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@ARTICLE{SreekantanNairLalithambika:428846,
author = {Sreekantan Nair Lalithambika, Sreeju and Golnak, Ronny and
Winter, Bernd and Atak, Kaan},
title = {{E}lectronic {S}tructure of {A}queous
$[{C}o(bpy)_{3}]^{2+/3+}$ {E}lectron {M}ediators},
journal = {Inorganic chemistry},
volume = {58},
number = {8},
issn = {1520-510X},
address = {Washington, DC},
publisher = {American Chemical Society},
reportid = {PUBDB-2019-04736},
pages = {4731 - 4740},
year = {2019},
note = {© American Chemical Society},
abstract = {We report on the electronic structure of cobalt(II)
tris-2,2′-bipyridine and cobalt(III)
tris-2,2′-bipyridine in aqueous solution using resonant
inelastic X-ray scattering (RIXS) spectroscopy at the Co
L-edge and N K-edge resonances. Partial fluorescence yield
X-ray absorption spectra at both edges were obtained by
signal integration of the respective RIXS spectra.
Experiments are complemented by calculations of the X-ray
absorption spectra for high- and low-spin configurations
using density functional theory/restricted open-shell
configuration interaction singles and time-dependent density
functional theory methods. We find that linear combinations
of the simulated X-ray absorption spectra for different spin
states reproduce the experimental spectra. Best agreement is
obtained for measurements at the Co L-edge, for both
samples. For cobalt(II) tris-2,2′-bipyridine, our combined
experimental and computational study reveals $∼40\%$
low-spin and $∼60\%$ high-spin state components. Much
stronger low-spin character is found for cobalt(III)
tris-2,2′-bipyridine, $∼80\%$ low spin and $∼20\%$
high spin. Prominent energy-loss features in the Co RIXS
spectra are indicative of d–d excitations and
charge-transfer excitations due to strong mixing between
metal and ligand orbitals in both complexes. Analysis of N
1s RIXS data reveals the emission from metal dominated
orbitals in the valence region, supporting the strong
metal–ligand mixing.},
cin = {FS-SCS / DOOR ; HAS-User},
ddc = {540},
cid = {I:(DE-H253)FS-SCS-20131031 / I:(DE-H253)HAS-User-20120731},
pnm = {6215 - Soft Matter, Health and Life Sciences (POF3-621) /
6G3 - PETRA III (POF3-622)},
pid = {G:(DE-HGF)POF3-6215 / G:(DE-HGF)POF3-6G3},
experiment = {EXP:(DE-H253)P-P11-20150101 / EXP:(DE-H253)P-P24-20150101},
typ = {PUB:(DE-HGF)16},
pubmed = {pmid:30932491},
UT = {WOS:000465188700006},
doi = {10.1021/acs.inorgchem.9b00167},
url = {https://bib-pubdb1.desy.de/record/428846},
}