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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

DOI: 10.1021/jacs.9b12797 DOI Help

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