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

Zhang, Xiaoyi (author)

Canton, Sophie (author): Lund University,Lunds universitet,Kemisk fysik,Enheten för fysikalisk och teoretisk kemi,Kemiska institutionen,Institutioner vid LTH,Lunds Tekniska Högskola,Chemical Physics,Physical and theoretical chemistry,Department of Chemistry,Departments at LTH,Faculty of Engineering, LTH

Smolentsev, Grigory (author)

Wallentin, Carl-Johan (author): Lund University,Lunds universitet,Centrum för analys och syntes,Kemiska institutionen,Institutioner vid LTH,Lunds Tekniska Högskola,Centre for Analysis and Synthesis,Department of Chemistry,Departments at LTH,Faculty of Engineering, LTH

Liu, Yizhu (author): Lund University,Lunds universitet,Centrum för analys och syntes,Kemiska institutionen,Institutioner vid LTH,Lunds Tekniska Högskola,Centre for Analysis and Synthesis,Department of Chemistry,Departments at LTH,Faculty of Engineering, LTH

Kong, Qingyu (author)

Attenkofer, Klaus (author)

Stickrath, Andrew B. (author)

Mara, Michael W. (author)

Chen, Lin X. (author)

Wärnmark, Kenneth (author): Lund University,Lunds universitet,Centrum för analys och syntes,Kemiska institutionen,Institutioner vid LTH,Lunds Tekniska Högskola,Centre for Analysis and Synthesis,Department of Chemistry,Departments at LTH,Faculty of Engineering, LTH

Sundström, Villy (author): Lund University,Lunds universitet,Kemisk fysik,Enheten för fysikalisk och teoretisk kemi,Kemiska institutionen,Institutioner vid LTH,Lunds Tekniska Högskola,Chemical Physics,Physical and theoretical chemistry,Department of Chemistry,Departments at LTH,Faculty of Engineering, LTH

(creator_code:org_t)

2014-06-09
2014
English.
In: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 1520-5126 .- 0002-7863. ; 136:24, s. 8804-8809

Related links:: http://dx.doi.org/10...; show more...; https://lup.lub.lu.s...; https://doi.org/10.1...; show less...

Abstract Subject headings

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.

By the author/editor: Zhang, Xiaoyi; Canton, Sophie; Smolentsev, Grig ...; Wallentin, Carl- ...; Liu, Yizhu; Kong, Qingyu; show more...; Attenkofer, Klau ...; Stickrath, Andre ...; Mara, Michael W.; Chen, Lin X.; Wärnmark, Kennet ...; Sundström, Villy; show less...

About the subject

NATURAL SCIENCES: NATURAL SCIENCES; and Physical Science ...; and Atom and Molecul ...

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