Is photoisomerization required for NO photorelease in ruthenium nitrosyl complexes?

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• 作者：Juan Sanz García ; Fabienne Alary ; Martial Boggio-Pasqua…
• 关键词：Computational study ; DFT ; Ruthenium complexes ; Photorelease ; Nitrosyl ; Photoisomerization pathway ; Chain ; of ; states method ; Bond dissociation energy
• 刊名：Journal of Molecular Modeling
• 出版年：2016
• 出版时间：November 2016
• 年：2016
• 卷：22
• 期：11
• 全文大小：1,614 KB
• 刊物类别：Chemistry and Materials Science
• 刊物主题：Chemistry
  Computer Applications in Chemistry
  Biomedicine
  Molecular Medicine
  Health Informatics and Administration
  Life Sciences
  Computer Application in Life Sciences
  
• 出版者：Springer Berlin / Heidelberg
• ISSN：0948-5023
• 卷排序：22

文摘

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.