ChemInform Abstract: [Ni(dmit)2] Salts with Supramolecular Cation Structure

Abstract

Abstract The dithiolate complex, [Ni(dmit) 2 ] (dmit=2-thioxo-1,3-dithiol-4,5-dithiolate) is an organic π-molecule which gives highly conducting salts with closed shell cations or organic donors. We have found that crown ether macrocycles can be incorporated into the salts in which the crown ethers include alkali metal cations forming supramolecular cation (SC) structures. The SC structural diversity was observed to depend on the size of the crown ether and cation. Three kinds of crown ethers, 12-crown-4, 15-crown-5 and 18-crown-6 in addition to an acyclic polyether analog of pentaetyleneglycol were incorporated in the conducting [Ni(dmit) 2 ] crystals. The structure of these crystals will be described with emphasis on both the structures of SC and Ni(dmit) 2 conducting layers. In one example, the crown ether forms a channel in which the cation has a translational freedom. The cation, otherwise merely forms a periodic Coulomb potential in the crystal, can influence the electrical conduction through the motion in the channel. The monovalent [Ni(dmit) 2 ] salts, which are possible candidates for molecular magnets will be described on a salt having SC structure.