一系列钌单核亚硝酰配合物中 N 到 O 键光致异构化效率的理论研究。
A Theoretical Study of the N to O Linkage Photoisomerization Efficiency in a Series of Ruthenium Mononitrosyl Complexes.
机构信息
Laboratoire de Chimie et Physique Quantiques, IRSAMC, CNRS et Université Toulouse 3, 118 route de Narbonne, 31062 Toulouse, France.
Present address: Institut de Recherche de Chimie Paris, PSL Research University, CNRS, Chimie ParisTech, 11 Rue Pierre et Marie Curie, F-75005 Paris, France.
出版信息
Molecules. 2017 Oct 6;22(10):1667. doi: 10.3390/molecules22101667.
Ruthenium nitrosyl complexes are fascinating versatile photoactive molecules that can either undergo NO linkage photoisomerization or NO photorelease. The photochromic response of three ruthenium mononitrosyl complexes, -[RuCl(NO)(py)₄], -[RuBr(NO)(py)₄], and -(Cl,Cl)[RuCl₂(NO)(tpy)]⁺, has been investigated using density functional theory and time-dependent density functional theory. The N to O photoisomerization pathways and absorption properties of the various stable and metastable species have been computed, providing a simple rationalization of the photoconversion trend in this series of complexes. The dramatic decrease of the N to O photoisomerization efficiency going from the first to the last complex is mainly attributed to an increase of the photoproduct absorption at the irradiation wavelength, rather than a change in the photoisomerization pathways.
钌亚硝酰配合物是一类非常有趣的多功能光活性分子，它们可以进行 NO 键光异构化或 NO 光释放。使用密度泛函理论和含时密度泛函理论研究了三种钌单核亚硝酰配合物 -[RuCl(NO)(py)₄]、-[RuBr(NO)(py)₄]和 -(Cl,Cl)[RuCl₂(NO)(tpy)]⁺的光致变色响应。计算了各种稳定和亚稳物种的 N 到 O 光异构化途径和吸收特性，为该系列配合物的光转化趋势提供了简单的解释。从第一个配合物到最后一个配合物，N 到 O 光异构化效率的急剧下降主要归因于光产物在辐照波长处吸收的增加，而不是光异构化途径的变化。
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