Highly accurate excited-state structure of [Os(bpy)2dcbpy] 2+ determined by X-ray transient absorption spectroscopy

Xiaoyi Zhang*, Sophie E. Canton, Grigory Smolentsev, Carl Johan Wallentin, Yizhu Liu, Qingyu Kong, Klaus Attenkofer, Andrew B. Stickrath, Michael W. Mara, Lin X. Chen, Kenneth Wärnmark, Villy Sundström

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

44 Scopus citations


Determining the electronic and geometric structures of photoexcited transient species with high accuracy is crucial for understanding their fundamental photochemistry and controlling their photoreactivity. We have applied X-ray transient absorption spectroscopy to measure the XANES and EXAFS spectra of a dilute (submillimolar) solution of the osmium(II) polypyridyl complex [Os(bpy)2dcbpy](PF6)2 (dcbpy = 4,4′-dicarboxy-2,2′-bipyridine) (OsL2L′) in methanol at the Os LIII edge. We have obtained spectra of superb quality for both the ground state and the photoinduced 3MLCT excited state that have allowed us not only to extract detailed information about the Os 5d orbitals but also to resolve very small differences of 0.010 ± 0.008 Å in the average Os-N bond lengths of the ground and excited states. Theoretical calculations using a recently developed DFT-based approach support the measured electronic structures and further identify the nature of the molecular orbitals that contribute to the main absorption bands in the XANES spectra.

Original languageEnglish (US)
Pages (from-to)8804-8809
Number of pages6
JournalJournal of the American Chemical Society
Issue number24
StatePublished - Jun 18 2014

ASJC Scopus subject areas

  • General Chemistry
  • Biochemistry
  • Catalysis
  • Colloid and Surface Chemistry


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