Insertion of a single-molecule magnet inside a ferromagnetic lattice based on a 3D bimetallic oxalate network: Towards molecular analogues of permanent magnets

The insertion of the single-molecule magnet (SMM) [MnIII(salen) (H2O)]2 2+ (salen2-=N,N-ethylenebis- (salicylideneiminate)) into a ferromagnetic bimetallic oxalate network affords the hybrid compound [MnIII(salen)(H2O)] 2[MnIICrIII(ox)3] 2×(CH3OH)×(CH3CN)2 (1). This cationic Mn2 cluster templates the growth of crystals formed by an unusual achiral 3D oxalate network. The magnetic properties of this hybrid magnet are compared with those of the analogous compounds [Mn III(salen)(H2O)]2[ZnIICr III(ox)3]2×(CH3OH) ×(CH3CN)2 (2) and [InIII(sal 2-trien)][MnIICrIII(ox)3] ×(H2O)0.25×(CH3OH) 0.25×(CH3CN)0.25 (3), which are used as reference compounds. In 2 it has been shown that the magnetic isolation of the Mn2 clusters provided by their insertion into a paramagnetic oxalate network of CrIII affords a SMM behavior, albeit with blocking temperatures well below 500 mK even for frequencies as high as 160 kHz. In 3 the onset of ferromagnetism in the bimetallic MnIICrIII network is observed at Tc=5 K. Finally, in the hybrid compound 1 the interaction between the two magnetic networks leads to the antiparallel arrangement of their respective magnetizations, that is, to a ferrimagnetic phase. This coupling induces also important changes on the magnetic properties of 1 with respect to those of the reference compounds 2 and 3. In particular, compound 1 shows a large magnetization hysteresis below 1 K, which is in sharp contrast with the near-reversible magnetizations that the SMMs and the oxalate ferromagnetic lattice show under the same conditions. Magnetic couple: The insertion of a single-molecule magnet (SMM) into a ferromagnetic bimetallic oxalate network affords the hybrid compound [MnIII(salen)(H 2O)]2[MnIICrIII(ox) 3]2×(MeOH)3×(H2O). The interaction between the two magnetic networks leads to the antiparallel arrangement of their respective magnetizations (see figure). This coupling induces a large magnetization hysteresis below 1 K, in sharp contrast with the near-reversible magnetizations that the SMMs and the oxalate ferromagnetic lattice show under the same conditions. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.Financial support from the European Union (Project HINTS and ERC Advanced Grant SPINMOL), the Spanish MINECO (Project Consolider-Ingenio in Molecular Nanoscience CSD2007–00010, and projects MAT2011–22785, MAT2012–38318-C03–01 and CTQ-2011–26507), the Generalitat Valenciana (Prometeo and ISIC-NANO Programs) and Gobierno de Aragón (MOLCHIP) are gratefully acknowledged.Peer Reviewe