Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 142, Issue 7, Pages 3336-3339Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.9b12797
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Funding
- Austrian Science Fund (FWF) [M2203, P27S34]
- University of Vienna
- Ministerio Espanol de Ciencia e InnovaciOn [CTQ2016-75068P, CTQ2016-75671P]
- NSF [DMR-1644779]
- State of Florida
- Ministerio Espanol de Ciencia e InnovaciOn (Unidad de Excelencia Maria de Maetzu) [MDM-2015-0538]
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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 [alpha-CrW12O40](5-) (CrW12), with the unusual tetrahedral coordination of Cr-III 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 a chromium(III) SIM, exhibits slow relaxation of magnetization and quantum tunneling with a singleion 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 nonlacunary Keggin anion is the foundation for a new research area in POM chemistry.
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