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Observation of the two triplet state conformations of alkyl phenylglyoxylates

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Abstract

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 α-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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Authors and Affiliations

  1. Center for Photochemical Sciences, Bowling Green State University, Bowling Green, OH, 43403, USA

    Alexei G. Merzlikine, Sergey V. Voskresensky, Eugene O. Danilov, Michael A. J. Rodgers & Douglas C. Neckers

  2. Wright Photoscience Laboratory, Department of Chemistry, Bowling Green State University, Bowling Green, OH, 43403, USA

    Andrei V. Fedorov

Authors
  1. Alexei G. Merzlikine
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  2. Sergey V. Voskresensky
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  3. Eugene O. Danilov
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  4. Andrei V. Fedorov
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  5. Michael A. J. Rodgers
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  6. Douglas C. Neckers
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Correspondence to Douglas C. Neckers.

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Dedicated to Professor Dr J. W. Neckers in honor of his 101st birthday.

Electronic supplementary information (ESI) available: Synthetic procedures and characterization of APGs, description of spectra processing procedures, time-resolved FTIR spectra and kinetic traces demonstrating steric and d-isotope effects, 3D structures of cyclohexyl phenylglyoxylate and t-Bu-cyclohexyl glyoxylate conformers. See http://www.rsc.org/suppdata/pp/b4/b404580g/

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Merzlikine, A.G., Voskresensky, S.V., Danilov, E.O. et al. Observation of the two triplet state conformations of alkyl phenylglyoxylates. Photochem Photobiol Sci 3, 892–897 (2004). https://doi.org/10.1039/b404580g

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  • DOI: https://doi.org/10.1039/b404580g

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