Theoretical Investigation of Phosphinidene Oxide Polypyridine Ruthenium(II) Complexes: Toward the Design of a New Class of Photochromic Compounds.

Olivier Vieuxmaire (1) , Rémi E. Piau (1) , Fabienne Alary (1) , Jean-Louis Heully (1) , Pierre Sutra (2) , Alain Igau (2) , Martial Boggio-Pasqua (1)

1 PTC - Photochimie théorique et computationnelle (LCPQ)
2 LCC - Laboratoire de chimie de coordination

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.

Domaines: Chimie théorique et/ou physique

Olivier Vieuxmaire, Rémi E. Piau, Fabienne Alary, Jean-Louis Heully, Pierre Sutra, et al.. Theoretical Investigation of Phosphinidene Oxide Polypyridine Ruthenium(II) Complexes: Toward the Design of a New Class of Photochromic Compounds.. Journal of Physical Chemistry A, 2013, 117 (48), pp.12821-30. ⟨10.1021/jp408898n⟩. ⟨hal-00915275⟩