EVIDENCE FROM PICOSECOND TRANSIENT ABSORPTION AND KINETIC STUDIES OF CHARGE-TRANSFER STATES IN COPPER(II) PORPHYRINS.

Dongho Kim; Dewey Holten; Martin Gouterman

doi:10.1021/ja00322a012

EVIDENCE FROM PICOSECOND TRANSIENT ABSORPTION AND KINETIC STUDIES OF CHARGE-TRANSFER STATES IN COPPER(II) PORPHYRINS.

Dongho Kim, Dewey Holten, Martin Gouterman

Department of Chemistry

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

89 Citations (Scopus)

Abstract

Excited-state dynamics of copper(II) tetraphenylporphyrin left bracket Cu(TPP) right bracket and copper(II) etioporphyrin left bracket Cu(Etio) right bracket depends dramatically on the coordinating properties of the solvent system. Relaxation of transient absorption and recovery of ground-state bleaching following excitation with 35-ps flashes at 355 nm range from greater than 10 ns in the noncoordinating solvent, toluene, to approx. 100 ps in the coordinating solvent, piperidine. Lifetimes of intermediate duration are observed in toluene/piperidine mixtures; for Cu(TPP) the time constants are 650 ps and 2. 1 ns in 1 and 0. 3 M piperidine, respectively. Analogous results are found for Cu(Etio) and in pyridine. Despite such variation in kinetic behavior, transient difference spectra observed for both Cu porphyrins are essentially independent of solvent.

Original language	English
Pages (from-to)	2793-2798
Number of pages	6
Journal	Journal of the American Chemical Society
Volume	106
Issue number	10
DOIs	https://doi.org/10.1021/ja00322a012
Publication status	Published - 1984

All Science Journal Classification (ASJC) codes

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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10.1021/ja00322a012

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title = "EVIDENCE FROM PICOSECOND TRANSIENT ABSORPTION AND KINETIC STUDIES OF CHARGE-TRANSFER STATES IN COPPER(II) PORPHYRINS.",

abstract = "Excited-state dynamics of copper(II) tetraphenylporphyrin left bracket Cu(TPP) right bracket and copper(II) etioporphyrin left bracket Cu(Etio) right bracket depends dramatically on the coordinating properties of the solvent system. Relaxation of transient absorption and recovery of ground-state bleaching following excitation with 35-ps flashes at 355 nm range from greater than 10 ns in the noncoordinating solvent, toluene, to approx. 100 ps in the coordinating solvent, piperidine. Lifetimes of intermediate duration are observed in toluene/piperidine mixtures; for Cu(TPP) the time constants are 650 ps and 2. 1 ns in 1 and 0. 3 M piperidine, respectively. Analogous results are found for Cu(Etio) and in pyridine. Despite such variation in kinetic behavior, transient difference spectra observed for both Cu porphyrins are essentially independent of solvent.",

author = "Dongho Kim and Dewey Holten and Martin Gouterman",

year = "1984",

doi = "10.1021/ja00322a012",

language = "English",

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journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

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AU - Kim, Dongho

AU - Holten, Dewey

AU - Gouterman, Martin

PY - 1984

Y1 - 1984

N2 - Excited-state dynamics of copper(II) tetraphenylporphyrin left bracket Cu(TPP) right bracket and copper(II) etioporphyrin left bracket Cu(Etio) right bracket depends dramatically on the coordinating properties of the solvent system. Relaxation of transient absorption and recovery of ground-state bleaching following excitation with 35-ps flashes at 355 nm range from greater than 10 ns in the noncoordinating solvent, toluene, to approx. 100 ps in the coordinating solvent, piperidine. Lifetimes of intermediate duration are observed in toluene/piperidine mixtures; for Cu(TPP) the time constants are 650 ps and 2. 1 ns in 1 and 0. 3 M piperidine, respectively. Analogous results are found for Cu(Etio) and in pyridine. Despite such variation in kinetic behavior, transient difference spectra observed for both Cu porphyrins are essentially independent of solvent.

AB - Excited-state dynamics of copper(II) tetraphenylporphyrin left bracket Cu(TPP) right bracket and copper(II) etioporphyrin left bracket Cu(Etio) right bracket depends dramatically on the coordinating properties of the solvent system. Relaxation of transient absorption and recovery of ground-state bleaching following excitation with 35-ps flashes at 355 nm range from greater than 10 ns in the noncoordinating solvent, toluene, to approx. 100 ps in the coordinating solvent, piperidine. Lifetimes of intermediate duration are observed in toluene/piperidine mixtures; for Cu(TPP) the time constants are 650 ps and 2. 1 ns in 1 and 0. 3 M piperidine, respectively. Analogous results are found for Cu(Etio) and in pyridine. Despite such variation in kinetic behavior, transient difference spectra observed for both Cu porphyrins are essentially independent of solvent.

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