%0 Journal Article
%T Pivotal Role of a Pentacoordinate 3MC State on the Photocleavage Efficiency of a Thioether Ligand in Ruthenium(II) Complexes: A Theoretical Mechanistic Study
%+ Photochimie théorique et computationnelle (LCPQ) (PTC)
%+ Leiden Institute of Chemistry
%A Göttle, Adrien, J.
%A Alary, Fabienne
%A Boggio-Pasqua, Martial
%A Dixon, Isabelle, M.
%A Heully, Jean-Louis
%A Bahreman, Azadeh
%A Askes, Sven, H.C.
%A Bonnet, Sylvestre
%< avec comité de lecture
%@ 0020-1669
%J Inorganic Chemistry
%I American Chemical Society
%V 55
%N 9
%P 4448–4456
%8 2016-04
%D 2016
%R 10.1021/acs.inorgchem.6b00268
%Z Chemical Sciences/Theoretical and/or physical chemistry
%Z Chemical Sciences/Coordination chemistryJournal articles
%X A mechanistic study of the photocleavage of the methylthioethanol ligand (Hmte) in the series of ruthenium complexes [Ru(tpy)(N-N)(Hmte)] 2+ (tpy = 2,2′:6′,2′′-terpyridine, N-N = bpy (2,2′-bipyridine), biq (2,2′-biquinoline), dcbpy (6,6′-dichloro-2,2′-bipyridine), dmbpy (6,6′-dimethyl-2,2′-bipyridine)) was performed using density functional theory. These studies reveal the decisive role of two quasi-degenerate triplet metal-centered states, denoted 3MC hexa and 3MC penta , on the lowest triplet potential energy surface. It also shows how the population of the specific pentacoordinate 3MC penta state, characterized by a geometry more accessible for the attack of a solvent molecule, is a key step for the efficiency of the photosubstitution reaction. The difference in the photosubstitution quantum yields experimentally observed for this series of complexes (from φ = 0.022 for N-N = bpy up to φ = 0.30 for N-N = dmbpy) is rationalized by the existence of this 3MC penta photoreactive state and by the different topologies of the triplet excited-state potential energy surfaces, rather than by the sole steric properties of these polypyridinyl ligands.
%G English
%2 https://hal.archives-ouvertes.fr/hal-01327047/document
%2 https://hal.archives-ouvertes.fr/hal-01327047/file/AAM_2016_IC_4448.pdf
%L hal-01327047
%U https://hal.archives-ouvertes.fr/hal-01327047
%~ IRSAMC
%~ UNIV-TLSE3
%~ LCPQ
%~ LCPQ_PTC
%~ CNRS
%~ INSA-TOULOUSE
%~ INC-CNRS