Exploration of Uncharted 3PES Territory for [Ru(bpy)3]2+: A New 3MC Minimum Prone to Ligand Loss Photochemistry - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Inorganic Chemistry Année : 2018

Exploration of Uncharted 3PES Territory for [Ru(bpy)3]2+: A New 3MC Minimum Prone to Ligand Loss Photochemistry

Résumé

We have identified a new 3 MC state bearing two elongated RuN bonds to the same ligand in [Ru(bpy) 3 ] 2+. This DFT-optimized structure is a local minimum on the 3 PES. This distal MC state (3 MC cis) is destabilized by less than 2 kcal/mol with respect to the classical MC state (3 MC trans), and energy barriers to populate 3 MC cis and 3 MC trans from the 3 MLCT state are similar according to nudged elastic band minimum energy path calculations. Distortions in the classical 3 MC trans , i.e. elongation of two RuN bonds towards two different bpy ligands, are not expected to favour the formation of ligand-loss photoproducts. On the contrary, the new 3 MC cis could be particularly relevant in the photodegradation of Ru(II) polypyridine complexes
Fichier principal
Vignette du fichier
AAM_2018_IC_3192.pdf (611.08 Ko) Télécharger le fichier
Origine : Fichiers produits par l'(les) auteur(s)
Loading...

Dates et versions

hal-01741450 , version 1 (18-02-2020)

Identifiants

Citer

Adrien Soupart, Fabienne Alary, Jean-Louis Heully, Elliott I.P. Paul, Isabelle M. Dixon. Exploration of Uncharted 3PES Territory for [Ru(bpy)3]2+: A New 3MC Minimum Prone to Ligand Loss Photochemistry. Inorganic Chemistry, 2018, 57, 6, pp.3192-3196. ⟨10.1021/acs.inorgchem.7b03229⟩. ⟨hal-01741450⟩
59 Consultations
244 Téléchargements

Altmetric

Partager

Gmail Facebook X LinkedIn More