title: Electronic structures and spectroscopic properties of rhenium (I) tricarbonyl photosensitizer: [Re(4,4'-(COOEt)2-2,2'-bpy)(CO)3py]PF6.
abstract: The ground state and lowest triplet-state structures of [Re(4,4'-(COOEt)(2)-2,2'-bpy)(CO)(3)py]PF(6) photosensitizer (bpy=bipyridine, py=pyridine) have been studied with density functional theory (DFT). Time-dependent density functional theory (TD-DFT) was carried out to predict the photophysical properties of the photosensitizer. The effects of the solvents were evaluated using the conductor-like polarizable continuum (CPCM) method in dichloromethane, chloroform, acetonitrile, acetone, ethanol and dimethylsulfoxide. The electronic transition energies computed with BLYP, MPWPW91, B3LYP and MPW1PW91 functionals are compared with the experimental spectra. Based on the calculated excited energies, the experimental absorption maximum is assigned as metal-to-ligand charge transfer (MLCT) and ligand-to-ligand charge transfer (LLCT) mixed transition, and the luminescence originates from the lowest triplet state that is ascribed as the mixed transition of MLCT/LLCT.
authors.affiliation: State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
authors.forename: Yunling
authors.initials: Y
authors.lastname: Gao
authors.forename: Shiguo
authors.initials: S
authors.lastname: Sun
authors.forename: Keli
authors.initials: K
authors.lastname: Han
mesh_terms: D000042:Absorption; D003198:Computer Simulation; D004583:Electrons; D046911:Macromolecular Substances / Q000737:chemistry; D008954:Models, Biological; D008958:Models, Molecular; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000737:chemistry*; D017319:Photosensitizing Agents / Q000737:chemistry*; D011725:Pyridines / Q000737:chemistry*; D012211:Rhenium / Q000737:chemistry*; D013054:Spectrophotometry, Atomic
chemical_list: D046911:Macromolecular Substances; D009942:Organometallic Compounds; D017319:Photosensitizing Agents; D011725:Pyridines; D012211:Rhenium