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 | |
| Publication status | Published - Oct 5 2005 |
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- Chemistry(all)
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Delocalization of free electron density through phenylene-ethynylene : Structural changes studied by time-resolved infrared spectroscopy. / Polyansky, Dmitry; 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
}
TY - JOUR
T1 - Delocalization of free electron density through phenylene-ethynylene
T2 - Structural changes studied by time-resolved infrared spectroscopy
AU - Polyansky, Dmitry
AU - Danilov, Evgeny O.
AU - Voskresensky, Sergey V.
AU - Rodgers, Michael A J
AU - Neckers, Douglas C.
PY - 2005/10/5
Y1 - 2005/10/5
N2 - 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.
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.
UR - http://www.scopus.com/inward/record.url?scp=25844461398&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=25844461398&partnerID=8YFLogxK
U2 - 10.1021/ja053120l
DO - 10.1021/ja053120l
M3 - Article
C2 - 16190681
AN - SCOPUS:25844461398
VL - 127
SP - 13452
EP - 13453
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 39
ER -