title: Theoretical insight on the S --> O photoisomerization of DMSO complexes of Ru(II).
abstract: Complexes of the type [Ru(tpy)(L)(dmso)](n+) (where tpy = 2,2':6',2''-terpyridine; L = 2,2'-bipyridine (bpy), n = 2; N,N,N',N'-tetramethylethylene diamine (tmen), n = 2; acetylacetonate (acac), n = 1; oxalate (ox), n = 0; malonate (mal), n = 0) were investigated by density functional theory (DFT). The results do not support a promoting role for the dsigma* ligand field (LF) states during excited state S --> O isomerization. Instead, the calculations show that the formation of a Ru(III) center is important in the isomerization, along with the identity of the ancillary bidentate ligand. The present work shows that the orbital contributions from the bidentate ligand to the HOMO, which is typically centered on the ruthenium, plays an important role in the photochemical and oxidative reactivity of the complexes.
authors.affiliation: Department of Chemistry, The Ohio State University, Columbus, Ohio 43210, USA.
authors.forename: Daniel A
authors.initials: DA
authors.lastname: Lutterman
authors.forename: Aaron A
authors.initials: AA
authors.lastname: Rachford
authors.forename: Jeffrey J
authors.initials: JJ
authors.lastname: Rack
authors.forename: Claudia
authors.initials: C
authors.lastname: Turro
mesh_terms: D003198:Computer Simulation; D004121:Dimethyl Sulfoxide / Q000737:chemistry*; D007536:Isomerism; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry; D010100:Oxygen / Q000737:chemistry*; D010777:Photochemistry; D011789:Quantum Theory; D012428:Ruthenium / Q000737:chemistry*; D013455:Sulfur / Q000737:chemistry*
chemical_list: D009942:Organometallic Compounds; D013455:Sulfur; D012428:Ruthenium; D010100:Oxygen; D004121:Dimethyl Sulfoxide