title: Theoretical investigation of phosphinidene oxide polypyridine ruthenium(II) complexes: toward the design of a new class of photochromic compounds.
abstract: A DFT-based computational study performed in the gas phase and in acetonitrile on polypyridine ruthenium isomer complexes [Ru(tpy)(bpy)(POPh)](2+) and [Ru(tpy)(bpy)(OPPh)](2+) (bpy = 2,2'-bipyridine, tpy = 2,2':6',2″-terpyridine, Ph = phenyl) predicts that they constitute a prototype for a new family of inorganic photochromic systems. The two isomers are found to absorb in different spectral regions to excited states that are connected adiabatically through a thermodynamically and kinetically favorable triplet potential energy profile. Nonadiabatic routes were identified and shown to be preferable over the adiabatic mechanism. The reverse isomerization reaction is found to be achievable only thermally. The current predictive work will be of prime importance to experimentalists for the design of new inorganic phosphorus-based compounds with attractive photochromic properties.
authors.affiliation: Laboratoire de Chimie et Physique Quantiques-IRSAMC, CNRS et Université de Toulouse , 118 route de Narbonne, 31062 Toulouse Cedex 09, France.
authors.forename: Olivier P J
authors.initials: OP
authors.lastname: Vieuxmaire
authors.forename: Rémi E
authors.initials: RE
authors.lastname: Piau
authors.forename: Fabienne
authors.initials: F
authors.lastname: Alary
authors.forename: Jean-Louis
authors.initials: JL
authors.lastname: Heully
authors.forename: Pierre
authors.initials: P
authors.lastname: Sutra
authors.forename: Alain
authors.initials: A
authors.lastname: Igau
authors.forename: Martial
authors.initials: M
authors.lastname: Boggio-Pasqua