Xu Shuang, Smith James E T, Weber J Mathias
JILA and Department of Physics, University of Colorado , Boulder, Colorado 80309-0440, United States.
JILA and Department of Chemistry and Biochemistry, University of Colorado , Boulder, Colorado 80309-0440, United States.
J Phys Chem A. 2016 Apr 21;120(15):2350-6. doi: 10.1021/acs.jpca.6b02926. Epub 2016 Apr 7.
We report electronic spectra of a series of ruthenium polypyridine complexes of the form (trpy)(bipy)Ru(II)-L (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.
