Establishing the Two-Photon Linkage Isomerization Mechanism in the Nitrosyl Complex trans-[RuCl(NO)(py)4]2+ by DFT and TDDFT

详细信息    查看全文

• 作者：Juan Sanz Garc铆a ; Fabienne Alary ; Martial Boggio-Pasqua ; Isabelle M. Dixon ; Isabelle Malfant ; Jean-Louis Heully
• 刊名：Inorganic Chemistry
• 出版年：2015
• 出版时间：September 8, 2015
• 年：2015
• 卷：54
• 期：17
• 页码：8310-8318
• 全文大小：440K
• ISSN：1520-510X

文摘

The density functional theory calculations presented in this work allow the first rationalization of the full linkage photoisomerization mechanism of trans-[RuCl(NO)(py)₄]²⁺, in both the forward and reverse directions. These mechanisms are consistent with the experimental data establishing that blue-light irradiation triggers the forward process, while red or IR photons trigger the reverse process. Characterization of the singlet and lowest triplet potential energy surfaces shows that, despite the unfavorable thermodynamic character of the forward process, the topologies of the surfaces and particularly some crucial surface crossings enable the isomerization. In the forward Ru鈥揘O 鈫?Ru鈥揙N direction, a sequential two-photon absorption mechanism is unraveled that involves a sideways-bonded metastable state. In contrast, in the reverse reaction, two mechanisms are proposed involving either one or two photons.