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

Research output: Contribution to journalArticle

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 languageEnglish (US)
Pages (from-to)10861-10867
Number of pages7
JournalJournal of the American Chemical Society
Volume124
Issue number36
DOIs
StatePublished - 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