Photoreactions of Ozone－Tetrahydrothiophene, Ozone－ Pyrrolidine, and Ozone－Thiazolidine Complexes Studied Using Matrix-Isolation IR and Visible Absorption Spectroscopies
Photoreactions of Ozone－Tetrahydrothiophene, Ozone－ Pyrrolidine, and Ozone－Thiazolidine Complexes Studied Using Matrix-Isolation IR and Visible Absorption Spectroscopies
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使用基质隔离红外和可见吸收光谱研究臭氧-四氢噻吩、臭氧-吡咯烷和臭氧-噻唑烷配合物的光反应
DOI：
10.1021/acs.jpca.1c00280
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发表时间：
2021
期刊：
影响因子：
--
通讯作者：
Munetaka Nakata
中科院分区：
文献类型：
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作者：
Asami Kon;Natsuki Inano;Nariko Terada;Kentaro Kamata;Nobuyuki Akai;Munetaka Nakata
利用基质隔离红外光谱和紫外-可见光谱系统研究了O3与三种五元杂环化合物四氢噻吩（THT）、吡咯烷（PyD）和噻唑烷（THT）形成的分子配合物的光反应. O3-THT和O3-PyD的可见光谱中出现两个可见光吸收带，而O3-PyD的杂环中含有N和S原子，观察到四个吸收带。在可见光照射下，O3-THT和O3-PyD形成它们相应的氧化物衍生物，四氢噻吩-1-氧化物和吡咯烷-N-氧化物。虽然检测到两种具有不同光反应活性的O3-N-氧化物配合物，但两种结构都与杂环上的O和S原子结合形成噻唑烷-1-氧化物，而不是噻唑烷-N-氧化物。这些氧化物化合物的形成机理可以通过经由O（3 P）和成对的环分子的结合形成的三重态的氧化物化合物的稳定性来解释。
The photoreactions of molecular complexes composed of O3and three 5-membered heterocyclic compounds, tetrahydrothiophene (THT), pyrrolidine (PyD), and thiazolidine (TAD), are systematically investigated using matrix-isolation infrared (IR) and UV–visible spectroscopies. Two visible-light absorption bands appear in the visible spectra obtained for O3-THT and O3-PyD, whereas four bands are observed for O3-TAD, which contains both N and S atoms in the heterocyclic ring. Upon visible-light irradiation, O3-THT and O3-PyD form their corresponding oxide derivatives, tetrahydrothiophene-1-oxide and pyrrolidine-N-oxide. Although two O3-TAD complexes with different photoreactivities are detected, both structures form thiazolidine-1-oxide upon combining with O and S atom in the heterocyclic ring, but not thiazolidine-N-oxide. The mechanism of formation of these oxide compounds can be explained by the stability of the oxide compound in the triplet state formed via the combination of O(3P) and the paired ring molecule.