Delocalization in platinum-alkynyl systems: A metal-bridged organic mixed-valence compound

Simon C. Jones; Veaceslav Coropceanu; Stephen Barlow; Tiffany Kinnibrugh; Tatiana Timofeeva; Jean Luc Brédas; Seth R. Marder

doi:10.1021/ja045869m

Delocalization in platinum-alkynyl systems: A metal-bridged organic mixed-valence compound

Simon C. Jones, Veaceslav Coropceanu, Stephen Barlow, Tiffany Kinnibrugh, Tatiana Timofeeva, Jean Luc Brédas, Seth R. Marder^*

^*Corresponding author for this work

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

120 Scopus citations

Abstract

A complex featuring two triarylamine redox centers bridged by Pt, trans-bis(triethylphosphine)-bis{4-[bis(4-methoxyphenyl)amino]phenylethynyl} platinum(II), has been synthesized as a model system for π-conjugated Pt-containing polymers. Analysis of the intervalence charge-transfer band displayed by its mixed-valence monocation affords a quantitative assessment of electronic delocalization through the Pt bridge; this is found to be only slightly smaller than that determined for a benzene-bridged analogue. These results are supported by density functional theory calculations, which show that the active orbitals involved in the electron-transfer process in both cases have similar delocalization through the bridging unit.

Original language	English (US)
Pages (from-to)	11782-11783
Number of pages	2
Journal	Journal of the American Chemical Society
Volume	126
Issue number	38
DOIs	https://doi.org/10.1021/ja045869m
State	Published - Sep 29 2004
Externally published	Yes

ASJC Scopus subject areas

General Chemistry
Biochemistry
Catalysis
Colloid and Surface Chemistry

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title = "Delocalization in platinum-alkynyl systems: A metal-bridged organic mixed-valence compound",

abstract = "A complex featuring two triarylamine redox centers bridged by Pt, trans-bis(triethylphosphine)-bis{4-[bis(4-methoxyphenyl)amino]phenylethynyl} platinum(II), has been synthesized as a model system for π-conjugated Pt-containing polymers. Analysis of the intervalence charge-transfer band displayed by its mixed-valence monocation affords a quantitative assessment of electronic delocalization through the Pt bridge; this is found to be only slightly smaller than that determined for a benzene-bridged analogue. These results are supported by density functional theory calculations, which show that the active orbitals involved in the electron-transfer process in both cases have similar delocalization through the bridging unit.",

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AU - Jones, Simon C.

AU - Coropceanu, Veaceslav

AU - Barlow, Stephen

AU - Kinnibrugh, Tiffany

AU - Timofeeva, Tatiana

AU - Brédas, Jean Luc

AU - Marder, Seth R.

PY - 2004/9/29

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N2 - A complex featuring two triarylamine redox centers bridged by Pt, trans-bis(triethylphosphine)-bis{4-[bis(4-methoxyphenyl)amino]phenylethynyl} platinum(II), has been synthesized as a model system for π-conjugated Pt-containing polymers. Analysis of the intervalence charge-transfer band displayed by its mixed-valence monocation affords a quantitative assessment of electronic delocalization through the Pt bridge; this is found to be only slightly smaller than that determined for a benzene-bridged analogue. These results are supported by density functional theory calculations, which show that the active orbitals involved in the electron-transfer process in both cases have similar delocalization through the bridging unit.

AB - A complex featuring two triarylamine redox centers bridged by Pt, trans-bis(triethylphosphine)-bis{4-[bis(4-methoxyphenyl)amino]phenylethynyl} platinum(II), has been synthesized as a model system for π-conjugated Pt-containing polymers. Analysis of the intervalence charge-transfer band displayed by its mixed-valence monocation affords a quantitative assessment of electronic delocalization through the Pt bridge; this is found to be only slightly smaller than that determined for a benzene-bridged analogue. These results are supported by density functional theory calculations, which show that the active orbitals involved in the electron-transfer process in both cases have similar delocalization through the bridging unit.

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Delocalization in platinum-alkynyl systems: A metal-bridged organic mixed-valence compound

Abstract

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