Time-Resolved Infrared Spectrum of the MLCT Excited State of W(CO)5(4-CNpyr) (4-CNpyr = 4-Cyanopyridine): Photophysics and Photochemistry

Paul Glyn; Frank P.A. Johnson; Michael W. George; James J. Turner; Alistair J. Lees

doi:10.1021/ic00018a029

Time-Resolved Infrared Spectrum of the MLCT Excited State of W(CO)₅(4-CNpyr) (4-CNpyr = 4-Cyanopyridine): Photophysics and Photochemistry

Paul Glyn, Frank P.A. Johnson, Michael W. George, James J. Turner, Alistair J. Lees

Research output: Journal Publication › Article › peer-review

29 Citations (Scopus)

Abstract

Fast time-resolved infrared spectroscopy is employed to probe the lower metal to 4-CNpyr charge-transfer (MLCT) excited state of W(CO)₅(4-CNpyr) (4-CNpyr = 4-cyanopyridine). On visible irradiation, the CO stretching vibrations shift to higher frequency, confirming that in this excited state the metal center is oxidized. The excited state decays back to the ground state and, via the LF excited state, decomposes to W(CO)₅ and 4-CNpyr. The rate constants for these processes are equal (ca. 4 × 10⁶ s^-1), suggesting that there is a rapid equilibrium between the MLCT and LF states.

Original language	English
Pages (from-to)	3543-3546
Number of pages	4
Journal	Inorganic Chemistry
Volume	30
Issue number	18
DOIs	https://doi.org/10.1021/ic00018a029
Publication status	Published - 1 Sept 1991
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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title = "Time-Resolved Infrared Spectrum of the MLCT Excited State of W(CO)5(4-CNpyr) (4-CNpyr = 4-Cyanopyridine): Photophysics and Photochemistry",

abstract = "Fast time-resolved infrared spectroscopy is employed to probe the lower metal to 4-CNpyr charge-transfer (MLCT) excited state of W(CO)5(4-CNpyr) (4-CNpyr = 4-cyanopyridine). On visible irradiation, the CO stretching vibrations shift to higher frequency, confirming that in this excited state the metal center is oxidized. The excited state decays back to the ground state and, via the LF excited state, decomposes to W(CO)5 and 4-CNpyr. The rate constants for these processes are equal (ca. 4 × 106 s-1), suggesting that there is a rapid equilibrium between the MLCT and LF states.",

author = "Paul Glyn and Johnson, {Frank P.A.} and George, {Michael W.} and Turner, {James J.} and Lees, {Alistair J.}",

year = "1991",

month = sep,

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language = "English",

volume = "30",

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journal = "Inorganic Chemistry",

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T1 - Time-Resolved Infrared Spectrum of the MLCT Excited State of W(CO)5(4-CNpyr) (4-CNpyr = 4-Cyanopyridine)

T2 - Photophysics and Photochemistry

AU - Glyn, Paul

AU - Johnson, Frank P.A.

AU - George, Michael W.

AU - Turner, James J.

AU - Lees, Alistair J.

PY - 1991/9/1

Y1 - 1991/9/1

N2 - Fast time-resolved infrared spectroscopy is employed to probe the lower metal to 4-CNpyr charge-transfer (MLCT) excited state of W(CO)5(4-CNpyr) (4-CNpyr = 4-cyanopyridine). On visible irradiation, the CO stretching vibrations shift to higher frequency, confirming that in this excited state the metal center is oxidized. The excited state decays back to the ground state and, via the LF excited state, decomposes to W(CO)5 and 4-CNpyr. The rate constants for these processes are equal (ca. 4 × 106 s-1), suggesting that there is a rapid equilibrium between the MLCT and LF states.

AB - Fast time-resolved infrared spectroscopy is employed to probe the lower metal to 4-CNpyr charge-transfer (MLCT) excited state of W(CO)5(4-CNpyr) (4-CNpyr = 4-cyanopyridine). On visible irradiation, the CO stretching vibrations shift to higher frequency, confirming that in this excited state the metal center is oxidized. The excited state decays back to the ground state and, via the LF excited state, decomposes to W(CO)5 and 4-CNpyr. The rate constants for these processes are equal (ca. 4 × 106 s-1), suggesting that there is a rapid equilibrium between the MLCT and LF states.

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Time-Resolved Infrared Spectrum of the MLCT Excited State of W(CO)₅(4-CNpyr) (4-CNpyr = 4-Cyanopyridine): Photophysics and Photochemistry

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