Photoisomerization in a Platinum-Amido Pincer Complex: An Excited-State Reaction Pathway Controlled by Localized Ligand Photochemistry
Photoisomerization in a Platinum-Amido Pincer Complex: An Excited-State Reaction Pathway Controlled by Localized Ligand Photochemistry
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铂-氨基钳配合物中的光异构化：局域配体光化学控制的激发态反应途径
DOI：
10.1021/jz100156p
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发表时间：
2010
期刊：
影响因子：
--
通讯作者：
Zurek J
中科院分区：
文献类型：
--
作者：
Zurek J
计算研究了双（8-喹啉基）氨基）PtMe_2 I配合物的电子光谱和光化学异构化。含时密度泛函理论，结合极化连续溶剂模型，再现实验光谱的mer和fac异构体。mer异构体的初始布居状态的性质在性质上是ππ*，并且定位在BQA配体上。几何优化表明，该系统在激发流形松弛到一个fac-like几何在S1电子状态。完整的活性空间自洽场（CASSCF）的计算表明，存在一个倾斜的圆锥形的交叉点，连接激发态和基态的fac物种，允许无辐射的面状几何形状的失活。
Computational investigations of the electronic spectroscopy and photochemical isomerization in the complex (bis(8-quinolinyl)amido)PtMe2I are presented. Time-dependent density functional theory, in conjunction with the polarizable continuum solvent model, reproduce the experimental spectra for the mer and fac isomers well. The nature of the initially populated states for the mer isomer are ππ* in nature and localized on the BQA ligand. Geometry optimization shows that the system relaxes in the excited manifold to a fac-like geometry in the S1electronic state. Complete active space self-consistent field (CASSCF) calculations show that there exists a sloped conical intersection that connects the excited- and ground-state fac species, allowing for radiationless deactivation in fac-like geometries.