Fedunov Roman G, Grivin Vjacheslav P, Pozdnyakov Ivan P, Melnikov Alexei A, Chekalin Sergei V, Vasilchenko Danila B, Glebov Evgeni M
V.V. Voevodsky Institute of Chemical Kinetics and Combustion, Siberian Branch of the Russian Academy of Sciences, 3 Institutskaya Str., 630090, Novosibirsk, Russian Federation.
Institute of Spectroscopy, Russian Academy of Sciences, 119333, Troitsk, Moscow, Russian Federation.
Photochem Photobiol Sci. 2024 Oct;23(10):1957-1970. doi: 10.1007/s43630-024-00645-z. Epub 2024 Oct 15.
The ultrafast processes caused by photoexcitation of (n-BuN)[Pt(NO)] complex in acetonitrile were studied by means of transient absorption (TA) pump-probe spectroscopy and verified by quantum chemical calculations. The primary photochemical process was found to be an inner-sphere electron transfer followed by an escape of an NO radical to the bulk solution. The reaction occurs via the dissociative triplet excited LMCT state of the initial complex. Based on the experimental data and quantum chemical calculations, the mechanism of ultrafast photophysical and photochemical processes is proposed.
通过瞬态吸收(TA)泵浦 - 探测光谱研究了乙腈中(正丁基胺)[铂(亚硝基)]配合物光激发引起的超快过程,并通过量子化学计算进行了验证。发现主要的光化学过程是内球电子转移,随后是亚硝基自由基逸出到本体溶液中。该反应通过初始配合物的离解三重态激发的配体到金属电荷转移(LMCT)态发生。基于实验数据和量子化学计算,提出了超快光物理和光化学过程的机理。