Characterization of the excited states of distal- and proximal-[Ru(tpy)(pynp)OH2]2+ in aqueous solution using time-resolved infrared spectroscopy

Sei'Ichi Tanaka, Kosuke Takahashi, Masanari Hirahara, Masayuki Yagi, Ken Onda

研究成果: Contribution to journalArticle査読

11 被引用数 (Scopus)

抄録

The quasi-stable excited states of distal- and proximal-[Ru(tpy)(pynp)OH2]2+ (tpy = 2,2′,6′,2″-terpyridine, pynp = 2-(2-pyridyl)-1,8-naphthyridine), which exhibits unique irreversible photoisomerization, were assessed in aqueous solution using time-resolved infrared vibrational spectroscopy and quantum chemical calculations. Transient vibrational spectra from 1300 to 1650 cm-1 were acquired 120 and 2 ps after photoexcitation with a 400 nm pulse for the distal- and proximal-isomers, respectively. The calculated vibrational spectra assuming the lowest triplet states were in good agreement with the experimentally observed spectra, and the vibrational bands are assigned to normal vibrational modes obtained from calculations. The lifetimes of the excited state were determined to be 9.7 ns and 6.4 ps for the distal- and proximal-isomers, respectively. Based on these results, we determined various characteristic features of these excited states. Despite the large difference in lifetime, both isomers were assigned to the triplet metal-to-ligand charge transfer (3MLCT) state and there was almost no difference in the positions of the atoms directly coordinated to the Ru atom. The dissimilarity between the isomers is that the pynp ligands are significantly distorted in the case of the distal-isomer while there is hydrogen bonding between the pynp and OH2 ligands in the proximal-isomer. The strong interaction between the low lying 3MLCT state and the ground state presumably causes the very short lifetime and the forbidden photoisomerization of the proximal-isomer, whereas photoisomerization occurs via the thermally populated metal centered (3MC) state from the high-lying 3MLCT state in the case of the distal-isomer.

本文言語英語
ページ(範囲)87-98
ページ数12
ジャーナルJournal of Photochemistry and Photobiology A: Chemistry
313
DOI
出版ステータス出版済み - 12 1 2015
外部発表はい

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Chemical Engineering(all)
  • Physics and Astronomy(all)

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