Influence of Topology on the Long-Range Electron-Transfer Phenomenon

Rovira, Concepció; Ruiz‐Molina, Daniel; Elsner, Olaf; Vidal-Gancedo, José; Bonvoisin, Jacques; Launay, Jean‐Pierre; Veciana, Jaume

doi:10.1002/1521-3765(20010105)7:1<240::aid-chem240>3.0.co;2-h

Cited by 96 publications

(47 citation statements)

References 49 publications

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“…[6][7][8][9][10][11][12][13][14] In a purely computational study, Lacroix and coworkers arrived at the conclusion that oligothiophene monocations may be described as organic mixed-valence species. 15 Indeed, the oneelectron oxidized or one-electron reduced forms of several oligo-p-phenylene and oligo-p-phenylene vinylene systems could be described well as organic mixed-valence compounds in various experimental studies, [16][17][18][19][20][21][22][23][24][25] but until now there has been comparatively little conceptually analogous work on thiophene systems. [26][27][28][29][30][31][32][33][34][35] A notable exception is the recent study of the oxidized forms of bis (4-(alkoxyphenyl)amino) derivatives of dithienylethene and bithiophene and the finding that a mixed-3 valence description of these cations is meaningful.…”

Section: Introductionmentioning

confidence: 86%

Charge Delocalization in a Homologous Series of α,α′-Bis(dianisylamino)-Substituted Thiophene Monocations

et al. 2012

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A homologous series of three molecules containing thiophene, bithiophene and terthiophene bridges between two redox-active tertiary amino-groups was synthesized and explored. Charge-delocalization in the one-electron oxidized forms of these molecules was investigated by a combination of cyclic voltammetry, near-infrared optical absorption spectroscopy, and EPR spectroscopy. All three cation radicals can be described as organic mixed-valence species, and for all of them the experimental data is consistent with strong delocalization of the unpaired electron. Depending on what model is used for 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 2 analysis of the optical absorption data, estimates for the electronic coupling matrix element (H AB ) range from ∼5000 cm -1 to ∼7000 cm -1 for the shortest member of the homologous series. According to optical absorption and EPR spectroscopy even the terthiophene radical appears to belong either to Robin-Day class III or to a category of radicals commonly denominated as borderline class II / class III systems. The finding of such a large extent of charge delocalization over up to three adjacent thiophene units is remarkable.

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Section: Introductionmentioning

confidence: 86%

Charge Delocalization in a Homologous Series of α,α′-Bis(dianisylamino)-Substituted Thiophene Monocations

et al. 2012

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“…The synthesis of all non-radical TTF-π-PTM derivatives 2a-2c was carried out by a Horner-Wadsworth-Emmons reaction of the phosphonated-functionalized non-radical PTM derivative 5 [38] with the formyl-TTF derivatives 3a-3c (Scheme 3). Compounds 2a and 2b were obtained in 70 % yield whereas 2c was obtained in moderate yield (40 %).…”

Section: Synthesismentioning

confidence: 99%

Tetrathiafulvalene–Polychlorotriphenylmethyl Dyads: Influence of Bridge and Open‐Shell Characteristics on Linear and Nonlinear Optical Properties

Souto

Calbo

Ratera

et al. 2017

Chemistry A European J

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Abstract:In this article, three conjugated donor-π-acceptor radical systems (1a-1c) based on a tetrathiafulvalene (TTF) unit, as electron-donor, connected to a polychlorotriphenylmethyl (PTM) radical, as electron-acceptor, through different vinylene units as bridge have been synthesized. The dependence of the intramolecular charge transfer on the length of the conjugated bridge has been analysed by different electrochemical and spectroscopic techniques. In addition, linear optical properties and the secondorder non-linear optical (NLO) response of these derivatives have been theoretically calculated by comparing with their non-radical analogues (2a-2c). Interestingly, an enhanced NLO response is predicted when the PTM is in its radical form as well as when the length of the bridge becomes longer. Theoretical calculations confirm the active role of the bridge in the electronic communication between the donor TTF and the acceptor PTM units.

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“…Typical redox centers are e.g. triarylamines, [5][6][7][8][9][10] perchlorotriphenylmethyl radicals, [11][12][13] hydrazines, 14,15 dimethoxybenzenes, 16,17 or quinones. 18,19 ET may proceed between the redox centers via the bridge, thermally or optically induced.…”

Section: Introductionmentioning

confidence: 99%

“…This is the situation in the bis-triarylamine radical cation 5 which has a large bridge separating the two triarylamine redox centers and which is clearly class II. If 2V 12 is larger than l, the barrier separating the two minima vanishes and we reach a situation with a single minimum (see Fig. 1b) as is realized in compound 4, where the two triarylamines share a single phenylene unit.…”

Section: Introductionmentioning

confidence: 99%

Computational and spectroscopic studies of organic mixed-valence compounds: where is the charge?

Kaupp

Renz

Parthey

et al. 2011

Phys. Chem. Chem. Phys.

128

157

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This article discusses recent progress by a combination of spectroscopy and quantum-chemical calculations in classifying and characterizing organic mixed-valence systems in terms of their localized vs. delocalized character. A recently developed quantum-chemical protocol based on non-standard hybrid functionals and continuum solvent models is evaluated for an extended set of mixed-valence bis-triarylamine radical cations, augmented by unsymmetrical neutral triarylamine-perchlorotriphenylmethyl radicals. It turns out that the protocol is able to provide a successful assignment to class II or class III Robin-Day behavior and gives quite accurate ground-and excited-state properties for the radical cations. The limits of the protocol are probed by the anthracene-bridged system 8, where it is suspected that specific solute-solvent interactions are important and not covered by the continuum solvent model. Intervalence charge-transfer excitation energies for the neutral unsymmetrical radicals are systematically overestimated, but dipole moments and a number of other properties are obtained accurately by the protocol.

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Influence of Topology on the Long-Range Electron-Transfer Phenomenon

Cited by 96 publications

References 49 publications

Charge Delocalization in a Homologous Series of α,α′-Bis(dianisylamino)-Substituted Thiophene Monocations

Charge Delocalization in a Homologous Series of α,α′-Bis(dianisylamino)-Substituted Thiophene Monocations

Tetrathiafulvalene–Polychlorotriphenylmethyl Dyads: Influence of Bridge and Open‐Shell Characteristics on Linear and Nonlinear Optical Properties

Computational and spectroscopic studies of organic mixed-valence compounds: where is the charge?

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