Hybridized molecular materials based on [Mn2III] single molecule magnets with molecular conductors [Ni(dmit)2]n−

A new hybridized molecular crystal [Mn(5-MeOsaltmen)(acetone)]2[Ni(dmit)2]6 (5-MeOsaltmen2−=N,N′-(1,1,2,2-tetramethylethylene)bis(5-methoxysalicylideneiminate), dmit2−=2-thioxo-1,3-dithiole-4,5-dithiolate) based on [Mn]22+ dimer as a single molecule magnet (SMM) and the dithiolene complex [Ni(dmit)2] as a conducting part was prepared by electrochemical crystallization of (Bu4N)[Ni(dmit)2] in acetone with [Mn(5-MeOsalmen)(H2O)](PF6). An segregating stacking arrangement of the SMM layers and conducting layers is formed, where the magnetic and conducting layers involve one crystallographically independent [Mn]+ monomer and three [Ni(dmit)2] molecules. The SMM units were formed by dimerization of the Mn complex. Ferromagnetic exchange parameter JF in the dimeric core (1.85 cm−1) can be estimated by Mn–O distance (2.298 Å) in the out-of-plane dimeric core. For conducting part, overlap integral calculation between [Ni(dmit)2] acceptors in the salt suggests the existence of quasi one-dimensional interactions among the acceptors. The compound exhibits semiconducting behavior from room temperature to 50 K (ρr.t=0.3 Ω cm, Ea=0.08 eV in a crystal) without structural phase transition at ambient pressure. Then, this is a new type of conducting SMM.