Estimation of marcus λ for <i>p</i>‐phenylenediamines from the optical spectrum of a dimeric derivative

Nelsen, Stephen F.; Yunta, María J. R.

doi:10.1002/poc.610070202

Cited by 53 publications

(66 citation statements)

References 28 publications

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“…[224] Von der Absorptionsbande abgesehen untermauern temperaturabhängige ESR-Messungen in Dichlormethan zumindest die Einordnung von 128 + als lokalisierte Klasse-II-MV-Verbindung. [223] Eine Carbonylgruppe wirkt aufgrund ihrer kreuzkonjugierten Natur als entkoppelnde Brücke im Bis(hydroxylamin)-Radikalkation 129 + (Schema 46). [223,226] Analyse ihrer IV-CT-Banden sowie durch ESR-Experimente mit Fokus auf den Einfluss der Topologie (para vs. meta).…”

Section: Mv-verbindungen Mit Diarylamin-redoxzentren Undunclassified

“…[223] Eine Carbonylgruppe wirkt aufgrund ihrer kreuzkonjugierten Natur als entkoppelnde Brücke im Bis(hydroxylamin)-Radikalkation 129 + (Schema 46). [223,226] Analyse ihrer IV-CT-Banden sowie durch ESR-Experimente mit Fokus auf den Einfluss der Topologie (para vs. meta). [3,233,234] Die Radikalanionen wurden für die optischen Untersuchungen durch Spektroelektrochemie in Dichlormethan/0.1m TBAH erzeugt.…”

Section: Mv-verbindungen Mit Diarylamin-redoxzentren Undunclassified

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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: Mv-verbindungen Mit Diarylamin-redoxzentren Undunclassified

Organische gemischtvalente Verbindungen: ein Spielplatz für Elektronen und Löcher

2011

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“…We calculated the internal reorganization energy λ for the self‐exchange hole‐transfer process via the Nelsen's four‐point method . It is described as the vertical ionization of a neutral molecule followed by geometric relaxation, and then vertical neutralization of a charged molecule followed by geometric relaxation

λ = λ_{1} + λ_{2} = E_{+} (|, Q_{0}) - E_{+} (|, Q_{+}) + E_{0} (|, Q_{+}) - E_{0} (|, Q_{0})

where E is energy, Q is geometry, and the subscripts 0 and + denote neutral and cationic states, respectively.…”

Section: Methodsmentioning

confidence: 99%

Applying strong external electric field to thiophene‐based oligomers: A promising approach to upgrade semiconducting performance

et al. 2016

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A key parameter dictating the rate of charge transfer (CT) is reorganization energy (λ), an energy associated with geometry changes during hole/electron transfer. We show that "ironing" the inter-ring dihedral angles of oligothiophenes via proper substitutions or insertions (e.g., -OR, -F or -C≡C-), decreases the λ and thus promotes CT according to Marcus equation. Our results demonstrate, to attain a smaller λ, extending oligomer length is only significant if the flattened backbone structure is realized. Of great interest is that external electric fields, which are ubiquitous in electronic devices yet commonly overlooked in the computation of λ, can have a significantly greater impact than conventional substitutions. It is important to emphasize, the responses of λ to external fields is system-dependent. Compared to fused-ring conjugated systems, single-bond connected thiophenes are more sensitive to external fields. F lowers the λ (552 meV) of quaterthiophene by almost 80% at the intensity of 1 V/Å, down to a value (125 meV) which is even lower than that of pentacene (154 meV) and rubrene (219 meV) at the same level of theory. © 2016 Wiley Periodicals, Inc.

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“…The inner reorganization energy, λi, for self-exchange consists of two terms (λi = λ1 + λ2) corresponding to the geometry relaxation energies going from the neutral-state geometry to the charged-state one and vice versa (Nelsen four-point method) 51,52 λ1 = E 0 (G * ) -E 0 (G 0 )…”

Section: Semiconducting Properties Of [N]cpymentioning

confidence: 99%

Theoretical Study of Cyclic Pyrene Oligomers and Their Resemblance with Cyclic Paraphenylenes: Disclosing Structure–Property Relationships for Cyclic Nanorings

et al. 2016

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We theoretically discuss here the relationships between the structure of recently synthesized nanorings, dubbed as cyclo-2,7-pyrenylene (CPY) and formed upon bending and bonding a finite number of pyrene units until self-cyclation, and a set of chemically relevant properties such as the induced structural and energetical strain, the electronic and optical properties, or the response to charge injection, as well as their transport mechanism through a concerted migration of charge-carriers. We also compare these properties, and their evolution with the number of pyrene-linked units, with those obtained for the closely related cycloparaphenylene (CPP) compounds, trying to disclose the underlying structure-property guidelines. To do it, we always employ dispersion-corrected DFT methods to systematically include the key effects affecting all the properties tackled. A correct match with some available experimental results, for the [4]CPY compound (the only one synthesized so far), anticipates the accuracy of the calculations done for the rest of compounds. Finally, since this kind of systems are envisioned as possible precursors for the fine-tuned and controlled synthesis of carbon nanotubes, we also address the stability of the dimers found in their crystalline structure, and the associated cohesive energy, which may drive the synthesis of the corresponding nanotubes after an adequate dehydrogenation reaction.

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Estimation of marcus λ for p‐phenylenediamines from the optical spectrum of a dimeric derivative

Cited by 53 publications

References 28 publications

Organische gemischtvalente Verbindungen: ein Spielplatz für Elektronen und Löcher

Organische gemischtvalente Verbindungen: ein Spielplatz für Elektronen und Löcher

Applying strong external electric field to thiophene‐based oligomers: A promising approach to upgrade semiconducting performance

Theoretical Study of Cyclic Pyrene Oligomers and Their Resemblance with Cyclic Paraphenylenes: Disclosing Structure–Property Relationships for Cyclic Nanorings

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