Delocalization of free electron density through phenylene-ethynylene: Structural changes studied by time-resolved infrared spectroscopy

Dmitry E. Polyansky; Evgeny O. Danilov; Sergey V. Voskresensky; Michael A.J. Rodgers; Douglas C. Neckers

doi:10.1021/ja053120l

Delocalization of free electron density through phenylene-ethynylene: Structural changes studied by time-resolved infrared spectroscopy

Dmitry E. Polyansky, Evgeny O. Danilov, Sergey V. Voskresensky, Michael A.J. Rodgers, Douglas C. Neckers

Brookhaven National Laboratory

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

11 Citations (Scopus)

Abstract

We have studied the photochemistry of 1,4-bis(2-[4-tert-butylperoxycarbonylphenyl]ethynyl)benzene (1) and tert-butyl 4-(2-{4-[2-(4-phenyloxycarbonylphenyl)-1-ethynyl]phenyl}-1-ethynyl)peroxybenzoate (2). Excitation of 1 and 2 by a 355-nm laser pulse leads to the rapid formation of aroyloxyl radicals. An unpaired electron conjugated with the phenylene-ethynylene core is substantially delocalized over the π-system of the chromophore. The -C_≡C- vibrational frequencies of these radicals are red-shifted relative to 1 and 2 as measured by time-resolved IR spectroscopy. This shift is attributed to the change in the triple bond character due to delocalization of the free electron.

Original language	English
Pages (from-to)	13452-13453
Number of pages	2
Journal	Journal of the American Chemical Society
Volume	127
Issue number	39
DOIs	https://doi.org/10.1021/ja053120l
Publication status	Published - Oct 5 2005

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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10.1021/ja053120l

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Delocalization of free electron density through phenylene-ethynylene : Structural changes studied by time-resolved infrared spectroscopy. / Polyansky, Dmitry E.; Danilov, Evgeny O.; Voskresensky, Sergey V.; Rodgers, Michael A.J.; Neckers, Douglas C.

In: Journal of the American Chemical Society, Vol. 127, No. 39, 05.10.2005, p. 13452-13453.

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

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AU - Rodgers, Michael A.J.

AU - Neckers, Douglas C.

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AB - We have studied the photochemistry of 1,4-bis(2-[4-tert-butylperoxycarbonylphenyl]ethynyl)benzene (1) and tert-butyl 4-(2-{4-[2-(4-phenyloxycarbonylphenyl)-1-ethynyl]phenyl}-1-ethynyl)peroxybenzoate (2). Excitation of 1 and 2 by a 355-nm laser pulse leads to the rapid formation of aroyloxyl radicals. An unpaired electron conjugated with the phenylene-ethynylene core is substantially delocalized over the π-system of the chromophore. The -C≡C- vibrational frequencies of these radicals are red-shifted relative to 1 and 2 as measured by time-resolved IR spectroscopy. This shift is attributed to the change in the triple bond character due to delocalization of the free electron.

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Delocalization of free electron density through phenylene-ethynylene: Structural changes studied by time-resolved infrared spectroscopy

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