Structure and Physical Properties of Molecule-Based Magnets Including Transition Metal Complexes of Crown Thioethers

Abstract

Abstract A new series of molecule-based magnets, including crown thioether (9S3 = 1,4,7-trithiacyclononane) complexes of transition metals (Ni, Co, Cu), are presented. TCNQ salts [M(9S3)2](TCNQ)2 (M = Ni, Co) are one-dimensional (1D), antiferromagnetic (AF) complexes with an intra-chain interaction J = −3.9 K and −1.3 K for M = Ni and Co, respectively, despite its long intermolecular distance, for which the large spin density on the sulfur atom in the magnetic [M(9S3)2]2+ cation is responsible. The mixed valence salt [M(9S3)2](TCNQ)3 (M = Ni, Co) is a paramagnetic semiconductor. 1D AF magnet [Cu(9S3)Br2] does not undergo any magnetic transition because of the weak inter-chain interaction. Substituting a very small amount (∼5%) of Cu with Ni causes a structural change. The change decreases the distances of inter-chain S–S contacts, resulting in the generation of an AF transition at TN = 4.5 K. [M(9S3)2][Ni(bdt)2]2 (M = Ni, Co; bdt = 1,2-benzenedithiolato) are weak-ferromagnets with TN = 6.2 K and 2.6 K for M = Ni and Co, respectively. In the crystals, [M(9S3)2]2+–[Ni(bdt)2]− alternate chains and [Ni(bdt)2]− uniform chains coexist. The appearance of weak-ferromagnetism is associated with a competition between two kinds of inter-chain AF interactions between [M(9S3)2]2+–[Ni(bdt)2]− alternate chains, where the stronger one is an indirect inter-chain interaction through [Ni(bdt)2]− uniform chains, while the weaker is a direct inter-chain interaction.