Efficient new methods of dmid complexes synthesis for advanced materials

Abstract

Efficient new methods of synthesis of 1,3-dithiol-2-one-4,5-dithiolate (dmid) salts are proposed, allowing one to obtain Kt 2[M(dmid) 2] and Kt n [M(dmid) 2] complexes with arbitrary extra-spheric cations and in 90% yield. Nickel and cobalt complexes are first synthesized, with the alkali metals Kt +=Li +, Na +, K +, Rb +, Cs + as extra-spheric cations. Oxidation of Ni complexes by excess iodine causes sharp (up to a 10 4 increase is observed) of their electric conductivity. It is also accompanied by the diminishing number bands in the IR spectra, explained by the increase in symmetry, namely, transition from the twisted to the flat (D 2h symmetry) form of the complex, which is proved by quantum-chemical calculations. The method proposed opens ways to the synthesis of novel synthetic metals and superconductors.