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Incorporation of Cr III into a Keggin polyoxometalate as a chemical strategy to stabilize a labile {Cr III O 4 } tetrahedral conformation and promote unattended single-ion magnet properties
Authors:
Nadiia I.
Gumerova
(Universität Wien)
,
Alexander
Roller
(Universität Wien)
,
Gerald
Giester
(Universität Wien)
,
Jurek
Krzystek
(Florida State University)
,
Joan
Cano
(Facultat de Quimica de la Universitat de València)
,
Annette
Rompel
(Universität Wien)
Co-authored by industrial partner:
No
Type:
Journal Paper
Journal:
Journal Of The American Chemical Society
State:
Published (Approved)
Published:
January 2020
Diamond Proposal Number(s):
24909
Abstract: Polyoxometalates (POMs) provide rigid and highly symmetric coordination sites and can be used as a strategy for the stabilization of magnetic ions. Herein, we report a new member of the Keggin archetype – the Cr-centered Keggin anion [α-CrW12O40]5- (CrW12) – with the unusual tetrahedral coordination of CrIII reported for the first time in POMs conferring unattended magnetic properties. POM chemistry has recently presented excellent examples of single molecule and single-ion magnets (SMMs and SIMs) as well as molecular spin qubits; however, the majority of POM-based SIMs reported to date contain lanthanoid ions. CrW12, as the first example of chromium (III) SIM, exhibits slow relaxation of magnetization and quantum tunneling with a single-ion magnetic behavior even above 10 K with an energy barrier for the reversal of the magnetization of 3.0 K. The first 3d-metal SIM based on a non-lacunary Keggin anion is the foundation for a new research area in POM chemistry.
Subject Areas:
Chemistry
Instruments:
B18-Core EXAFS
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