title: Energy Dependence of the Ruthenium(II)-Bipyridine Metal-to-Ligand-Charge-Transfer Excited State Radiative Lifetimes: Effects of ππ*(bipyridine) Mixing.
abstract: The variations in band shape with excited state energy found for the triplet metal to ligand charge transfer ((3)MLCT) emission spectra of ruthenium-bipyridine (Ru-bpy) chromophores at 77 K have been postulated to arise from excited state/excited state configurational mixing. This issue is more critically examined through the determination of the excited state energy dependence of the radiative rate constants (kRAD) for these emissions. Experimental values for kRAD were determined relative to known literature references for Ru-bpy complexes. When the lowest energy excited states are metal centered, kRAD can be anomalously small and such complexes have been identified using density functional theory (DFT) modeling. When such complexes are removed from the energy correlation, there is a strong (3)MLCT energy-dependent contribution to kRAD in addition to the expected classical energy cubed factor for complexes with excited state energies greater than 10 000 cm(-1). This correlates with the DFT calculations which show significant excited state electronic delocalization between a π(bpy-orbital) and a half-filled dπ*-(Ru(III)-orbital) for Ru-bpy complexes with (3)MLCT excited state energies greater than about 16 000 cm(-1). Overall, this work implicates the "stealing" of emission bandshapes as well as intensity from the higher energy, strongly allowed bpy-centered singlet ππ* excited state.
authors.affiliation: ‡Department of Chemistry, Wayne State University, Detroit, Michigan 48202, United States.
authors.forename: Ryan A
authors.initials: RA
authors.lastname: Thomas
authors.affiliation: †Department of Chemistry, Fu-Jen Catholic University, New Taipei City 24205, Taiwan, R.O.C.
authors.forename: Chia Nung
authors.initials: CN
authors.lastname: Tsai
authors.affiliation: ‡Department of Chemistry, Wayne State University, Detroit, Michigan 48202, United States.
authors.forename: Shivnath
authors.initials: S
authors.lastname: Mazumder
authors.affiliation: †Department of Chemistry, Fu-Jen Catholic University, New Taipei City 24205, Taiwan, R.O.C.
authors.forename: I Chen
authors.initials: IC
authors.lastname: Lu
authors.affiliation: ∥Grand Valley State University, 1 Campus Drive, Allendale, Michigan 49401-9403, United States.
authors.forename: Richard L
authors.initials: RL
authors.lastname: Lord
authors.affiliation: ‡Department of Chemistry, Wayne State University, Detroit, Michigan 48202, United States.
authors.forename: H Bernhard
authors.initials: HB
authors.lastname: Schlegel
authors.affiliation: †Department of Chemistry, Fu-Jen Catholic University, New Taipei City 24205, Taiwan, R.O.C.
authors.forename: Yuan Jang
authors.initials: YJ
authors.lastname: Chen
authors.affiliation: ‡Department of Chemistry, Wayne State University, Detroit, Michigan 48202, United States.
authors.forename: John F
authors.initials: JF
authors.lastname: Endicott