A mixed-valence bis(diarylamino)stilbene: crystal structure and comparison of electronic coupling with biphenyl and tolane analogues

Barlow, Stephen; Risko, Chad; Coropceanu, Veaceslav; Tucker, Neil M.; Jones, Simon C.; Levi, Zerubba; Khrustalev, Victor N.; Antipin, M. Yu.; Kinnibrugh, Tiffany L.; Timofeeva, Tatiana V.; Marder, Seth R.; Brédas, Jean‐Luc

doi:10.1039/b415018j

Cited by 57 publications

(122 citation statements)

References 13 publications

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“…Ein weiteres Beispiel, das die unterschiedlichen Auswirkungen oberflächlich sehr ähnlicher Abstandhalter auf das ET-Verhalten zeigt, ist ein Bis(triarylamin)-Radikalkation, das von Robin-Day-Klasse II zu III wechselt, wenn man den Acetylen-Abstandhalter durch eine Ethylen-Einheit ersetzt, wobei der Abstand zwischen den Redoxzentren in beiden Verbindungen fast gleich ist (Schema 6). [158] All die oben genannten Faktoren beeinflussen die elektronische Kopplung und, wie durch Gleichung (2) zusammen mit Gleichung (6) und (16) [51] (siehe Abschnitt 3.1.1). Während diese Redoxzentren im Allgemeinen eine relativ hohe innere Reorganisationsenergie aufweisen, besitzen Triarylamine und perchlorierte Triphenylmethyl-Radikale eine relativ kleine innere Reorganisationsenergie.…”

Section: Angewandte Chemieunclassified

Organische gemischtvalente Verbindungen: ein Spielplatz für Elektronen und Löcher

2011

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Gemischtvalente (MV) Verbindungen sind ausgezeichnete Modellsysteme, um grundlegende Elektronentransport(ET)‐ und Ladungstransfer(CT)‐Phänomene zu untersuchen. Diese sind in komplexen biophysikalischen Prozessen wie der Photosynthese, aber auch in artifiziellen elektronischen Bauteilen von großer Bedeutung. So sind organische MV‐Verbindungen effiziente Lochtransportmaterialien in organischen lichtemittierenden Dioden (OLEDs), Solarzellen und photochromen Fenstern. Die Bedeutung der organischen gemischtvalenten Chemie sollte jedoch weniger in ihrer direkten Anwendbarkeit gesehen werden, als vielmehr in dem riesigen Kenntnisschatz über Elektronentransferphänomene, der durch ihr Studium gewonnen wurde. Die große Vielfalt an organischen Redoxzentren und Brückeneinheiten, die zu MV‐Verbindungen kombiniert werden können, sowie die stete Weiterentwicklung von ET‐Theorien und ET‐Untersuchungsmethoden förderten das enorme Interesse an organischen MV‐Verbindungen in den letzten Jahrzehnten und zeigen das große Potential dieser Verbindungsklasse auf. Das Ziel dieses Aufsatzes ist es, das letzte Jahrzehnt der organischen gemischtvalenten Chemie zusammenzufassen und ihren Einfluss auf moderne funktionelle Materialien hervorzuheben.

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Section: Angewandte Chemieunclassified

Organische gemischtvalente Verbindungen: ein Spielplatz für Elektronen und Löcher

2011

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“…with the planes of the terminal aryl groups (Ar), consistent with the amine acting as a p-donor primarily to the bridging groups. However, it should be noted that, although all three angles in triarylamines are often comparable, both in simple compounds 46 and other triarylamine-based extended p-systems without strong p-acceptors, 47,48 they can show similar patterns of interplanar angles at the amine to that found in 1,…”

Section: Crystal Structurementioning

confidence: 99%

Characterisation of a dipolar chromophore with third-harmonic generation applications in the near-IR

et al. 2012

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E-2-Tricyanovinyl-3-n-hexyl-5-[4-{bis(4-n-butylphenyl)amino}-2-methoxystyryl]-thiophene, 1, has previously been used to demonstrate applications relying on frequency tripling of 1.55 mm light. Here we report the synthesis and chemical characterisation of 1, along with quantum-chemical calculations and additional experimental investigations of its third-order nonlinear properties that give more insight into its frequency tripling properties. Although 1 can be processed into amorphous films, crystals can also be grown by slow evaporation of solutions; the crystal structure determined by X-ray diffraction shows evidence of significant contributions from zwitterionic resonance forms to the ground-state structure, and reveals centrosymmetric packing exhibiting p-p and C-H/N^C interactions. Both solutions and films of 1 exhibit near-infrared two-photon absorption into the low-lying one-photon-allowed state with a peak two-photon cross-section of ca. 290 GM (measured using the white-light continuum method with a pump wavelength of 1800 nm) at a transition energy equivalent to degenerate two-photon absorption at ca. 1360 nm; two related chromophores are also found to show comparable near-IR two-photon crosssections. Closed-aperture Z-scan measurements and quantum-chemical calculations indicate that the nonlinear refractive index and third-harmonic generation properties of 1 are strongly dependent on frequency in the telecommunications range, due the aforementioned two-photon resonance.

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“…[36][37]50 Indeed, these absorptions fall into the spectral range in which intervalence absorptions of bis(triarylamine) radical cations are commonly observed. 16,20,[34][35][51][52][53][54][55][56][57][58][59][60][61] An important difference to the intervalence absorptions of coordination compounds 40,[62][63][64][65] are the comparatively large extinction coefficients of these bands, but this is a (favorable) peculiarity of organic mixed-valence compounds which has been noted many times before. Table 2.…”

Section: -49mentioning

confidence: 99%

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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A mixed-valence bis(diarylamino)stilbene: crystal structure and comparison of electronic coupling with biphenyl and tolane analogues

Abstract: The E-4,4'-bis[di(p-anisyl)amino]stilbene cation is a class-III mixed-valence species with electronic coupling comparable to that in its biphenyl-bridged analogue, whereas its tolane-bridged analogue belongs to class II.

Cited by 57 publications

References 13 publications

Organische gemischtvalente Verbindungen: ein Spielplatz für Elektronen und Löcher

Organische gemischtvalente Verbindungen: ein Spielplatz für Elektronen und Löcher

Characterisation of a dipolar chromophore with third-harmonic generation applications in the near-IR

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

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