Hybridized molecular materials based on [Mn~III)_2] single molecule magnets with molecular conductors [Ni(dmit)_2]~(n-)

摘要

A new hybridized molecular crystal [Mn(5-MeOsaltmen)(acetone)]_2[Ni(dmit)_2]_6 (5-MeOsaltmen~(2-)=N,N'-(1,1,2,2-tetramethylethylene)bis(5-methoxysalicylideneiminate), dmit~(2-)=2-thioxo-1,3-dithiole-4,5-dithiolate) based on [Mn]~(2+)_2 dimer as a single molecule magnet (SMM) and the dithiolene complex [Ni(dmit)_2] as a conducting part was prepared by electrochemical crystallization of (Bu_4N)[Ni(dmit)_2] in acetone with [Mn(5-MeOsalmen)(H_2O)](PF_6). 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 J_F in the dimeric core (1.85cm~(-1)) can be estimated by Mn-O distance (2.298 ?) 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 50K (ρ_(r.t)=0.3 ?cm, E_a=0.08eV in a crystal) without structural phase transition at ambient pressure. Then, this is a new type of conducting SMM.