Crystal and electronic structure of new molecular semiconductors (ET)5[M(NCS)6NO3]·C2H5OH (M=Dy, Y, Ho) and (TMTSF)3[Y(NO3)5]·2C6H5Cl

The new molecular semiconductors containing rare-earth elements (ET)5[M(NCS)6NO3]·C2H5OH (M=Dy (1), Y (2), Ho (3)) and (TMTSF)3[Y(NO3)5]·2C6H5Cl (4) have been prepared and studied by X-ray crystallography at 110 K, and electronic band structures of the salts have been examined. The salts (1–3) are isostructural and have a layered structure with a new packing type of the radical cation layers, called ω-type, in which the ET donors perform the role of the host in the conductive layer for the alcohol molecules. The calculations of the electronic structure of the compounds (1–3) showed that the ET radical cations in pairs have a positive charge +1 and the single ET molecules are neutral. rections of the TMTSF stacks in the neighboring organic layers in (4) are practically perpendicular so that the (TMTSF)3[Y(NO3)5]·2C6H5Cl salt can be regarded as a precursor of 2D conductors characterized by layers with mutually perpendicular 1D directions of conductivity.