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 intramolecular 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.