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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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organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Journal of the American Chemical Society
volume
136
issue
24
pages
8804 - 8809
publisher
The American Chemical Society (ACS)
external identifiers
  • wos:000337720200047
  • scopus:84902650826
  • pmid:24875220
ISSN
1520-5126
DOI
10.1021/ja5040733
language
English
LU publication?
yes
additional info
The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Synchrotron Radiation Research (011013009), Chemical Physics (S) (011001060), Centre for Analysis and Synthesis (011001266), Organic chemistry (S/LTH) (011001240)
id
1f76ffc8-33dc-4a48-9cfb-25944b77ff40 (old id 4609531)
date added to LUP
2016-04-01 14:43:16
date last changed
2022-04-22 04:51:47
@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 (ACS)}},
  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}},
  doi          = {{10.1021/ja5040733}},
  volume       = {{136}},
  year         = {{2014}},
}