Polarizability as a landmark property for fullerene chemistry and materials science

Sabirov, Denis Sh.

doi:10.1039/c4ra06116k

Cited by 76 publications

(90 citation statements)

References 242 publications

(377 reference statements)

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“…According to these data, all studied structures show great values for static polarizability which is due to many delocalized π-electrons over these molecules. The value of 69.5 Å 3 , calculated at the mentioned level of theory for polarizability of C 60 fullerene, is in satisfactory agreement with previous experimental and theoretical results [62,63], for instant the value of 76.5±8.0 Å 3 by molecular beam deflection technique [64]. According to the calculation, differences in mean polarizabilities of SN-and NBisomers of both target azafullerenes are noticeable.…”

Section: Molecular Electronic Propertiessupporting

confidence: 87%

“…According to the calculation, differences in mean polarizabilities of SN-and NBisomers of both target azafullerenes are noticeable. This is while the previous studies on different exohedral fullerene derivatives (e.g., C 60 (CH 2 ) n and C 60 (NH) n cycloadducts [65]) by Sabirov [63] have shown that mean polarizability of those compounds does not significantly depend on the isomerism. However, for those regioisomeric fullerene bisand multiadducts, differences are observed in anisotropy (a 2 ) of their polarizability [63].…”

Section: Molecular Electronic Propertiesmentioning

confidence: 58%

“…For comparison, the values for a 2 , calculated using the components of diagonalized polarizability tensors, and also the obtained values for optical anisotropy (δ 2 ) [63] of the target fullerenes in this study are also given in Table 6. Anisotropy plays significant role in the application of fullerene derivatives as electron acceptor materials for organic solar cells [66,67].…”

Section: Molecular Electronic Propertiesmentioning

confidence: 99%

See 2 more Smart Citations

Introduction and theoretical investigation of new azafullerene structures with nitrogen belts

Nekoei

Haghgoo

2015

Computational and Theoretical Chemistry

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Section: Molecular Electronic Propertiessupporting

confidence: 87%

Section: Molecular Electronic Propertiesmentioning

confidence: 58%

Section: Molecular Electronic Propertiesmentioning

confidence: 99%

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Introduction and theoretical investigation of new azafullerene structures with nitrogen belts

Nekoei

Haghgoo

2015

Computational and Theoretical Chemistry

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“…24 In contrast to what is often believed, 25 dispersive and not electrostatic effects seem to be the major stabilizing factor in π−π and C−H−π interactions. 26 Substituent effects in π stacking can be explained solely in terms of direct interactions with the substituents.…”

Section: Stacking and Dispersive Interactions In Selected Supramolecumentioning

confidence: 88%

Dispersive Interactions in Solution Complexes

Schneider

2015

Acc. Chem. Res.

110

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Dispersive interactions are known to play a major role in molecular associations in the gas phase and in the solid state. In solution, however, their significance has been disputed in recent years on the basis of several arguments. A major problem until now has been the separation of dispersive and hydrophobic effects, which are both maximized in water due the low polarizability of this most important medium. Analyses of complexes between porphyrins and systematically varied substrates in water have allowed us to discriminate dispersive from hydrophobic effects, as the latter turned out to be negligible for complexations with flat surfaces such as porphyrins. Also, for the first time, it has become possible to obtain binding free energy increments ΔΔG for a multitude of organic residues including halogen, amide, amino, ether, carbonyl, ester, nitro, sulfur, unsatured, and cyclopropane groups, which turned out to be additive. Binding contributions for saturated residues are unmeasurably small, with ΔΔG > 1 kJ/mol, but they increase to, e.g., ΔΔG = 5 kJ/mol for a nitro group, a value not far from, e.g., that of a stacking pyridine ring. Stacking interactions of heteroarenes with porphyrins depend essentially on the size of the arenes, in line with polarizabilities, and seem to be rather independent of the position of nitrogen within the rings. Measurements of halogen derivatives indicate that complexes with porphyrins, cyclodextrins, and pillarenes as hosts in different media consistently show increasing stability from fluorine to iodine as the substituent. This, and the observed sequence with other substrates, is in line with the expected increase in dispersive forces with increasing polarizability. Induced dipoles, which also would increase with polarizability, can be ruled out as providing the driving source in view of the data with halides: the observed stability sequence is opposite the change of electronegativity from fluorine to iodine. The same holds for the solvent effect observed in ethanol-water mixtures. Dispersive contributions vary not only with the polarizability of the used media but also with the interacting receptor sites; it has been shown that for cucurbiturils the polarizability inside the cavity is extremely low, which also explains why hydrophobic effects are maximized with these hosts. Complexations with other known host compounds, however, such as those between cryptands or cavitands with, e.g., noble gases, bear the signature of dominating dispersive forces. Some recent examples illustrate that such van der Waals forces can also play an important role in complexations with proteins. Again, a clue for this is the increase in ΔG for inhibitor binding by 7 kJ/mol for, e.g., a bromine in comparison to a fluorine derivative.

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“…The optically generated dipoles have been estimated by calculating the dipole-moment change from ground state to excited state 13, 15 -17 . It should be pointed out that the widely used acceptor molecules of fullerene derivatives possess very high polarizabilities in exposure to an electric field 18,19,20 . With the high polarizabilities a photoexcitation can largely polarize the fullerene molecules, leading to optically polarized acceptor molecules.…”

Section: Introductionmentioning

confidence: 99%

Revealing optically induced dipole-dipole interaction effects on charge dissociation at donor:acceptor interfaces in organic solar cells under device-operating condition

Hsiao

et al. 2016

Nano Energy

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Organic materials normally have low dielectric constants and are often formed with high electron-hole binding energy, which are detrimental to the generation of photovoltaic actions in solution-processing thin-film solar cells. Here, we show that optically induced dipoledipole interaction can largely decrease the electron-hole binding energy at donor:acceptor (D:A) based on the PTB7:PCBM bulk-heterojunctions. Our experimental measurements combine (i) double-beam 325 nm and 532 nm excitations to establish dipole-dipole interaction by selectively exciting the intramolecular charge-transfer donor and optically polarizable acceptor and (ii) magneto-photocurrent to monitor the electron-hole binding energy through charge dissociation at D:A interfaces. We find that the electron-hole binding energy at D:A interfaces can be significantly decreased when the dipole-dipole interaction is optically established in PTB7:PCBM solar cells. Furthermore, the dipole-dipole interaction forms a drifting field to facilitate charge transport, and consequently enhancing the V oc and FF in developing photovoltaic actions in organic solar cells.

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Polarizability as a landmark property for fullerene chemistry and materials science

Abstract: The review summarizes data on dipole polarizability of fullerenes and their derivatives, covering the most widespread classes of fullerene-containing molecules (fullerenes, fullerene exohedral derivatives, fullerene dimers, endofullerenes, fullerene ions, and derivatives with ionic bonds).

Cited by 76 publications

References 242 publications

Introduction and theoretical investigation of new azafullerene structures with nitrogen belts

Introduction and theoretical investigation of new azafullerene structures with nitrogen belts

Dispersive Interactions in Solution Complexes

Revealing optically induced dipole-dipole interaction effects on charge dissociation at donor:acceptor interfaces in organic solar cells under device-operating condition

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