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@ARTICLE{Wang:637933,
author = {Wang, Yu and Bayarjargal, Lkhamsuren and Bykov, Maxim and
Bykova, Elena and Spahr, Dominik and Glazyrin, Konstantin
and Milman, Victor and Winkler, Bjoern},
title = {{C}r$^{3+}$ -{C}ontaining {C}arbonates and {C}r$_2${O}$_3$
- {P}bcn at {E}xtreme {C}onditions},
journal = {Inorganic chemistry},
volume = {64},
number = {10},
issn = {0020-1669},
address = {Washington, DC},
publisher = {American Chemical Society},
reportid = {PUBDB-2025-03923},
pages = {4996 - 5003},
year = {2025},
note = {We gratefully acknowledge funding from the DFG
(projectsWI1232 and BA4020) and the DFG-Research Unit
FOR2125/CarboPaT.},
abstract = {We synthesized three carbonates, Cr$_2$[CO$_3$]$_3$,
Cr$_2$[C$_2$O$_5$][CO$_3$]$_2$, and Cr$_2$[CO$_3$][O]$_2$,
containing Cr$^{3+}$ by laser heating of chromium oxides in
CO$_2$ at pressures between 45 and 55 GPa. All phases were
characterized by single-crystal X-ray diffraction and Raman
spectroscopy, while density functional theory calculations
complemented the experimental results. The structure of
Cr$_2$[CO$_3$]$_3$-P6$_3$/m contains coplanar groups, and a
4f Wyckoff site is half occupied by Cr$^{3+}$.
Cr$_2$[C$_2$O$_5$][CO$_3$]$_2$-C$_2$/c is characterized by
coplanar [CO$_3$]$_2$− and pyro- [C$_2$O$_5$]$_2$−
anions and is isostructural to
Al$_2$[C$_2$O$_5$][CO$_3$]$_2$. It was obtained only after
prolonged laser heating. The oxycarbonate
Cr$_2$[CO$_3$][O]$_2$-Pbcn was synthesized at the highest
pressure (55 GPa) studied here. In this structure, half of
the oxygen atoms coordinate one carbon and two Cr atoms,
while the other half coordinate three chromium atoms. The
oxidation state of chromium in the carbonates is +3,
independent of the oxidation state (+3 or +4) of chromium in
the oxide starting material. We observed the transformation
of Cr$_2$O$_3$-R3̅c to Cr$_2$O$_3$-Pbcn above 45(2) GPa
after laser heating.},
cin = {DOOR ; HAS-User / FS-PETRA-D},
ddc = {540},
cid = {I:(DE-H253)HAS-User-20120731 /
I:(DE-H253)FS-PETRA-D-20210408},
pnm = {631 - Matter – Dynamics, Mechanisms and Control
(POF4-631) / 6G3 - PETRA III (DESY) (POF4-6G3) / DFG project
G:(GEPRIS)264049573 - Carbonate und Schock-Kompression:
Stabilität, Phasentransformation und chemische Reaktionen
mit Silikaten (264049573) / FS-Proposal: I-20231276
(I-20231276)},
pid = {G:(DE-HGF)POF4-631 / G:(DE-HGF)POF4-6G3 /
G:(GEPRIS)264049573 / G:(DE-H253)I-20231276},
experiment = {EXP:(DE-H253)P-P02.2-20150101},
typ = {PUB:(DE-HGF)16},
doi = {10.1021/acs.inorgchem.4c05003},
url = {https://bib-pubdb1.desy.de/record/637933},
}