luminescence (CPL) responses (glum values up to 1.1 × 10-2), which are consistent with homochiral helically folded structures. In the presence of Ag(I), a change in the CPL emission is obsd., representing the first example of CPL active small org. mol. emitters, which can be modulated by carbophilic interactions in a reversible manner.(b) Fuentes, N.; Martin-Lasanta, A.; Alvarez de Cienfuegos, L.; Robles, R.; Choquesillo-Lazarte, D.; Garcia-Ruiz, J. M.; Martinez-Fernandez, L.; Corral, I.; Ribagorda, M.; Mota, A. J.; Cárdenas, D. J.; Carreño, M. C.; Cuerva, J. M. Angew. Chem., Int. Ed. 2012, 51, 13036– 13040, DOI: 10.1002/anie.201206259
- 6
The corresponding enantiomers (M,1R,2R)-2 and (M,1R,2R)-3 were also prepared using ditosilate (1R,2R)-5, showing mirror-image chiroptical properties. See the Supporting Information.
There is no corresponding record for this reference. - 7Reiné, P.; Justicia, J.; Morcillo, S. P.; Mazzeo, G.; García-Fernández, E.; Rodríguez-Diéguez, A.; Álvarez de Cienfuegos, L.; Abbate, S.; Cuerva, J. M.; Longhi, G.; Miguel, D. Chirality 2018, 30, 43– 54, DOI: 10.1002/chir.22774
- 8(a) Kanaya, T.; Goshiki, K.; Yamamoto, M.; Nishijima, Y. J. Am. Chem. Soc. 1982, 104, 3580– 3587, DOI: 10.1021/ja00377a007 .(b) Yamamoto, M.; Goshiki, K.; Kanaya, T.; Nishijima, Y. Chem. Phys. Lett. 1978, 56, 333– 335, DOI: 10.1016/0009-2614(78)80253-X .(c) Miguel, D.; Morcillo, S. P.; Martín-Lasanta, A.; Fuentes, N.; Martínez-Fernández, L.; Corral, I.; Ruedas-Rama, M. J.; Cárdenas, D. J.; Álvarez de Cienfuegos, L.; Orte, A.; Cuerva, J. M. Org. Lett. 2015, 17, 2844– 2847, DOI: 10.1021/acs.orglett.5b01275
- 9(a) Kano, K.; Matsumoto, H.; Hashimoto, S.; Sisido, M.; Imanishi, Y. J. Am. Chem. Soc. 1985, 107, 6117– 6118, DOI: 10.1021/ja00307a055 .(b) Nakabayashi, K.; Amako, T.; Tajima, N.; Fujiki, M.; Imai, Y. Chem. Commun. 2014, 50, 13228– 13230, DOI: 10.1039/C4CC02946A .(c) Amako, T.; Nakabayashi, K.; Suzuki, N.; Guo, S.; Rahim, N. A. A.; Harada, T.; Fujiki, M.; Imai, Y. Chem. Commun. 2015, 51, 8237– 8240, DOI: 10.1039/C5CC01465D .(d) Nakabayashi, K.; Kitamura, S.; Suzuki, N.; Guo, S.; Fujiki, M.; Imai, Y. Eur. J. Org. Chem. 2016, 2016, 64– 69, DOI: 10.1002/ejoc.201501316 .(e) Mimura, Y.; Nishikawa, T.; Fuchino, R.; Nakai, S.; Tajima, N.; Kitamatsu, M.; Fujiki, M.; Imai, Y. Org. Biomol. Chem. 2017, 15, 4548– 4553, DOI: 10.1039/C7OB00503B .(f) Takaishi, K.; Takehana, R.; Ema, T. Chem. Commun. 2018, 54, 1449– 1452, DOI: 10.1039/C7CC09187G[Crossref], [PubMed], [CAS], Google Scholar9fhttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXosFWnuw%253D%253D&md5=4036c50eccb46c7a11d15632d48a114dIntense excimer CPL of pyrenes linked to a quaternaphthylTakaishi, Kazuto; Takehana, Ryosuke; Ema, TadashiChemical Communications (Cambridge, United Kingdom) (2018), 54 (12), 1449-1452CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)(R,R,R)-Quaternaphthyls possessing eight and six pyrenes (compds. 4 and 3) displayed intense excimer-CPL. The glum values in soln. and in the solid state were +0.034-0.037 and +0.0053-0.0056, resp. The glum values of 3 and 4 were indistinguishable, indicating that the pyrenes of 3 and 4 assumed the same conformation, even in excited states. The intense CPL was caused by conformationally rigid pyrenes arranged via the cumulative steric effects along the quaternaphthyl axis.
- 10Martín-Lasanta, A.; Álvarez de Cienfuegos, L.; Johnson, A.; Miguel, D.; Mota, A. J.; Orte, A.; Ruedas-Rama, M. J.; Ribagorda, M.; Cárdenas, D. J.; Carreño, M. C.; Echavarren, A. M.; Cuerva, J. M. Chem. Sci. 2014, 5, 4582– 4591, DOI: 10.1039/C4SC01988A[Crossref], [CAS], Google Scholar10https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXht1amtrrK&md5=f1235d2297ef5d218d19507e31da4a08Novel ortho-OPE metallofoldamers: binding-induced folding promoted by nucleating Ag(I)-alkyne interactionsMartin-Lasanta, Ana; Alvarez de Cienfuegos, Luis; Johnson, Alice; Miguel, Delia; Mota, Antonio J.; Orte, Angel; Ruedas-Rama, Maria Jose; Ribagorda, Maria; Cardenas, Diego J.; Carmen Carreno, M.; Echavarren, Antonio M.; Cuerva, Juan M.Chemical Science (2014), 5 (12), 4582-4591CODEN: CSHCCN; ISSN:2041-6520. (Royal Society of Chemistry)We have developed a new family of ortho-oligophenylene ethynylene (o-OPE) metallofoldamers. The folding of these helicates is induced by nucleating carbon-metal interactions between Ag(I) cations and the alkynes of the inner core of the o-OPEs. These o-OPEs form metal-org. assemblies where at least three alkyne moieties are held in close proximity to form novel Ag(I)-complexes with the metal ion lodged into the helical cavity. NMR titrn. expts. and photokinetic studies have provided quant. data about the thermodn. and kinetic features of such binding/folding phenomena. X-ray diffraction and DFT studies have been performed to ext. structural information on how the Ag(I) cation is accommodated into the cavity. The great simplicity and versatility of these new metallofoldamers open up the possibility to develop novel structures with applications in material science and/or in asym. catalysis.
- 12DynaFit program was used to study guest-host complexation equilibria:Gasa, T.; Spruell, J.; Dichtel, W.; Sorensen, T.; Philp, D.; Stoddart, J.; Kuzmič, P. Chem. - Eur. J. 2009, 15, 106– 116, DOI: 10.1002/chem.200801827[Crossref], [PubMed], [CAS], Google Scholar12https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXkvVOgsQ%253D%253D&md5=f5cd8f54e5001530f7322a105e7c9d69Complexation between methyl viologen (paraquat) bis(hexafluorophosphate) and dibenzo[24]crown-8 revisitedGasa, Travis B.; Spruell, Jason M.; Dichtel, William R.; Sorensen, Thomas J.; Philp, Douglas; Stoddart, J. Fraser; Kuzmic, PetrChemistry - A European Journal (2009), 15 (1), 106-116CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)Paraquat bis(hexafluorophosphate) undergoes stepwise dissocn. in acetone. All three species-the neutral mol., and the mono- and dication are represented significantly under the exptl. conditions typically used in host-guest binding studies. Paraquat forms at least four host-guest complexes with dibenzo[24]crown-8. They are characterized by both 1:1 and 1:2 stoichiometries, and an overall charge of either zero (neutral mol.) or one (monocation). The mono-cationic 1:1 host-guest complex is the most abundant species under typical (0.5-20 mM) exptl. conditions. The presence of the dicationic 1:1 host-guest complex cannot be excluded on the basis of our exptl. data, but neither is it unambiguously confirmed to be present. The two confirmed forms of paraquat that do undergo complexation - the neutral mol. and the monocation - exhibit approx. identical binding affinities toward dibenzo[24]crown-8. Thus, the relative abundance of neutral, singly, and doubly charged pseudorotaxanes is identical to the relative abundance of neutral, singly, and doubly charged paraquat unbound with respect to the crown ether in acetone. In the specific case of paraquat/dibenzo[24]crown-8, ion-pairing does not contribute to host-guest complex formation, as has been suggested previously in the literature.
- 13
Some explanations about bisignated signals in CPL have been described:
(a) Longhi, G.; Castiglioni, E.; Abbate, S.; Lebon, F.; Lightner, D. A. Chirality 2013, 25, 589– 599, DOI: 10.1002/chir.22176 .(b) Hall, J.; Renger, T.; Picorel, R.; Krausz, E. Biochim. Biophys. Acta, Bioenerg. 2016, 1857, 115– 128, DOI: 10.1016/j.bbabio.2015.09.012[Crossref], [PubMed], [CAS], Google Scholar.13bhttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhs1ersLnP&md5=74a23263d95551bf6cf974f035db77d3Circularly polarized luminescence spectroscopy reveals low-energy excited states and dynamic localization of vibronic transitions in CP43Hall, Jeremy; Renger, Thomas; Picorel, Rafael; Krausz, ElmarsBiochimica et Biophysica Acta, Bioenergetics (2016), 1857 (1), 115-128CODEN: BBBEB4; ISSN:0005-2728. (Elsevier B. V.)Circularly polarized luminescence (CPL) spectroscopy is an established but relatively little-used technique that monitors the chirality of an emission. When applied to photosynthetic pigment assemblies, we find that CPL provides sensitive and detailed information on low-energy exciton states, reflecting the interactions, site energies and geometries of interacting pigments. CPL is the emission analog of CD (CD) and thus spectra explore the optical activity only of fluorescent states of the pigment-protein complex and consequently the nature of the lowest-energy excited states (trap states), whose study is a crit. area of photosynthesis research. In this work, we develop the new approach of temp.-dependent CPL spectroscopy, over the 2-120 K temp. range, and apply it to the CP43 proximal antenna protein of photosystem II. Our results confirm strong excitonic interactions for at least one of the two well-established emitting states of CP43 named "A" and "B". Previous structure-based models of CP43 spectra are evaluated in the light of the new CPL data. Our anal. supports the assignments of Shibata et al., particularly for the highly-delocalized B-state. This state dominates CPL spectra and is attributed predominantly to chlorophyll a's labeled Chl 634 and Chl 636 (alternatively labeled Chl 43 and 45 by Shibata et al.). The absence of any CPL intensity in intramol. vibrational sidebands assocd. with the delocalized "B" excited state is attributed to the dynamic localization of intramol. vibronic transitions.(c) Duong, S. T.; Fujiki, M. Polym. Chem. 2017, 8, 4673– 4679, DOI: 10.1039/C7PY00958E[Crossref], [CAS], Google Scholar13chttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhtFOlurzJ&md5=3e398c825f4127e8113ed89d963f297bThe origin of bisignate circularly polarized luminescence (CPL) spectra from chiral polymer aggregates and molecular camphor: anti-Kasha's rule revealed by CPL excitation (CPLE) spectraDuong, Sang Thi; Fujiki, MichiyaPolymer Chemistry (2017), 8 (32), 4673-4679CODEN: PCOHC2; ISSN:1759-9962. (Royal Society of Chemistry)The first circularly polarized luminescence (CPL) excitation (CPLE) measurements of poly(fluorene-alt-bithiophene) (PF8T2) aggregates with bisignate CPL/CD (CD) signals and, for comparison, bisignate CPL signal camphor were achieved. Based on this finding, we propose that Kasha's rule can be broken in chiral luminophore systems. The |gem| values of PF8T2 hetero-aggregate with help of helical polysilanes (PSi-S/-R) as sacrificial scaffoldings boosted to 0.05-0.08 at ≈510 and ≈540 nm assocd. with a high quantum yield of 0.33. The gem values arose from hugely amplified |gabs| values of 0.15-0.25 at ≈500 nm and ≈510 nm. Moreover, PF8T2 homo-aggregate, maintaining the bisignate CPL and CD spectral profiles, was generated by PSi-S/-R selective photoscissoring reaction at 313 nm for 10 s. - 14Due to the complexity of the molecular system and also the limitation of the TD-DFT approximation, a calculation explaining the observed rotational strengths is beyond the scope of this work:Levine, B. G.; Ko, C.; Quenneville, J.; Martinez, T. J. Mol. Phys. 2006, 104, 1039– 1051, DOI: 10.1080/00268970500417762
- 15
The linear response is observed up to 3 Ag(I) equivalents, taking into account that two fluorophores with different quantum yields must be recorded at the same time and the most intense peak determines the detector saturation and optimization process was carried out to minimize the spectral noise. Beyond such equivalents, the signals (ΔI) became too low that the errors in the measurement did not guarantee a reliable value of the ratio. With this limitation in the linear range, the resulted profile was exactly the expected one for a ratiometric probe.
There is no corresponding record for this reference. - 16
Although such apparatus is in its infancy, interesting real prototypes have been reported:
(a) Tsumatori, H.; Harada, T.; Yuasa, J.; Hasegawa, Y.; Kawai, T. Appl. Phys. Express 2011, 4, 011601, DOI: 10.1143/APEX.4.011601[Crossref], [CAS], Google Scholar.16ahttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXitVyhsbY%253D&md5=12ba8fe501af2d227a860ceb27846626Circularly polarized light from chiral lanthanide(III) complexes in single crystalsTsumatori, Hiroyuki; Harada, Takashi; Yuasa, Junpei; Hasegawa, Yasuchika; Kawai, TsuyoshiApplied Physics Express (2011), 4 (1), 011601/1-011601/3CODEN: APEPC4; ISSN:1882-0778. (Japan Society of Applied Physics)A circularly polarized emission (CPE) microscope system was designed for measuring circularly polarized light (CPL) from small single crystals of lanthanide(III) complexes with different crystal structures. CPL under excitation with 370-nm laser light was successfully obsd. from the crystals, and the CPL spectra were significantly different from those obsd. in soln. Dependence of the CPL spectra on the lattice plane of the crystals was also demonstrated.(b) Frawley, A. T.; Pal, R.; Parker, D. Chem. Commun. 2016, 52, 13349– 13352, DOI: 10.1039/C6CC07313A
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Abstract
Figure 1
Figure 1. Working hypothesis of a CPL-based ratiometric probe based on (P,1S,2S)-1.
Scheme 1
Scheme 1. Enantioespecific Synthesis of (P,1S,2S)-2 and (P,1S,2S)-3aaReaction conditions: (a) (1S,2S)-5, Cs2CO3, MeCN, 80 °C, 22 h, 77%; (b) p-TsOH, EtOH/H2O, reflux, 85%; (c) 1-chloromethylpyrene, NaH, DMF, rt, 12 h, 58%; (d) 1-pyrenecarboxylic acid, DCC, DMAP, rt, 24 h, 85%.
Figure 2
Figure 2. (a) TRES spectra of (P,1S,2S)-2 after a δ-pulse excitation as a function of time and emission wavelength in CH2Cl2 as a solvent. (b) SAEMS spectra of compound (P,1S,2S)-2 in CH2Cl2 as a solvent.
Figure 3
Figure 3. (a) TRES spectra of (P,1S,2S)-3 after a δ-pulse excitation as a function of time and emission wavelength in CH2Cl2 as a solvent. (b) SAEMS spectra of compound (P,1S,2S)-3 in CH2Cl2 as a solvent.
Figure 4
Figure 4. (a) Left: experimental (solid line) and average of the main calculated (dash-dotted line) CD spectra of compound (P,1S,2S)-2 in the absence (black) and presence (red) of Ag(I). Experimental intensity of the silver complex has been multiplied by 5. Right: calculated main conformer of (P,1S,2S)-2 in the absence (light blue) and presence (blue) of Ag(I). (b) Left: experimental (solid line) and average of the main calculated (dash-dotted line) CD spectra of compound (P,1S,2S)-3 in the absence (green) and presence (violet) of Ag(I). Right: CD titration of compound (P,1S,2S)-3. Offsets of 15 nm have been applied to theoretical data.
Figure 5
Figure 5. (a) Calculated first two conformers of (P,1S,2S)-2 in the absence (light blue) and presence (blue) of Ag(I).
Figure 6
Figure 6. Examples of different orbitals of the main conformer of (P,1S,2S)-2 (left) and (P,1S,2S)-3 (right) in the absence of Ag(I).
Figure 7
Figure 7. Fluorescence spectra (dashed line) and left–right (ΔI) intensities (solid line) of compounds (a) (P,1S,2S)-2 and (b) (P,1S,2S)-3. (ΔI intensities of the Ag(I) complex are referred to as right axis.) (c) CPL titration of compound (P,1S,2S)-2 with AgBF4. Inset: linear fitting of the ratio between left–right fluorescence intensity (ΔI) at 400 and 500 nm versus Ag(I) concentration.
References
ARTICLE SECTIONSThis article references 16 other publications.
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Recent interest, which has increased in the field of material science particularly, where the emission properties are more attractive and important than the absorption ones, has motivated new application fields and may change the situation in the future.(d) Berova, N.; Di Bari, L.; Pescitelli, G. Chem. Soc. Rev. 2007, 36, 914– 931, DOI: 10.1039/b515476f[Crossref], [PubMed], [CAS], Google Scholar.2dhttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2sXlvVShtbw%253D&md5=70f665606d761c4028555f760d1d3e19Application of electronic circular dichroism in configurational and conformational analysis of organic compoundsBerova, Nina; Di Bari, Lorenzo; Pescitelli, GennaroChemical Society Reviews (2007), 36 (6), 914-931CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)This tutorial review is addressed to readers with a background in basic org. chem. and spectroscopy, but without a specific knowledge of electronic CD. 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For recent examples, see:
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Its π-elongated and twisted structure resulted in the Cotton effect in the red region (λmax = 614 nm, Δε = 60 M-1·cm-1) as well as the strong fluorescence (ΦF = 0.73) and circularly polarized luminescence (CPL). [Bis(trifluoroacetoxy)iodo]benzene (808 mg, 1.88 mmol) and BF3≥OEt2.(b) Nishimura, H.; Tanaka, K.; Morisaki, Y.; Chujo, Y.; Wakamiya, A.; Murata, Y. J. Org. Chem. 2017, 82, 5242– 5249, DOI: 10.1021/acs.joc.7b00511[ACS Full Text.], [CAS], Google Scholar3bhttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXmsFajsb4%253D&md5=7bc0e85a51e5bb0ad1ef144e580d91f4Oxygen-Bridged Diphenylnaphthylamine as a Scaffold for Full-Color Circularly Polarized Luminescent MaterialsNishimura, Hidetaka; Tanaka, Kazuo; Morisaki, Yasuhiro; Chujo, Yoshiki; Wakamiya, Atsushi; Murata, YasujiroJournal of Organic Chemistry (2017), 82 (10), 5242-5249CODEN: JOCEAH; ISSN:0022-3263. 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F.; Kusaka, S.; Sakamoto, R.; Iwashima, T.; Tsuchiya, M.; Toyoda, R.; Matsuoka, R.; Tsukamoto, T.; Yuasa, J.; Kitagawa, Y.; Kawai, T.; Nishihara, H. Angew. Chem., Int. Ed. 2016, 55, 1377– 1381, DOI: 10.1002/anie.201509411 .(d) Feuillastre, S.; Pauton, M.; Gao, L.; Desmarchelier, A.; Riives, A. J.; Prim, D.; Tondelier, D.; Geffroy, B.; Muller, G.; Clavier, G.; Pieters, G. J. Am. Chem. Soc. 2016, 138, 3990– 3993, DOI: 10.1021/jacs.6b00850 .(e) Xiong, J.-B.; Feng, H.-T.; Sun, J.-P.; Xie, W.-Z.; Yang, D.; Liu, M.; Zheng, Y.-S. J. Am. Chem. Soc. 2016, 138, 11469– 11472, DOI: 10.1021/jacs.6b07087[ACS Full Text.], [CAS], Google Scholar3ehttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhsVWlsbjE&md5=91fbc770cdde21cb614ec76335c9a84cThe Fixed Propeller-Like Conformation of Tetraphenylethylene that Reveals Aggregation-Induced Emission Effect, Chiral Recognition, and Enhanced Chiroptical PropertyXiong, Jia-Bin; Feng, Hai-Tao; Sun, Jian-Ping; Xie, Wen-Zhao; Yang, Dong; Liu, Minghua; Zheng, Yan-SongJournal of the American Chemical Society (2016), 138 (36), 11469-11472CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)The propeller-like conformation of tetraphenylethylene (TPE) with aggregation-induced emission (AIE) effect was partially and completely fixed by intramol. cyclization for the first time. The immobilization of propeller-like conformation was found to show great advantages in detg. the enantiomer purity, identifying the chiral amines. The completely fixed conformers are resolved into M- and P-enantiomer, which showed mirror imaged CD and almost quant. fluorescence quantum yield. Also, it also showed a mirror and large circularly polarized luminescence dissym. factor, depending on the helicity of the enantiomer. The result provides the most direct and persuasive evidence for AIE via the restriction of intramol. rotation and finds the new insight of the compds. in chiroptical property.(f) Hellou, N.; Srebro-Hooper, M.; Favereau, L.; Zinna, F.; Caytan, E.; Toupet, L.; Dorcet, V.; Jean, M.; Vanthuyne, N.; Williams, J. A. G.; Di Bari, L.; Autschbach, J.; Crassous, J. Angew. Chem., Int. Ed. 2017, 56, 8236– 8239, DOI: 10.1002/anie.201704263 .(g) Schulte, T. R.; Holstein, J. J.; Krause, L.; Michel, R.; Stalke, D.; Sakuda, E.; Umakoshi, K.; Longhi, G.; Abbate, S.; Clever, G. H. J. Am. Chem. Soc. 2017, 139, 6863– 6866, DOI: 10.1021/jacs.7b03963 .(h) Gon, M.; Morisaki, Y.; Chujo, Y. Chem. Commun. 2017, 53, 8304– 8307, DOI: 10.1039/C7CC03615A .(i) Resa, S.; Miguel, D.; Guisán-Ceinos, S.; Mazzeo, G.; Choquesillo-Lazarte, D.; Abbate, S.; Crovetto, L.; Cárdenas, D. J.; Carreño, M. C.; Ribagorda, M.; Longhi, G.; Mota, A. J.; Álvarez de Cienfuegos, L.; Cuerva, J. M. Chem. - Eur. J. 2018, 24, 2653– 2662, DOI: 10.1002/chem.201704897[Crossref], [PubMed], [CAS], Google Scholar3ihttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhsVKisbs%253D&md5=b99f6171feca6587b46247c282b4631dSulfoxide-Induced Homochiral Folding of ortho-Phenylene Ethynylenes (o-OPEs) by Silver(I) Templating: Structure and Chiroptical PropertiesResa, Sandra; Miguel, Delia; Guisan-Ceinos, Santiago; Mazzeo, Giuseppe; Choquesillo-Lazarte, Duane; Abbate, Sergio; Crovetto, Luis; Cardenas, Diego J.; Carreno, M. Carmen; Ribagorda, Maria; Longhi, Giovanna; Mota, Antonio J.; Alvarez de Cienfuegos, Luis; Cuerva, Juan M.Chemistry - A European Journal (2018), 24 (11), 2653-2662CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)A new family of homochiral silver complexes based on carbophilic interactions with ortho-phenylene ethynylene (o-OPE) scaffolds contg. up to two silver atoms are described. These compds. represent a unique class of complexes with chirality at the metal. Chiral induction is based on the inclusion of chiral sulfoxides, which allow efficient transfer of chirality to the helically folded o-OPE, leading to circularly polarized luminescence (CPL)- and vibrational CD (VCD)-active compds. In the presence of silver(I) cations, carbophilic interactions dominate, which promote helical structures with a defined helicity. This is one of the very scarce examples of the use of such interactions in the attractive field of abiotic foldamers. The switching event has been extensively studied by using different chiroptical techniques, including CD, CPL, and VCD, and represents one of the few CPL switches described in the literature. - 4
For example, see:
(a) Maeda, H.; Bando, Y.; Shimomura, K.; Yamada, I.; Naito, M.; Nobusawa, K.; Tsumatori, H.; Kawai, T. J. Am. Chem. Soc. 2011, 133, 9266– 9269, DOI: 10.1021/ja203206g .(b) Maeda, H.; Shirai, T.; Bando, Y.; Takaishi, K.; Uchiyama, M.; Muranaka, A.; Kawai, T.; Naito, M. Org. Lett. 2013, 15, 6006– 6009, DOI: 10.1021/ol402895r .(c) Saleh, N.; Moore, B.; Srebro, M.; Vanthuyne, N.; Toupet, L.; Williams, J. A. G.; Roussel, C.; Deol, K. K.; Muller, G.; Autschbach, J.; Crassous, J. Chem. - Eur. J. 2015, 21, 1673– 1681, DOI: 10.1002/chem.201405176[Crossref], [PubMed], [CAS], Google Scholar.4chttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhvFKmtb7L&md5=076f30defb61cc784b70a3c1f58bafcdAcid/Base-Triggered Switching of Circularly Polarized Luminescence and Electronic Circular Dichroism in Organic and Organometallic HelicenesSaleh, Nidal; Moore, Barry II; Srebro, Monika; Vanthuyne, Nicolas; Toupet, Loic; Williams, J. A. Gareth; Roussel, Christian; Deol, Kirandeep K.; Muller, Gilles; Autschbach, Jochen; Crassous, JeanneChemistry - A European Journal (2015), 21 (4), 1673-1681CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)Electronic CD and circularly polarized luminescence acid/base switching activity has been demonstrated in helicene-bipyridine proligand 1a and in its "rollover" cycloplatinated deriv. 2a. Whereas proligand 1a displays a strong bathochromic shift (>160 nm) of the nonpolarized and circularly polarized luminescence upon protonation, complex 2a displays slightly stronger emission. This strikingly different behavior between singlet emission in the org. helicene and triplet emission in the organometallic deriv. has been rationalized by using quantum-chem. calcns. The very large bathochromic shift of the emission obsd. upon protonation of azahelicene-bipyridine 1a has been attributed to the decrease in aromaticity (promoting a charge-transfer-type transition rather than a π-π* transition) as well as an increase in the HOMO-LUMO character of the transition and stabilization of the LUMO level upon protonation.(d) Hashimoto, Y.; Nakashima, T.; Shimizu, D.; Kawai, T. Chem. Commun. 2016, 52, 5171– 5174, DOI: 10.1039/C6CC01277A .(e) Isla, H.; Srbo-Hooper, M.; Jean, M.; Vanthuyne, N.; Roisnel, T.; Lunkley, J. L.; Muller, G.; Willians, J. A. G.; Autschbach, J.; Crassous, J. Chem. Commun. 2016, 52, 5932– 5935 - 5(a) Morcillo, S. P.; Miguel, D.; Álvarez de Cienfuegos, L.; Justicia, J.; Abbate, S.; Castiglioni, E.; Bour, C.; Ribagorda, M.; Cárdenas, D. J.; Paredes, J. M.; Crovetto, L.; Choquesillo-Lazarte, D.; Mota, A. J.; Carreño, M. C.; Longhi, G.; Cuerva, J. M. Chem. Sci. 2016, 7, 5663– 5670, DOI: 10.1039/C6SC01808D[Crossref], [PubMed], [CAS], Google Scholar.5ahttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XotVWlsrY%253D&md5=d9a83ef62dc2df47f742e07a630dae59Stapled helical o-OPE foldamers as new circularly polarized luminescence emitters based on carbophilic interactions with Ag(I)-sensitivityMorcillo, Sara P.; Miguel, Delia; Alvarez de Cienfuegos, Luis; Justicia, Jose; Abbate, Sergio; Castiglioni, Ettore; Bour, Christophe; Ribagorda, Maria; Cardenas, Diego J.; Paredes, Jose Manuel; Crovetto, Luis; Choquesillo-Lazarte, Duane; Mota, Antonio J.; Carreno, M. Carmen; Longhi, Giovanna; Cuerva, Juan M.Chemical Science (2016), 7 (9), 5663-5670CODEN: CSHCCN; ISSN:2041-6520. (Royal Society of Chemistry)Ortho-Oligo(phenylene)ethynylenes (o-OPEs) stapled with enantiopure 2,3-dihydroxybutane diethers have highly intense CD (CD) spectra and excellent circular polarized luminescence (CPL) responses (glum values up to 1.1 × 10-2), which are consistent with homochiral helically folded structures. In the presence of Ag(I), a change in the CPL emission is obsd., representing the first example of CPL active small org. mol. emitters, which can be modulated by carbophilic interactions in a reversible manner.(b) Fuentes, N.; Martin-Lasanta, A.; Alvarez de Cienfuegos, L.; Robles, R.; Choquesillo-Lazarte, D.; Garcia-Ruiz, J. M.; Martinez-Fernandez, L.; Corral, I.; Ribagorda, M.; Mota, A. J.; Cárdenas, D. J.; Carreño, M. C.; Cuerva, J. M. Angew. Chem., Int. Ed. 2012, 51, 13036– 13040, DOI: 10.1002/anie.201206259
- 6
The corresponding enantiomers (M,1R,2R)-2 and (M,1R,2R)-3 were also prepared using ditosilate (1R,2R)-5, showing mirror-image chiroptical properties. See the Supporting Information.
There is no corresponding record for this reference. - 7Reiné, P.; Justicia, J.; Morcillo, S. P.; Mazzeo, G.; García-Fernández, E.; Rodríguez-Diéguez, A.; Álvarez de Cienfuegos, L.; Abbate, S.; Cuerva, J. M.; Longhi, G.; Miguel, D. Chirality 2018, 30, 43– 54, DOI: 10.1002/chir.22774
- 8(a) Kanaya, T.; Goshiki, K.; Yamamoto, M.; Nishijima, Y. J. Am. Chem. Soc. 1982, 104, 3580– 3587, DOI: 10.1021/ja00377a007 .(b) Yamamoto, M.; Goshiki, K.; Kanaya, T.; Nishijima, Y. Chem. Phys. Lett. 1978, 56, 333– 335, DOI: 10.1016/0009-2614(78)80253-X .(c) Miguel, D.; Morcillo, S. P.; Martín-Lasanta, A.; Fuentes, N.; Martínez-Fernández, L.; Corral, I.; Ruedas-Rama, M. J.; Cárdenas, D. J.; Álvarez de Cienfuegos, L.; Orte, A.; Cuerva, J. M. Org. Lett. 2015, 17, 2844– 2847, DOI: 10.1021/acs.orglett.5b01275
- 9(a) Kano, K.; Matsumoto, H.; Hashimoto, S.; Sisido, M.; Imanishi, Y. J. Am. Chem. Soc. 1985, 107, 6117– 6118, DOI: 10.1021/ja00307a055 .(b) Nakabayashi, K.; Amako, T.; Tajima, N.; Fujiki, M.; Imai, Y. Chem. Commun. 2014, 50, 13228– 13230, DOI: 10.1039/C4CC02946A .(c) Amako, T.; Nakabayashi, K.; Suzuki, N.; Guo, S.; Rahim, N. A. A.; Harada, T.; Fujiki, M.; Imai, Y. Chem. Commun. 2015, 51, 8237– 8240, DOI: 10.1039/C5CC01465D .(d) Nakabayashi, K.; Kitamura, S.; Suzuki, N.; Guo, S.; Fujiki, M.; Imai, Y. Eur. J. Org. Chem. 2016, 2016, 64– 69, DOI: 10.1002/ejoc.201501316 .(e) Mimura, Y.; Nishikawa, T.; Fuchino, R.; Nakai, S.; Tajima, N.; Kitamatsu, M.; Fujiki, M.; Imai, Y. Org. Biomol. Chem. 2017, 15, 4548– 4553, DOI: 10.1039/C7OB00503B .(f) Takaishi, K.; Takehana, R.; Ema, T. Chem. Commun. 2018, 54, 1449– 1452, DOI: 10.1039/C7CC09187G[Crossref], [PubMed], [CAS], Google Scholar9fhttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXosFWnuw%253D%253D&md5=4036c50eccb46c7a11d15632d48a114dIntense excimer CPL of pyrenes linked to a quaternaphthylTakaishi, Kazuto; Takehana, Ryosuke; Ema, TadashiChemical Communications (Cambridge, United Kingdom) (2018), 54 (12), 1449-1452CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)(R,R,R)-Quaternaphthyls possessing eight and six pyrenes (compds. 4 and 3) displayed intense excimer-CPL. The glum values in soln. and in the solid state were +0.034-0.037 and +0.0053-0.0056, resp. The glum values of 3 and 4 were indistinguishable, indicating that the pyrenes of 3 and 4 assumed the same conformation, even in excited states. The intense CPL was caused by conformationally rigid pyrenes arranged via the cumulative steric effects along the quaternaphthyl axis.
- 10Martín-Lasanta, A.; Álvarez de Cienfuegos, L.; Johnson, A.; Miguel, D.; Mota, A. J.; Orte, A.; Ruedas-Rama, M. J.; Ribagorda, M.; Cárdenas, D. J.; Carreño, M. C.; Echavarren, A. M.; Cuerva, J. M. Chem. Sci. 2014, 5, 4582– 4591, DOI: 10.1039/C4SC01988A[Crossref], [CAS], Google Scholar10https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXht1amtrrK&md5=f1235d2297ef5d218d19507e31da4a08Novel ortho-OPE metallofoldamers: binding-induced folding promoted by nucleating Ag(I)-alkyne interactionsMartin-Lasanta, Ana; Alvarez de Cienfuegos, Luis; Johnson, Alice; Miguel, Delia; Mota, Antonio J.; Orte, Angel; Ruedas-Rama, Maria Jose; Ribagorda, Maria; Cardenas, Diego J.; Carmen Carreno, M.; Echavarren, Antonio M.; Cuerva, Juan M.Chemical Science (2014), 5 (12), 4582-4591CODEN: CSHCCN; ISSN:2041-6520. (Royal Society of Chemistry)We have developed a new family of ortho-oligophenylene ethynylene (o-OPE) metallofoldamers. The folding of these helicates is induced by nucleating carbon-metal interactions between Ag(I) cations and the alkynes of the inner core of the o-OPEs. These o-OPEs form metal-org. assemblies where at least three alkyne moieties are held in close proximity to form novel Ag(I)-complexes with the metal ion lodged into the helical cavity. NMR titrn. expts. and photokinetic studies have provided quant. data about the thermodn. and kinetic features of such binding/folding phenomena. X-ray diffraction and DFT studies have been performed to ext. structural information on how the Ag(I) cation is accommodated into the cavity. The great simplicity and versatility of these new metallofoldamers open up the possibility to develop novel structures with applications in material science and/or in asym. catalysis.
- 12DynaFit program was used to study guest-host complexation equilibria:Gasa, T.; Spruell, J.; Dichtel, W.; Sorensen, T.; Philp, D.; Stoddart, J.; Kuzmič, P. Chem. - Eur. J. 2009, 15, 106– 116, DOI: 10.1002/chem.200801827[Crossref], [PubMed], [CAS], Google Scholar12https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXkvVOgsQ%253D%253D&md5=f5cd8f54e5001530f7322a105e7c9d69Complexation between methyl viologen (paraquat) bis(hexafluorophosphate) and dibenzo[24]crown-8 revisitedGasa, Travis B.; Spruell, Jason M.; Dichtel, William R.; Sorensen, Thomas J.; Philp, Douglas; Stoddart, J. Fraser; Kuzmic, PetrChemistry - A European Journal (2009), 15 (1), 106-116CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)Paraquat bis(hexafluorophosphate) undergoes stepwise dissocn. in acetone. All three species-the neutral mol., and the mono- and dication are represented significantly under the exptl. conditions typically used in host-guest binding studies. Paraquat forms at least four host-guest complexes with dibenzo[24]crown-8. They are characterized by both 1:1 and 1:2 stoichiometries, and an overall charge of either zero (neutral mol.) or one (monocation). The mono-cationic 1:1 host-guest complex is the most abundant species under typical (0.5-20 mM) exptl. conditions. The presence of the dicationic 1:1 host-guest complex cannot be excluded on the basis of our exptl. data, but neither is it unambiguously confirmed to be present. The two confirmed forms of paraquat that do undergo complexation - the neutral mol. and the monocation - exhibit approx. identical binding affinities toward dibenzo[24]crown-8. Thus, the relative abundance of neutral, singly, and doubly charged pseudorotaxanes is identical to the relative abundance of neutral, singly, and doubly charged paraquat unbound with respect to the crown ether in acetone. In the specific case of paraquat/dibenzo[24]crown-8, ion-pairing does not contribute to host-guest complex formation, as has been suggested previously in the literature.
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Some explanations about bisignated signals in CPL have been described:
(a) Longhi, G.; Castiglioni, E.; Abbate, S.; Lebon, F.; Lightner, D. A. Chirality 2013, 25, 589– 599, DOI: 10.1002/chir.22176 .(b) Hall, J.; Renger, T.; Picorel, R.; Krausz, E. Biochim. Biophys. Acta, Bioenerg. 2016, 1857, 115– 128, DOI: 10.1016/j.bbabio.2015.09.012[Crossref], [PubMed], [CAS], Google Scholar.13bhttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhs1ersLnP&md5=74a23263d95551bf6cf974f035db77d3Circularly polarized luminescence spectroscopy reveals low-energy excited states and dynamic localization of vibronic transitions in CP43Hall, Jeremy; Renger, Thomas; Picorel, Rafael; Krausz, ElmarsBiochimica et Biophysica Acta, Bioenergetics (2016), 1857 (1), 115-128CODEN: BBBEB4; ISSN:0005-2728. (Elsevier B. V.)Circularly polarized luminescence (CPL) spectroscopy is an established but relatively little-used technique that monitors the chirality of an emission. When applied to photosynthetic pigment assemblies, we find that CPL provides sensitive and detailed information on low-energy exciton states, reflecting the interactions, site energies and geometries of interacting pigments. CPL is the emission analog of CD (CD) and thus spectra explore the optical activity only of fluorescent states of the pigment-protein complex and consequently the nature of the lowest-energy excited states (trap states), whose study is a crit. area of photosynthesis research. In this work, we develop the new approach of temp.-dependent CPL spectroscopy, over the 2-120 K temp. range, and apply it to the CP43 proximal antenna protein of photosystem II. Our results confirm strong excitonic interactions for at least one of the two well-established emitting states of CP43 named "A" and "B". Previous structure-based models of CP43 spectra are evaluated in the light of the new CPL data. Our anal. supports the assignments of Shibata et al., particularly for the highly-delocalized B-state. This state dominates CPL spectra and is attributed predominantly to chlorophyll a's labeled Chl 634 and Chl 636 (alternatively labeled Chl 43 and 45 by Shibata et al.). The absence of any CPL intensity in intramol. vibrational sidebands assocd. with the delocalized "B" excited state is attributed to the dynamic localization of intramol. vibronic transitions.(c) Duong, S. T.; Fujiki, M. Polym. Chem. 2017, 8, 4673– 4679, DOI: 10.1039/C7PY00958E[Crossref], [CAS], Google Scholar13chttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhtFOlurzJ&md5=3e398c825f4127e8113ed89d963f297bThe origin of bisignate circularly polarized luminescence (CPL) spectra from chiral polymer aggregates and molecular camphor: anti-Kasha's rule revealed by CPL excitation (CPLE) spectraDuong, Sang Thi; Fujiki, MichiyaPolymer Chemistry (2017), 8 (32), 4673-4679CODEN: PCOHC2; ISSN:1759-9962. (Royal Society of Chemistry)The first circularly polarized luminescence (CPL) excitation (CPLE) measurements of poly(fluorene-alt-bithiophene) (PF8T2) aggregates with bisignate CPL/CD (CD) signals and, for comparison, bisignate CPL signal camphor were achieved. Based on this finding, we propose that Kasha's rule can be broken in chiral luminophore systems. The |gem| values of PF8T2 hetero-aggregate with help of helical polysilanes (PSi-S/-R) as sacrificial scaffoldings boosted to 0.05-0.08 at ≈510 and ≈540 nm assocd. with a high quantum yield of 0.33. The gem values arose from hugely amplified |gabs| values of 0.15-0.25 at ≈500 nm and ≈510 nm. Moreover, PF8T2 homo-aggregate, maintaining the bisignate CPL and CD spectral profiles, was generated by PSi-S/-R selective photoscissoring reaction at 313 nm for 10 s. - 14Due to the complexity of the molecular system and also the limitation of the TD-DFT approximation, a calculation explaining the observed rotational strengths is beyond the scope of this work:Levine, B. G.; Ko, C.; Quenneville, J.; Martinez, T. J. Mol. Phys. 2006, 104, 1039– 1051, DOI: 10.1080/00268970500417762
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The linear response is observed up to 3 Ag(I) equivalents, taking into account that two fluorophores with different quantum yields must be recorded at the same time and the most intense peak determines the detector saturation and optimization process was carried out to minimize the spectral noise. Beyond such equivalents, the signals (ΔI) became too low that the errors in the measurement did not guarantee a reliable value of the ratio. With this limitation in the linear range, the resulted profile was exactly the expected one for a ratiometric probe.
There is no corresponding record for this reference. - 16
Although such apparatus is in its infancy, interesting real prototypes have been reported:
(a) Tsumatori, H.; Harada, T.; Yuasa, J.; Hasegawa, Y.; Kawai, T. Appl. Phys. Express 2011, 4, 011601, DOI: 10.1143/APEX.4.011601[Crossref], [CAS], Google Scholar.16ahttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXitVyhsbY%253D&md5=12ba8fe501af2d227a860ceb27846626Circularly polarized light from chiral lanthanide(III) complexes in single crystalsTsumatori, Hiroyuki; Harada, Takashi; Yuasa, Junpei; Hasegawa, Yasuchika; Kawai, TsuyoshiApplied Physics Express (2011), 4 (1), 011601/1-011601/3CODEN: APEPC4; ISSN:1882-0778. (Japan Society of Applied Physics)A circularly polarized emission (CPE) microscope system was designed for measuring circularly polarized light (CPL) from small single crystals of lanthanide(III) complexes with different crystal structures. CPL under excitation with 370-nm laser light was successfully obsd. from the crystals, and the CPL spectra were significantly different from those obsd. in soln. Dependence of the CPL spectra on the lattice plane of the crystals was also demonstrated.(b) Frawley, A. T.; Pal, R.; Parker, D. Chem. Commun. 2016, 52, 13349– 13352, DOI: 10.1039/C6CC07313A
Supporting Information
Supporting Information
ARTICLE SECTIONSThe Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.joc.8b00162.
Experimental details on optical measurements, further details on theoretical calculations of computed structures, and spectral data (PDF)
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