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Mukhina OA, Cronk WC, Kumar NN, et al. Intramolecular cycloadditions of photogenerated azaxylylenes: an experimental and theoretical study. J Phys Chem A. 2014;118(45):10487-96doi: 10.1021/jp504281y.
Mukhina, O. A., Cronk, W. C., Kumar, N. N., Sekhar, M. C., Samanta, A., & Kutateladze, A. G. (2014). Intramolecular cycloadditions of photogenerated azaxylylenes: an experimental and theoretical study. The journal of physical chemistry. A, 118(45), 10487-96. https://doi.org/10.1021/jp504281y
Mukhina, Olga A, et al. "Intramolecular cycloadditions of photogenerated azaxylylenes: an experimental and theoretical study." The journal of physical chemistry. A vol. 118,45 (2014): 10487-96. doi: https://doi.org/10.1021/jp504281y
Mukhina OA, Cronk WC, Kumar NN, Sekhar MC, Samanta A, Kutateladze AG. Intramolecular cycloadditions of photogenerated azaxylylenes: an experimental and theoretical study. J Phys Chem A. 2014 Nov 13;118(45):10487-96. doi: 10.1021/jp504281y. Epub 2014 Jun 24. PMID: 24958234.
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J Phys Chem A. 2014 Nov 13;118(45):10487-96. doi: 10.1021/jp504281y. Epub 2014 Jun 24.

Intramolecular cycloadditions of photogenerated azaxylylenes: an experimental and theoretical study.

The journal of physical chemistry. A

Olga A Mukhina, W Cole Cronk, N N Bhuvan Kumar, M Chandra Sekhar, Anunay Samanta, Andrei G Kutateladze

Affiliations

  1. Department of Chemistry and Biochemistry, University of Denver , Denver, Colorado 80208, United States.

PMID: 24958234 DOI: 10.1021/jp504281y

Abstract

The mechanism of intramolecular cycloadditions of azaxylylenes photogenerated via excited-state intramolecular proton transfer (ESIPT) in aromatic o-amido ketones and aldehydes bearing unsaturated functionalities was studied experimentally and computationally. In time-correlated single-photon counting experiments, no relation was found between lifetimes of singlet species and the nature of the amide pendant, either unsaturated furanpropanamide, capable of photocyclization, or the acetamide control. Steady-state emission for amido-tetralone derivatives showed comparable dual emission bands, but bromo substitution decreased the intensity of the ESIPT band. The most reactive derivatives of amidobenzaldehydes were virtually lacking the ESIPT band. The quantum yield of cycloaddition is decreased in the presence of triplet quenchers, O2 or trans-piperylene, and improved with heavy atom substitution in the aromatic ring, providing further evidence for the initial mechanistic hypothesis in which the fast singlet-state ESIPT is accompanied by the ISC in the tautomer (azaxylylene), which undergoes stepwise addition to the tethered unsaturated pendants.

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