Rapid excited-state structural reorganization captured by pulsed x-rays

Lin X. Chen; Guy Jennings; Tao Liu; David J. Gosztola; Jan P. Hessler; Donald V. Scaltrito; Gerald J. Meyer

doi:10.1021/ja017214g

Rapid excited-state structural reorganization captured by pulsed x-rays

Lin X. Chen^*, Guy Jennings, Tao Liu, David J. Gosztola, Jan P. Hessler, Donald V. Scaltrito, Gerald J. Meyer

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article

135 Scopus citations

Abstract

Visible light excitation of [Cu¹(dmp)₂](BArF), where dmp is 2,9-dimethyl-1,10-phenanthroline and BArF is tetrakis(3,5-bis(trifluoromethylphenyl))borate, in toluene produces a photoluminescent, metal-to-ligand charge-transfer (MLCT) excited state with a lifetime of 98 ± 5 ns. Probing this state within 14 ns after photoexcitation with pulsed X-rays establishes that a Cu¹ center, borne in a Cu¹ geometry, binds an additional ligand to form a five-coordinate complex with increased bond lengths and a coordination geometry of distorted trigonal bipyramid. The average Cu-N bond length increases in the excited state by 0.07 Å. The transiently formed five-coordinate MLCT state is photoluminescent under the condition studied, indicating that the absorptive and emissive states have distinct geometries. The data represent the first X-ray characterization of a molecular excited state in fluid solution on a nanosecond time scale.

Original language	English (US)
Pages (from-to)	10861-10867
Number of pages	7
Journal	Journal of the American Chemical Society
Volume	124
Issue number	36
DOIs	https://doi.org/10.1021/ja017214g
State	Published - Sep 11 2002

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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Chen, L. X., Jennings, G., Liu, T., Gosztola, D. J., Hessler, J. P., Scaltrito, D. V., & Meyer, G. J. (2002). Rapid excited-state structural reorganization captured by pulsed x-rays. Journal of the American Chemical Society, 124(36), 10861-10867. https://doi.org/10.1021/ja017214g

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title = "Rapid excited-state structural reorganization captured by pulsed x-rays",

abstract = "Visible light excitation of [Cu1(dmp)2](BArF), where dmp is 2,9-dimethyl-1,10-phenanthroline and BArF is tetrakis(3,5-bis(trifluoromethylphenyl))borate, in toluene produces a photoluminescent, metal-to-ligand charge-transfer (MLCT) excited state with a lifetime of 98 ± 5 ns. Probing this state within 14 ns after photoexcitation with pulsed X-rays establishes that a Cu1 center, borne in a Cu1 geometry, binds an additional ligand to form a five-coordinate complex with increased bond lengths and a coordination geometry of distorted trigonal bipyramid. The average Cu-N bond length increases in the excited state by 0.07 {\AA}. The transiently formed five-coordinate MLCT state is photoluminescent under the condition studied, indicating that the absorptive and emissive states have distinct geometries. The data represent the first X-ray characterization of a molecular excited state in fluid solution on a nanosecond time scale.",

author = "Chen, {Lin X.} and Guy Jennings and Tao Liu and Gosztola, {David J.} and Hessler, {Jan P.} and Scaltrito, {Donald V.} and Meyer, {Gerald J.}",

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AU - Chen, Lin X.

AU - Jennings, Guy

AU - Liu, Tao

AU - Gosztola, David J.

AU - Hessler, Jan P.

AU - Scaltrito, Donald V.

AU - Meyer, Gerald J.

PY - 2002/9/11

Y1 - 2002/9/11

N2 - Visible light excitation of [Cu1(dmp)2](BArF), where dmp is 2,9-dimethyl-1,10-phenanthroline and BArF is tetrakis(3,5-bis(trifluoromethylphenyl))borate, in toluene produces a photoluminescent, metal-to-ligand charge-transfer (MLCT) excited state with a lifetime of 98 ± 5 ns. Probing this state within 14 ns after photoexcitation with pulsed X-rays establishes that a Cu1 center, borne in a Cu1 geometry, binds an additional ligand to form a five-coordinate complex with increased bond lengths and a coordination geometry of distorted trigonal bipyramid. The average Cu-N bond length increases in the excited state by 0.07 Å. The transiently formed five-coordinate MLCT state is photoluminescent under the condition studied, indicating that the absorptive and emissive states have distinct geometries. The data represent the first X-ray characterization of a molecular excited state in fluid solution on a nanosecond time scale.

AB - Visible light excitation of [Cu1(dmp)2](BArF), where dmp is 2,9-dimethyl-1,10-phenanthroline and BArF is tetrakis(3,5-bis(trifluoromethylphenyl))borate, in toluene produces a photoluminescent, metal-to-ligand charge-transfer (MLCT) excited state with a lifetime of 98 ± 5 ns. Probing this state within 14 ns after photoexcitation with pulsed X-rays establishes that a Cu1 center, borne in a Cu1 geometry, binds an additional ligand to form a five-coordinate complex with increased bond lengths and a coordination geometry of distorted trigonal bipyramid. The average Cu-N bond length increases in the excited state by 0.07 Å. The transiently formed five-coordinate MLCT state is photoluminescent under the condition studied, indicating that the absorptive and emissive states have distinct geometries. The data represent the first X-ray characterization of a molecular excited state in fluid solution on a nanosecond time scale.

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