Rapid excited state structural reorganization captured by pulsed x-rays.
Visible light excitation of [CuI(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 CuII center, borne in a CuI 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 Angstroms. 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.
- Research Organization:
- Argonne National Laboratory (ANL)
- Sponsoring Organization:
- SC; OUS
- DOE Contract Number:
- AC02-06CH11357
- OSTI ID:
- 949431
- Report Number(s):
- ANL/CHM/JA-40876
- Journal Information:
- J. Am. Chem. Soc., Journal Name: J. Am. Chem. Soc. Journal Issue: 36 ; Sep. 11, 2002 Vol. 124; ISSN JACSAT; ISSN 0002-7863
- Country of Publication:
- United States
- Language:
- ENGLISH
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