Journal
JOURNAL OF PHYSICAL CHEMISTRY A
Volume 116, Issue 13, Pages 3359-3365Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jp300313s
Keywords
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Funding
- U.S. National Science Foundation [CHE0843922]
- National Institutes of Health, National Center for Research Resources [RR007707]
- NIH/NIDDK
- U.S. Department of Energy, Office of Basic Energy Sciences [W-31-109-ENG-38]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [0843922] Funding Source: National Science Foundation
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The excited-state structure of [Cu-I[(1,10-phenanthro-line-N,N') bis(triphenylphosphine)] cations in their crystalline [BF4] salt has been determined at both 180 and 90 K by single-pulse time-resolved synchrotron experiments with the modified polychromatic Laue method. The two independent molecules in the crystal show distortions on MLCT excitation that differ in magnitude and direction, a difference attributed to a pronounced difference in the molecular environment of the two complexes. As the excited states differ, the decay of the emission is biexponential with two strongly different lifetimes, the longer lifetime, assigned to the more restricted molecule, becoming more prevalent as the temperature increases. Standard deviations in the current Laue study are very much lower than those achieved in a previous monochromatic study of a Cu(I) 2,9-dimethyl-phenanthroline substituted complex (J. Am. Chem. Soc. 2009, 131, 6566), but the magnitudes of the shifts on excitation are similar, indicating that lattice restrictions dominate,over the steric effect of the methyl substitution. Above all, the study illustrates emphatically that molecules in solids have physical properties different from those of isolated molecules and that their properties depend on the specific molecular environment. This conclusion is relevant for the understanding of the properties of molecular solid-state devices, which are increasingly used in current technology.
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