Highly Accurate Excited-State Structure of [Os(bpy)(2)dcbpy](2+) Determined by X-ray Transient Absorption Spectroscopy

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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)(2)dcbpy](PF6)(2) (dcbpy = 4,4'-dicarboxy-2,2'-bipyridine) (OsL2L') in methanol at the Os L-III edge. We have obtained spectra of superb quality for both the ground state and the photoinduced (MLCT)-M-3 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 angstrom 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.


  • Xiaoyi Zhang
  • Sophie 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
Enheter & grupper

Ämnesklassifikation (UKÄ) – OBLIGATORISK

  • Atom- och molekylfysik och optik
Sidor (från-till)8804-8809
TidskriftJournal of the American Chemical Society
StatusPublished - 2014
Peer review utfördJa