title: Ligand Influence on the Electronic Spectra of Dicationic Ruthenium-Bipyridine-Terpyridine Complexes.
abstract: We report electronic spectra of a series of ruthenium polypyridine complexes of the form [(trpy)(bipy)Ru(II)-L](2+) (bipy = 2,2'-bipyridine and trpy = 2,2':6',2″-terpyridine), where L represents a small molecular ligand that occupies the last coordination site. Species with L = H2O, CO2, CH3CN, and N2 were investigated in vacuo using photodissociation spectroscopy. All species exhibit bright metal-to-ligand charger transfer (MLCT) bands in the visible and near UV, but with different spectral envelopes and peak energies, encoding the influence of the ligand L on the electronic structure of the complex. Several individual electronic bands can be resolved for L = H2O and CO2, while the spectra for L = N2 and CH3CN are more congested, even at low ion temperatures. The experimental results are discussed in the framework of time-dependent density functional theory.
authors.affiliation: JILA and Department of Physics, University of Colorado , Boulder, Colorado 80309-0440, United States.
authors.forename: Shuang
authors.initials: S
authors.lastname: Xu
authors.affiliation: JILA and Department of Chemistry and Biochemistry, University of Colorado , Boulder, Colorado 80309-0440, United States.
authors.forename: James E T
authors.initials: JE
authors.lastname: Smith
authors.affiliation: JILA and Department of Chemistry and Biochemistry, University of Colorado , Boulder, Colorado 80309-0440, United States.
authors.forename: J Mathias
authors.initials: JM
authors.lastname: Weber