Hybrid organic–inorganic materials based on polypyrrole and 1,3-dithiole-2-thione-4,5-dithiolate (DMIT) containing dianions

The synthesis of hybrid materials by electropolymerization of pyrrole and inorganic complexes based on the DMIT ligand (1,3-dithiole-2-thione-4,5-dithiolate), e.g. [NEt₄]₂[M(DMIT)_n] (M = Ni, Pd or Pd, n = 2; M = Sn, n = 3], in acetonitrile solution is reported. Spectroscopic data showed that DMIT-containing anions, [M(DMIT)_n]²⁻, were inserted into the polypyrrole framework without chemical modification during the electropolymerization process. Cyclic voltammetry showed that materials obtained were electroactive, undergoing redox processes related to both the conducting polymer and the counteranions. The electrochemical results also suggest that, in the case of the transition metal containing films, the counteranions are not trapped in the PPy matrix but undergo anion exchange during the redox cycle of PPy. However, an opposite behaviour was observed with the film with [M(DMIT)_n]²⁻. The films exhibit good thermal stabilities and have conductivity values expected for semiconductors. This study of these hybrid materials highlights the importance of targeting specific materials for specific applications.