García Juan Sanz, Alary Fabienne, Boggio-Pasqua Martial, Dixon Isabelle M, Heully Jean-Louis
Laboratoire de Chimie et Physique Quantiques, UMR 5626, IRSAMC, CNRS et Université de Toulouse, 118 route de Narbonne, 31062, Toulouse, France.
J Mol Model. 2016 Nov;22(11):284. doi: 10.1007/s00894-016-3138-2. Epub 2016 Oct 29.
The factors that explain the competition between intramolecular NO linkage photoisomerization and NO photorelease in five ruthenium nitrosyl complexes were investigated. By applying DFT-based methods, it was possible to characterize the ground states and lowest triplet potential energy surfaces of these species, and to establish that both photoisomerization and photorelease processes can occur in the lowest triplet state of each species. This work highlights the crucial role of the sideways-bonded isomer, a metastable state also known as the MS2 isomer, in the photochemical loss of NO, while the results obtained also indicate that the population of the triplet state of this isomer is compulsory for both processes and show how photoisomerization and photorelease interfere. Graphical Abstract Illustration of the crucial role of the MS2 state in the photoreactivities of ruthenium nitrosyl complexes.
研究了在五种钌亚硝酰配合物中，解释分子内NO键光异构化与NO光释放之间竞争关系的因素。通过应用基于密度泛函理论（DFT）的方法，能够表征这些物种的基态和最低三重态势能面，并确定光异构化和光释放过程均可在每个物种的最低三重态中发生。这项工作突出了侧向键合异构体（一种也称为MS2异构体的亚稳态）在NO光化学损失中的关键作用，而所得结果还表明，该异构体三重态的布居数对于这两个过程都是必不可少的，并展示了光异构化和光释放是如何相互干扰的。图形摘要：MS2态在钌亚硝酰配合物光反应性中的关键作用示意图。
