Photophysical Behavior of a New CO2 Reduction Catalyst, Re(CO)2(bpy){P(OEt)3}2+

Osamu Ishitani; Michael W. George; Takashi Ibusuki; Frank P.A. Johnson; Kazuhide Koike; Koichi Nozaki; Chyongjin Pac; James J. Turner; Jeremy R. Westwell

doi:10.1021/ic00099a022

Photophysical Behavior of a New CO₂ Reduction Catalyst, Re(CO)₂(bpy){P(OEt)₃}₂⁺

Osamu Ishitani, Michael W. George, Takashi Ibusuki, Frank P.A. Johnson, Kazuhide Koike, Koichi Nozaki, Chyongjin Pac, James J. Turner, Jeremy R. Westwell

Research output: Journal Publication › Article › peer-review

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Abstract

The photophysical and photochemical properties of the cation Re(CO)₂(2,2′-bipyridyl){P(OEt)₃}₂⁺ (P⁺), which is an effective photochemical reductant of CO₂, are examined by time-resolved infrared spectroscopy (TRIR) of the v(CO) absorption bands, by UV/visible flash photolysis in both emission and absorption, and by spectroelectrochemistry in both infrared and UV/visible regions. It is shown that P⁺ is first excited into a metal to ligand charge transfer state (MLCT) in which the charge is localized on the bpy ligand, resulting in an upward shift in the v(CO) bands. This excited state is quenched by 1,4-diazabicyclo[2.2.2]octane to form the neutral species P with lowered v(CO) infrared bands; there is a rapid back-reaction between P and DABCO. The kinetics of these processes are obtained. Preliminary experiments suggest that P must be further activated before the CO₂ reduction cycle starts.

Original language	English
Pages (from-to)	4712-4717
Number of pages	6
Journal	Inorganic Chemistry
Volume	33
Issue number	21
DOIs	https://doi.org/10.1021/ic00099a022
Publication status	Published - 1 Oct 1994
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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@article{5a5355a0c62d4df4b417f6e8b811af38,

title = "Photophysical Behavior of a New CO2 Reduction Catalyst, Re(CO)2(bpy){P(OEt)3}2+",

abstract = "The photophysical and photochemical properties of the cation Re(CO)2(2,2′-bipyridyl){P(OEt)3}2+ (P+), which is an effective photochemical reductant of CO2, are examined by time-resolved infrared spectroscopy (TRIR) of the v(CO) absorption bands, by UV/visible flash photolysis in both emission and absorption, and by spectroelectrochemistry in both infrared and UV/visible regions. It is shown that P+ is first excited into a metal to ligand charge transfer state (MLCT) in which the charge is localized on the bpy ligand, resulting in an upward shift in the v(CO) bands. This excited state is quenched by 1,4-diazabicyclo[2.2.2]octane to form the neutral species P with lowered v(CO) infrared bands; there is a rapid back-reaction between P and DABCO. The kinetics of these processes are obtained. Preliminary experiments suggest that P must be further activated before the CO2 reduction cycle starts.",

author = "Osamu Ishitani and George, {Michael W.} and Takashi Ibusuki and Johnson, {Frank P.A.} and Kazuhide Koike and Koichi Nozaki and Chyongjin Pac and Turner, {James J.} and Westwell, {Jeremy R.}",

year = "1994",

month = oct,

day = "1",

doi = "10.1021/ic00099a022",

language = "English",

volume = "33",

pages = "4712--4717",

journal = "Inorganic Chemistry",

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T1 - Photophysical Behavior of a New CO2 Reduction Catalyst, Re(CO)2(bpy){P(OEt)3}2+

AU - Ishitani, Osamu

AU - George, Michael W.

AU - Ibusuki, Takashi

AU - Johnson, Frank P.A.

AU - Koike, Kazuhide

AU - Nozaki, Koichi

AU - Pac, Chyongjin

AU - Turner, James J.

AU - Westwell, Jeremy R.

PY - 1994/10/1

Y1 - 1994/10/1

N2 - The photophysical and photochemical properties of the cation Re(CO)2(2,2′-bipyridyl){P(OEt)3}2+ (P+), which is an effective photochemical reductant of CO2, are examined by time-resolved infrared spectroscopy (TRIR) of the v(CO) absorption bands, by UV/visible flash photolysis in both emission and absorption, and by spectroelectrochemistry in both infrared and UV/visible regions. It is shown that P+ is first excited into a metal to ligand charge transfer state (MLCT) in which the charge is localized on the bpy ligand, resulting in an upward shift in the v(CO) bands. This excited state is quenched by 1,4-diazabicyclo[2.2.2]octane to form the neutral species P with lowered v(CO) infrared bands; there is a rapid back-reaction between P and DABCO. The kinetics of these processes are obtained. Preliminary experiments suggest that P must be further activated before the CO2 reduction cycle starts.

AB - The photophysical and photochemical properties of the cation Re(CO)2(2,2′-bipyridyl){P(OEt)3}2+ (P+), which is an effective photochemical reductant of CO2, are examined by time-resolved infrared spectroscopy (TRIR) of the v(CO) absorption bands, by UV/visible flash photolysis in both emission and absorption, and by spectroelectrochemistry in both infrared and UV/visible regions. It is shown that P+ is first excited into a metal to ligand charge transfer state (MLCT) in which the charge is localized on the bpy ligand, resulting in an upward shift in the v(CO) bands. This excited state is quenched by 1,4-diazabicyclo[2.2.2]octane to form the neutral species P with lowered v(CO) infrared bands; there is a rapid back-reaction between P and DABCO. The kinetics of these processes are obtained. Preliminary experiments suggest that P must be further activated before the CO2 reduction cycle starts.

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VL - 33

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 21

ER -

Photophysical Behavior of a New CO₂ Reduction Catalyst, Re(CO)₂(bpy){P(OEt)₃}₂⁺

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