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

Spectroscopic investigation and characterization of polypyrrole film doped with [MeN4]2[Ni(dmit)2] complex salt

“…1) for the galvanostatic polymerization of PPy doped with [Ni(dmit) 2 ] 2À followed an instantaneous nucleation regime, similarly to the profile obtained for other PPy/M-dmit films [5,8,9,11]. As expected, the PPy/[Ni(dmit) 2 ] 2À film presented a growth potential value higher than those obtained in a previous work, due to the higher current density applied during the synthesis [9].…”

“…The deconvolution of the spectral data revealed that the [Ni(dmit) 2 ] 2À spectrum is better described by eight Gaussian functions. This spectrum has a similar profile to those observed by da Cruz et al [9,11], showing only have not defined the same transition for [Zn(dmit) 2 ] complex, probably due to the smaller participation of the ZnAS moiety to this transition energy. These calculations also indicated that several states have multiconfiguration character, especially those involving intra-ligand transitions [26].…”

“…From the previous chronopotentiometric curves for PPy/M-dmit growth, it was possible to define three different polymerization stages described in the literature [5,8,9,11]. From A to B, after few seconds that the current was applied, an overshoot indicated the occurrence of a starting monomer oxidation in solution controlled by diffusion.…”

“…The synthesis and characterization of PPy and polyaniline (PANI) doped with [M(dmit) n ] mÀ , for different metals (M = Bi, Sn, Pd, Pt, Ni, and In) have been already reported by Rocco et al and Picciani et al [5,[7][8][9][10][11][12]. These polymer/metal complex materials are, therefore, of great interest, since they can open up new perspectives on nanoscience, surface science, as well as material science.…”

“…The low conductivity value was attributed to the tetrahedral geometry of the complex counter-anion, being not readily accommodated onto the linear structure of the polymer backbones. In order to gain insight into the influence of the counter-anion geometry and the transition-metal on the properties of the PPy films, Da Cruz et al [5,9,11] investigated PPy films doped with different [Et 4 N] 2 [M(dmit) n ] complexes (M = Sn (n = 3); M = Pd, Pt, and Ni (n = 2)). PPy/[Sn(dmit) 3 ] 2À showed greater electrochemical properties and higher thermal stability, but even lower conductivity value ($10 À5 S cm À1 ).…”