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

Tatsuhiko Mukuta; Naoto Fukazawa; Kei Murata; Akiko Inagaki; Munetaka Akita; Sei'Ichi Tanaka; Shin Ya Koshihara; Ken Onda

doi:10.1021/ic402474t

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

Tatsuhiko Mukuta, Naoto Fukazawa, Kei Murata, Akiko Inagaki, Munetaka Akita, Sei'Ichi Tanaka, Shin Ya Koshihara, Ken Onda

Research output: Contribution to journal › Article › peer-review

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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.

Original language	English
Pages (from-to)	2481-2490
Number of pages	10
Journal	Inorganic chemistry
Volume	53
Issue number	5
DOIs	https://doi.org/10.1021/ic402474t
Publication status	Published - Mar 3 2014
Externally published	Yes

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Inorganic Chemistry

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

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.",

author = "Tatsuhiko Mukuta and Naoto Fukazawa and Kei Murata and Akiko Inagaki and Munetaka Akita and Sei'Ichi Tanaka and Koshihara, {Shin Ya} and Ken Onda",

year = "2014",

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doi = "10.1021/ic402474t",

language = "English",

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T1 - Infrared vibrational spectroscopy of [Ru(bpy)2(bpm)] 2+ and [Ru(bpy)3]2+ in the excited triplet state

AU - Mukuta, Tatsuhiko

AU - Fukazawa, Naoto

AU - Murata, Kei

AU - Inagaki, Akiko

AU - Akita, Munetaka

AU - Tanaka, Sei'Ichi

AU - Koshihara, Shin Ya

AU - Onda, Ken

PY - 2014/3/3

Y1 - 2014/3/3

N2 - 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.

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

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