Observation of the two triplet state conformations of alkyl phenylglyoxylates

Step-scan time-resolved FT-IR spectra of alkyl phenylglyoxylates in hexane with a 4 cm(-1) spectral resolution reveal splitting of the transient absorption signal near 1650 cm(-1) into two closely located peaks with different lifetimes on the nanosecond time scale. This signal had been previously as...

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Published inPhotochemical & photobiological sciences Vol. 3; no. 9; pp. 892 - 897
Main Authors Merzlikine, AG, Voskresensky, SV, Danilov, EO, Fedorov, AV, Rodgers, MAJ, Neckers, DC
Format Journal Article
LanguageEnglish
Published LONDON Springer Nature 01.09.2004
Subjects
Biochemistry & Molecular Biology
Biophysics
Chemistry
Chemistry, Physical
Life Sciences & Biomedicine
Physical Sciences
Science & Technology
TRANSFORM INFRARED-SPECTROSCOPY
COMPLEXES
REACTIVITY
RADICALS
PHOTOCHEMICAL-REACTIONS
ZEOLITE
TIME-RESOLVED IR
ELECTRONIC-STRUCTURE
EXCITED-STATES
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Summary:Step-scan time-resolved FT-IR spectra of alkyl phenylglyoxylates in hexane with a 4 cm(-1) spectral resolution reveal splitting of the transient absorption signal near 1650 cm(-1) into two closely located peaks with different lifetimes on the nanosecond time scale. This signal had been previously assigned to the triplet state of the starting material that gives rise to the alpha-hydroxyphenylketene. In the current article, evidence is presented to assign these two peaks to different triplet state conformers only one of which undergoes fast Norrish Type II photoelimination. This assignment was made on the basis of chemical reactivity, steric effects, and kinetic data.
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ISSN:1474-905X
1474-9092
DOI:10.1039/b404580g