Infrared Vibrational Spectroscopy of [Ru(bpy)2(bpm)]2+ and [Ru(bpy)3]2+ in the Excited Triplet State
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- 作者：Tatsuhiko Mukuta ; Naoto Fukazawa ; Kei Murata ; Akiko Inagaki ; Munetaka Akita ; Sei鈥檌chi Tanaka ; Shin-ya Koshihara ; Ken Onda
- 刊名：Inorganic Chemistry
- 出版年：2014
- 出版时间：March 3, 2014
- 年：2014
- 卷：53
- 期：5
- 页码：2481-2490
- 全文大小：783K
- 年卷期：v.53,no.5(March 3, 2014)
- ISSN：1520-510X
文摘
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鈥?bipyridine and bpm = 2,2鈥?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鈥?. These assignments should allow the study of the reaction dynamics of various photofunctional systems including ruthenium polypyridyl complexes.