Electronic Couplings in Organic Mixed-Valence Compounds: The Contribution of Photoelectron Spectroscopy

Veaceslav Coropceanu; Nadine E. Gruhn; Stephen Barlow; Christoph Lambert; Jason C. Durivage; Tonja G. Bill; Gilbert Nöll; Seth R. Marder; Jean Luc Brédas

doi:10.1021/ja039263u

Electronic Couplings in Organic Mixed-Valence Compounds: The Contribution of Photoelectron Spectroscopy

Veaceslav Coropceanu^*, Nadine E. Gruhn, Stephen Barlow, Christoph Lambert, Jason C. Durivage, Tonja G. Bill, Gilbert Nöll, Seth R. Marder, Jean Luc Brédas

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

80 Scopus citations

Abstract

We show that the electronic coupling in strongly coupled organic mixed-valence systems can be effectively probed by means of gas-phase ultraviolet photoelectron spectroscopy (UPS). Taking six diamines as examples, the UPS estimates for the electronic couplings H_ab are compared with the corresponding values determined from the intervalence charge-transfer absorption bands and from electronic structure calculations. Similar trends are observed for the H_ab values estimated from UPS and optical spectra; this provides support for the applicability of Hush theory to strongly coupled organic mixed-valence systems. The UPS electronic couplings are found to be somewhat smaller than those from optical spectroscopy, which is attributed to the role of vibronic coupling to symmetrical modes; when corrected for this vibronic coupling, the UPS H_ab estimates confirm that triarylamine-based mixed-valence systems are close to the class-II/class-III borderline.

Original language	English (US)
Pages (from-to)	2727-2731
Number of pages	5
Journal	Journal of the American Chemical Society
Volume	126
Issue number	9
DOIs	https://doi.org/10.1021/ja039263u
State	Published - Mar 10 2004
Externally published	Yes

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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title = "Electronic Couplings in Organic Mixed-Valence Compounds: The Contribution of Photoelectron Spectroscopy",

abstract = "We show that the electronic coupling in strongly coupled organic mixed-valence systems can be effectively probed by means of gas-phase ultraviolet photoelectron spectroscopy (UPS). Taking six diamines as examples, the UPS estimates for the electronic couplings Hab are compared with the corresponding values determined from the intervalence charge-transfer absorption bands and from electronic structure calculations. Similar trends are observed for the Hab values estimated from UPS and optical spectra; this provides support for the applicability of Hush theory to strongly coupled organic mixed-valence systems. The UPS electronic couplings are found to be somewhat smaller than those from optical spectroscopy, which is attributed to the role of vibronic coupling to symmetrical modes; when corrected for this vibronic coupling, the UPS Hab estimates confirm that triarylamine-based mixed-valence systems are close to the class-II/class-III borderline.",

author = "Veaceslav Coropceanu and Gruhn, {Nadine E.} and Stephen Barlow and Christoph Lambert and Durivage, {Jason C.} and Bill, {Tonja G.} and Gilbert N{\"o}ll and Marder, {Seth R.} and Br{\'e}das, {Jean Luc}",

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T1 - Electronic Couplings in Organic Mixed-Valence Compounds

T2 - The Contribution of Photoelectron Spectroscopy

AU - Coropceanu, Veaceslav

AU - Gruhn, Nadine E.

AU - Barlow, Stephen

AU - Lambert, Christoph

AU - Durivage, Jason C.

AU - Bill, Tonja G.

AU - Nöll, Gilbert

AU - Marder, Seth R.

AU - Brédas, Jean Luc

PY - 2004/3/10

Y1 - 2004/3/10

N2 - We show that the electronic coupling in strongly coupled organic mixed-valence systems can be effectively probed by means of gas-phase ultraviolet photoelectron spectroscopy (UPS). Taking six diamines as examples, the UPS estimates for the electronic couplings Hab are compared with the corresponding values determined from the intervalence charge-transfer absorption bands and from electronic structure calculations. Similar trends are observed for the Hab values estimated from UPS and optical spectra; this provides support for the applicability of Hush theory to strongly coupled organic mixed-valence systems. The UPS electronic couplings are found to be somewhat smaller than those from optical spectroscopy, which is attributed to the role of vibronic coupling to symmetrical modes; when corrected for this vibronic coupling, the UPS Hab estimates confirm that triarylamine-based mixed-valence systems are close to the class-II/class-III borderline.

AB - We show that the electronic coupling in strongly coupled organic mixed-valence systems can be effectively probed by means of gas-phase ultraviolet photoelectron spectroscopy (UPS). Taking six diamines as examples, the UPS estimates for the electronic couplings Hab are compared with the corresponding values determined from the intervalence charge-transfer absorption bands and from electronic structure calculations. Similar trends are observed for the Hab values estimated from UPS and optical spectra; this provides support for the applicability of Hush theory to strongly coupled organic mixed-valence systems. The UPS electronic couplings are found to be somewhat smaller than those from optical spectroscopy, which is attributed to the role of vibronic coupling to symmetrical modes; when corrected for this vibronic coupling, the UPS Hab estimates confirm that triarylamine-based mixed-valence systems are close to the class-II/class-III borderline.

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Electronic Couplings in Organic Mixed-Valence Compounds: The Contribution of Photoelectron Spectroscopy

Abstract

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