Construction of Three-Dimensional Organic Molecular Metals and Realization of Superconductivity

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The main purpose of this research is construction of molecular metals with three-dimensional electronic structure by means of chemical modification to tetrathiapentalene (TTP) type donors which are known to have a strong tendency to give two-dimensional metals. The obtained results are as follows.(1) It has been found that TM-TPDS and TM-PDS afford cation radical salts with three-dimensional molecular array by means of orthogonally arranged one-dimensional stacks. Most of them show metallic electrical conductivity, and exhibit metal to semiconductor transition in the low temperature region.(2) SM-(T) PDT and SM-(T) PDS with the selenomethyl group have been synthesized, and their cation radical salts have been prepared. X-Ray structure analyses of (SM-PDT) X (PhCl)m(X=PF_6, AsF_6) reveal that they are quasi two-dimensional conductors, in which selenium-selenium contacts in the selenomethyl groups along the donor long axis are observed. Though this salt was also semiconductors owing to 1 : 1 composition, these salts exhibit considerably high conductivity of 10^0 S cm^<-1> at room temperature.(3) TTP dimer is an interesting molecular system which is expected to be realized three-dimensional intermolecular interaction by the so-called spanning overlap thanks to the long molecular length as well as the side-by-side interaction. Then, TTP dimer with alkyldithio unit as a spacer have been synthesized, and their electrochemical property was clarified by cyclic voltammetry.The papers which summarized the results mentioned above have been submitted except for the part.