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

Zhang, Xiaoyi; Canton, Sophie LU ; Smolentsev, Grigory; Wallentin, Carl-Johan LU ; Liu, Yizhu LU ; Kong, Qingyu; Attenkofer, Klaus; Stickrath, Andrew B.; Mara, Michael W. and Chen, Lin X., et al. (2014) In Journal of the American Chemical Society 136(24). p.8804-8809
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... (More)
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. (Less)
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publication status
published
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in
Journal of the American Chemical Society
volume
136
issue
24
pages
8804 - 8809
publisher
The American Chemical Society
external identifiers
  • wos:000337720200047
  • scopus:84902650826
ISSN
1520-5126
DOI
10.1021/ja5040733
language
English
LU publication?
yes
id
1f76ffc8-33dc-4a48-9cfb-25944b77ff40 (old id 4609531)
date added to LUP
2014-08-26 11:03:03
date last changed
2017-07-23 04:25:13
@article{1f76ffc8-33dc-4a48-9cfb-25944b77ff40,
  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.},
  author       = {Zhang, Xiaoyi and Canton, Sophie and Smolentsev, Grigory and Wallentin, Carl-Johan and Liu, Yizhu and Kong, Qingyu and Attenkofer, Klaus and Stickrath, Andrew B. and Mara, Michael W. and Chen, Lin X. and Wärnmark, Kenneth and Sundström, Villy},
  issn         = {1520-5126},
  language     = {eng},
  number       = {24},
  pages        = {8804--8809},
  publisher    = {The American Chemical Society},
  series       = {Journal of the American Chemical Society},
  title        = {Highly Accurate Excited-State Structure of [Os(bpy)(2)dcbpy](2+) Determined by X-ray Transient Absorption Spectroscopy},
  url          = {http://dx.doi.org/10.1021/ja5040733},
  volume       = {136},
  year         = {2014},
}