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Incorporation of Cr<sup>III</sup> into a Keggin Polyoxometalate as a Chemical Strategy to Stabilize a Labile {Cr<sup>III</sup>O<sub>4</sub>} Tetrahedral Conformation and Promote Unattended Single-Ion Magnet Properties.

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 a 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 nonlacunary Keggin anion is the foundation for a new research area in POM chemistry.

SUBMITTER: Gumerova NI 

PROVIDER: S-EPMC7052816 | biostudies-literature | 2020 Feb

REPOSITORIES: biostudies-literature

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Incorporation of Cr&lt;sup&gt;III&lt;/sup&gt; into a Keggin Polyoxometalate as a Chemical Strategy to Stabilize a Labile {Cr&lt;sup&gt;III&lt;/sup&gt;O&lt;sub&gt;4&lt;/sub&gt;} Tetrahedral Conformation and Promote Unattended Single-Ion Magnet Properties.

Gumerova Nadiia I NI   Roller Alexander A   Giester Gerald G   Krzystek J J   Cano Joan J   Rompel Annette A  

Journal of the American Chemical Society 20200206 7

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-CrW<sub>12</sub>O<sub>40</sub>]<sup>5-</sup> (CrW<sub>12</sub>), with the unusual tetrahedral coordination of Cr<sup>III</sup> reported for the first time in POMs conferring unattended magnetic properties. POM chemistry has recently presented excellent examples of  ...[more]

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