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Li13Mn(SeO3)8: Lithium-Rich Transition Metal Selenite Containing Jahn–Teller Distortive Cations
journal contribution
posted on 2017-07-25, 13:43 authored by Hongil Jo, Seung Yoon Song, Eunjeong Cho, Jongho So, Suheon Lee, Kwang Yong Choi, Kang Min OkA novel lithium-rich
transition metal selenite, Li13Mn(SeO3)8, that is composed of a Jahn–Teller distortive cation,
Mn3+, in the high spin d4 state, and a second-order
Jahn–Teller (SOJT) distortive lone pair cation, Se4+, has been synthesized via hydrothermal and high temperature solid
state reactions. The selenite is classified as a molecular compound
consisting of MnO6 octahedra, SeO3 trigonal
pyramids, and Li+ cations. Considering the Li–O
interactions, the structure of Li13Mn(SeO3)8 may be described as a pseudo-three-dimensional framework
as well. The title compound is thermally stable up to 500 °C
and starts decomposing above the temperature attributable to the volatilization
of SeO2. While the MnO6 octahedra in Li13Mn(SeO3)8 exhibit six identical Mn–O
bond distances at room temperature due to the dynamic Jahn–Teller
effect, a clear elongation of two Mn–O bonds along a specific
direction is observed at 100 K. A series of isostructural selenites
with different transition metals, i.e., Li13M(SeO3)8 (M = Sc, Cr, and Fe), have been also successfully obtained
in phase pure forms using similar synthetic methods. Magnetic properties,
spectroscopic characterizations, and local dipole moments calculations
for all the synthesized selenites are presented.
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pair cationtitle compound8 exhibitpseudo-three-dimensional frameworkSOJTspectroscopic characterizationsSeO 3state reactionsmoments calculationsJahnMnO 6 octahedratransition metalsSeO 2novel lithium-rich transition metal seleniteLiroom temperature4 stateMagnetic properties100 Kisostructural selenites
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