Results Towards Synthesizing the Potential Electrical Conductor Poly(1,2-dithiolo-1,2-dithiole-2,6-diylidene)

Abstract

Abstract Complex-catalyzed polymerization of bis-alkylthio-acetylenes 4 with nickel catalysts leads to the poly(bis-alkylthio-acetylenes) 2 (P[nbar]: 3–50). The influence of the catalysts, of the structure of the monomers and of the solvent on the polymerization is described. The polymers 2 are insulators and become semiconductors by doping with electron acceptors. Compounds 2 decompose thermically at temperatures higher than 250°C by a splitting off of dialkyldisulfides, dialkylsulfides and alkanethioles. By laser-induced pyrolysis electrical conductors are formed. The 4 are useful starting compounds for synthesizing dimeric 1,4-dithiafulvenes 8. The 1,2-dithiole-thione 3a is available from 2,3-di-tert-butylthiofumarates or perchlorobutadiene with sulfuration reagents. The reactions of 3a with electrophiles and nucleophiles are studied. From 3a, the 3H,6H-2,5-bis-aryl-1,2-thiazolino [5,4-d] 1,2-thiazoline-3,6-dithiones 28 are easily obtainable. Their isomerization to the 3H,6H-3,6-bisarylimino-1,2-dithio...