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  • Title: Infrared vibrational spectroscopy of [Ru(bpy)2(bpm)]2+ and [Ru(bpy)3]2+ in the excited triplet state.
    Author: Mukuta T, Fukazawa N, Murata K, Inagaki A, Akita M, Tanaka S, Koshihara SY, Onda K.
    Journal: Inorg Chem; 2014 Mar 03; 53(5):2481-90. PubMed ID: 24528148.
    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.
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