title: Is photoisomerization required for NO photorelease in ruthenium nitrosyl complexes?
abstract: 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 the3MS2 state in the photoreactivities of ruthenium nitrosyl complexes.
authors: Laboratoire de Chimie et Physique Quantiques, UMR 5626, IRSAMC, CNRS et Université de Toulouse, 118 route de Narbonne, 31062, Toulouse, France.
authors: Juan Sanz
authors: JS
authors: García
authors: Laboratoire de Chimie et Physique Quantiques, UMR 5626, IRSAMC, CNRS et Université de Toulouse, 118 route de Narbonne, 31062, Toulouse, France. fabienne.alary@irsamc.ups-tlse.fr.
authors: Fabienne
authors: http://orcid.org/0000-0003-4154-0815
authors: F
authors: Alary
authors: Laboratoire de Chimie et Physique Quantiques, UMR 5626, IRSAMC, CNRS et Université de Toulouse, 118 route de Narbonne, 31062, Toulouse, France.
authors: Martial
authors: M
authors: Boggio-Pasqua
authors: Laboratoire de Chimie et Physique Quantiques, UMR 5626, IRSAMC, CNRS et Université de Toulouse, 118 route de Narbonne, 31062, Toulouse, France.
authors: Isabelle M
authors: IM
authors: Dixon
authors: Laboratoire de Chimie et Physique Quantiques, UMR 5626, IRSAMC, CNRS et Université de Toulouse, 118 route de Narbonne, 31062, Toulouse, France.
authors: Jean-Louis
authors: JL
authors: Heully
keywords: Bond dissociation energy; Chain-of-states method; Computational study; DFT; Nitrosyl; Photoisomerization pathway; Photorelease; Ruthenium complexes