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) |
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Pages (from-to) | 10861-10867 |
Number of pages | 7 |
Journal | Journal of the American Chemical Society |
Volume | 124 |
Issue number | 36 |
DOIs | |
State | Published - Sep 11 2002 |
ASJC Scopus subject areas
- Catalysis
- Chemistry(all)
- Biochemistry
- Colloid and Surface Chemistry