Journal
INORGANIC CHEMISTRY
Volume 53, Issue 5, Pages 2481-2490Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ic402474t
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Funding
- JST, PRESTO (Precursory Research for Embryonic Science and Technology)
- G-COE program of the Tokyo Institute of Technology
- Japan Society for the Promotion of Science, JSPS
- Grants-in-Aid for Scientific Research [24550071, 12J09686] Funding Source: KAKEN
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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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