Self-Assembly of a 3d-5f Trinuclear Single-Molecule Magnet from a Pentavalent Uranyl Complex

Mixed-metal uranium compounds are very attractive candidates in the design of single-molecule magnets (SMMs), but only one 3d-5f hetero-polymetallic SMM containing a uranium center is known. Herein, we report two trimeric heterodimetallic 3d-5f complexes self-assembled by cation-cation interactions between a uranyl(V) complex and a TPA-capped M-II complex (M=Mn (1), Cd (2); TPA = tris(2-pyridylmethyl) amine). The metal centers were strategically chosen to promote the formation of discrete molecules rather than extended chains. Compound 1, which contains an almost linear {Mn-O=U=O-Mn} core, exhibits SMM behavior with a relaxation barrier of 81 +/- 0.5 K-the highest reported for a mono-uranium system-arising from intra-molecular Mn-U exchange interactions combined with the high Ising anisotropy of the uranyl(V) moiety. Compound 1 also exhibits an open magnetic hysteresis loop at temperatures less than 3 K, with a significant coercive field of 1.9 T at 1.8 K.


Published in:
Angewandte Chemie-International Edition, 53, 49, 13434-13438
Year:
2014
Publisher:
Weinheim, Wiley-V C H Verlag Gmbh
ISSN:
1433-7851
Keywords:
Laboratories:




 Record created 2014-12-30, last modified 2018-03-17


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