(n-Bu4N)2[Pt(NO3)6]在乙腈中的光物理和光化学：超快泵探光谱学和量子化学洞察力。

IF 2.7 3区化学 Q3 BIOCHEMISTRY & MOLECULAR BIOLOGY

Photochemical & Photobiological Sciences Pub Date : 2024-10-01 Epub Date: 2024-10-15 DOI:10.1007/s43630-024-00645-z

Roman G Fedunov, Vjacheslav P Grivin, Ivan P Pozdnyakov, Alexei A Melnikov, Sergei V Chekalin, Danila B Vasilchenko, Evgeni M Glebov

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引用次数: 0

摘要

通过瞬态吸收（TA）泵探光谱法研究了乙腈中 (n-Bu4N)2[Pt(NO3)6] 复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。研究发现，主要的光化学过程是一个内球电子转移过程，随后一个 -NO3 自由基逸出到溶液中。反应是通过初始复合物的离解三重激发 LMCT 状态发生的。根据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。

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Photophysics and photochemistry of (n-Bu₄N)₂[Pt(NO₃)₆] in acetonitrile: ultrafast pump-probe spectroscopy and quantum chemical insight.

The ultrafast processes caused by photoexcitation of (n-Bu₄N)₂[Pt(NO₃)₆] 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 ^•NO₃ 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.

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