Rare-earth elements in molecular conductors: Crystal and electronic structures

摘要

The new molecular conductors with some rare-earth metal-complex anions (ET)(5)[M(NCS)(6)NO3] . C2H5OH (M=Dy (1), Y (2), Ho (3)) and (TMTSF)(3)[Y(NO3)(5)] . 2C(6)H(5)Cl (4) as well as a new low-temperature modification of tetra-n-buthylammonium dysprosium(III) complex, (Bu4N)(3)[Dy(NCS)(4)(NO3)(2) (5) used for the preparation of salt I were synthesized and studied by Xray crystallography at 295 and 110K. Salts 1-3 have a layered crystal structure with a new packing type of the radical cation layers, called an (omega-type. Electronic structure calculations for the compounds 1-3 showed that the paired ET molecules have a positive charge + 1 and the single ET molecules are neutral. The directions of the TMTSF stacks in the neighboring organic layers of 4 are practically perpendicular so that salt 4 can be regarded as a precursor of 2D conductors formed by mutually perpendicular directions of conductivity. (C) 2002 Elsevier Science (USA). [References: 25]