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Title: Communication: Does a single CH{sub 3}CN molecule attached to Ru(bipy){sub 3}{sup 2+} affect its absorption spectrum?

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4919781· OSTI ID:22415728
;  [1]
  1. Department of Physics and Astronomy, Aarhus University, Aarhus (Denmark)

Tris(bipyridine)ruthenium(II) (Ru(bipy){sub 3}{sup 2+}) is a prototypical transition metal coordination complex whose photophysical properties have attracted considerable attention. A much debated issue is whether the metal-to-ligand charge transfer (MLCT) transition that accounts for the complex’s beautiful red color is fully delocalized across all three bipyridine ligands or located on just one ligand. Here, we show based on gas-phase action spectroscopy that attachment of a single acetonitrile molecule does not change the absorption spectrum from that of the bare ions, which is indicative of a delocalized state. However, the gas-phase spectra of the bare and one solvent molecule complexes are significantly blueshifted relative to that obtained in bulk acetonitrile, which suggests that in solution the polarizability of many solvent molecules working together can localize the MLCT state. Our data clearly show that more than one solvent molecule is needed to break the symmetry of the MLCT excited state and reproduce its solution-phase characteristics.

OSTI ID:
22415728
Journal Information:
Journal of Chemical Physics, Vol. 142, Issue 17; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
Country of Publication:
United States
Language:
English