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

Zhang, X.; Canton, S. E.; Smolentsev, G.; Wallentin, C. J.; Liu, Y.; Kong, Q.; Attenkofer, K.; Stickrath, A. B.; Mara, M. W.; Chen, L. X.; Warnmark, K.; Sundstrom, V.

doi:10.1021/ja5040733

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

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Canton, S. E.
Research Group of Structural Dynamics of (Bio)Chemical Systems, MPI for Biophysical Chemistry, Max Planck Society;

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Citation

Zhang, X., Canton, S. E., Smolentsev, G., Wallentin, C. J., Liu, Y., Kong, Q., et al. (2014). Highly accurate excited-state structure of [Os(bpy)₂dcbpy]⁽²⁺⁾ determined by X-ray transient absorption spectroscopy. Journal of the American Chemical Society, 136(24), 8804-8809. doi:10.1021/ja5040733.

Cite as: https://hdl.handle.net/11858/00-001M-0000-002D-7D97-C

Abstract

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.