title: The photophysics of fac-[Re(CO)3(dppz)(py)]+ in CH3CN: a comparative picosecond flash photolysis, transient infrared, transient resonance Raman and density functional theoretical study.
abstract: The photophysical properties of fac-[Re(CO)3(dppz)(py)]+ (1, where dppz = dipyrido[3,2-a: 2',3'-c]phenazine) in CH3CN have been investigated using a series of complementary techniques including visible and infrared transient absorption and resonance Raman spectroscopy on the picosecond and nanosecond timescales. The results confirm previous reports that the lowest-lying emissive state in 1 is a triplet intra-ligand (3IL) state localised on the dppz ligand and have provided detailed information on the dynamics of 1 upon photoexcitation, including the relative energies of the excited state species encountered and the electronic distribution within these. If the dppz ligand is viewed in terms of phenanthroline (phen) and phenazine (phz) moieties, the emissive state is probably more accurately described as a 3 pi-->pi *(phz) IL state. The picosecond studies have shown that this emissive state is formed, at least in part, within 30 ps of excitation from a precursor, which is possibly a 3 pi-->pi *(phen) IL state. On the nanosecond timescale, TRIR has been employed to elucidate further dynamics and reveal the presence of an energetically close-lying state in equilibrium with the emissive state. This has tentatively been assigned as being 3d pi(Re)-->pi *(phz) metal-to-ligand charge transfer (MLCT) in nature. A summary of the photophysics is proposed in the form of a Jablonski scheme. Time dependent density functional theory (TD-DFT) calculations support the relative ordering and suggested electronic character of the excited state species involved.
authors.affiliation: School of Chemistry, University of Nottingham, University Park, Nottingham, UK NG7 2RD.
authors.forename: Joanne
authors.initials: J
authors.lastname: Dyer
authors.forename: Werner J
authors.initials: WJ
authors.lastname: Blau
authors.forename: Colin G
authors.initials: CG
authors.lastname: Coates
authors.forename: Caitriona M
authors.initials: CM
authors.lastname: Creely
authors.forename: John D
authors.initials: JD
authors.lastname: Gavey
authors.forename: Michael W
authors.initials: MW
authors.lastname: George
authors.forename: David C
authors.initials: DC
authors.lastname: Grills
authors.forename: Sarah
authors.initials: S
authors.lastname: Hudson
authors.forename: John M
authors.initials: JM
authors.lastname: Kelly
authors.forename: Pavel
authors.initials: P
authors.lastname: Matousek
authors.forename: John J
authors.initials: JJ
authors.lastname: McGarvey
authors.forename: Jonathan
authors.initials: J
authors.lastname: McMaster
authors.forename: Anthony W
authors.initials: AW
authors.lastname: Parker
authors.forename: Michael
authors.initials: M
authors.lastname: Towrie
authors.forename: Julia A
authors.initials: JA
authors.lastname: Weinstein