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Inorg Chem. 2014 Mar 3;53(5):2481-90. doi: 10.1021/ic402474t. Epub 2014 Feb 14.

Infrared vibrational spectroscopy of [Ru(bpy)2(bpm)]2+ and [Ru(bpy)3]2+ in the excited triplet state.

Author information

1
Department of Chemistry and Materials Science, Tokyo Institute of Technology , O-okayama, Meguro-ku, Tokyo 152-8551, Japan.

Abstract

This work involved a detailed investigation into the infrared vibrational spectra of ruthenium polypyridyl complexes, specifically heteroleptic [Ru(bpy)2(bpm)](2+) (bpy = 2,2'-bipyridine and bpm = 2,2'-bipyrimidine) and homoleptic [Ru(bpy)3](2+), in the excited triplet state. Transient spectra were acquired 500 ps after photoexcitation, corresponding to the vibrational ground state of the excited triplet state, using time-resolved infrared spectroscopy. We assigned the observed bands to specific ligands in [Ru(bpy)2(bpm)](2+) based on the results of deuterium substitution and identified the corresponding normal vibrational modes using quantum-chemical calculations. Through this process, the more complex vibrational bands of [Ru(bpy)3](2+) were assigned to normal vibrational modes. The results are in good agreement with the model in which excited electrons are localized on a single ligand. We also found that the vibrational bands of both complexes associated with the ligands on which electrons are little localized appear at approximately 1317 and 1608 cm(-1). These assignments should allow the study of the reaction dynamics of various photofunctional systems including ruthenium polypyridyl complexes.

PMID:
24528148
DOI:
10.1021/ic402474t
[Indexed for MEDLINE]

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