Photolysis of labile bonds towards radical generation: case study of alkyl verdazyls; Physical Chemistry Chemical Physics; Vol. 27, iss. 30

Detalhes bibliográficos
Parent link:Physical Chemistry Chemical Physics.— .— London: Royal Society of Chemistry
Vol. 27, iss. 30.— 2025.— P. 16057-16066
Outros Autores: Kovalskaya E. S. Ekaterina Sergeevna, Kurtsevich A. E. Aleksandr Evgenjevich, Votkina D. E. Darjya Evgenjevna, Valiev R. R. Rashid Rinatovich, Postnikov P. S. Pavel Sergeevich, Petunin P. V. Pavel Vasilievich
Resumo:Title screen
Two series of stable verdazyl radical derivatives, specifically 1,2,4,6-substituted-1,4-dihydro-1,2,4,5-tetrazin-3(2H)-ones (also called “alkylverdazyls” or “AlkVZs”), were systematically investigated in photoactivated C–N bond homolysis. In-depth evaluation of their mechanisms indicated that several factors played a pivotal role in the generation of radicals during photon absorbance. From quantum chemical calculations, it was found that the most influential factor is the generation of charge-separated excited states, where one electron is located at the verdazyl moiety and the second one is distributed at the alkyl part. The theoretical approach also allows one to predict the reaction rate constant based on the oscillator strengths of the S0 → S1 transition in AlkVZs. Surprisingly, the photon density of the LED source has a strong impact on controlling the reaction direction, and decreasing the light power could lower the yield of radicals by twofold with the full conversion of the starting materials in all cases. Our results delineate prospective approaches for achieving high yields in photochemical transformations via the variation of the wavelength of light, the careful design of the molecular structure and alterations in the LED power
Текстовый файл
AM_Agreement
Idioma:inglês
Publicado em: 2025
Assuntos:
Acesso em linha:https://doi.org/10.1039/D5CP01625H
Formato: Recurso Electrónico Capítulo de Livro
KOHA link:https://koha.lib.tpu.ru/cgi-bin/koha/opac-detail.pl?biblionumber=685059

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330 |a Two series of stable verdazyl radical derivatives, specifically 1,2,4,6-substituted-1,4-dihydro-1,2,4,5-tetrazin-3(2H)-ones (also called “alkylverdazyls” or “AlkVZs”), were systematically investigated in photoactivated C–N bond homolysis. In-depth evaluation of their mechanisms indicated that several factors played a pivotal role in the generation of radicals during photon absorbance. From quantum chemical calculations, it was found that the most influential factor is the generation of charge-separated excited states, where one electron is located at the verdazyl moiety and the second one is distributed at the alkyl part. The theoretical approach also allows one to predict the reaction rate constant based on the oscillator strengths of the S0 → S1 transition in AlkVZs. Surprisingly, the photon density of the LED source has a strong impact on controlling the reaction direction, and decreasing the light power could lower the yield of radicals by twofold with the full conversion of the starting materials in all cases. Our results delineate prospective approaches for achieving high yields in photochemical transformations via the variation of the wavelength of light, the careful design of the molecular structure and alterations in the LED power 
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701 1 |a Kovalskaya  |b E. S.  |c biotechnologist  |c research engineer of Tomsk Polytechnic University  |f 1999-  |g Ekaterina Sergeevna  |9 23115 
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701 1 |a Votkina  |b D. E.  |c chemical engineer  |c Associate Scientist of the Tomsk Polytechnic University  |f 1995-  |g Darjya Evgenjevna  |9 21944 
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701 1 |a Petunin  |b P. V.  |c chemist  |c Associate Professor of Tomsk Polytechnic University, Candidate of Chemical Sciences  |f 1982-  |g Pavel Vasilievich  |9 19933 
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