Simultaneous Novel Synthesis of Conducting and Non-Conducting Halogenated Polymers by Electroinitiation of (2,4,6-Trichloro or 2,6-Dichlorophenolato)ni(ii) Complexes

Abstract

NiL2(Ph)(2)(.)xH(2)O [L=3,5-dimethylpyrazole or N-methyl imidazole; Ph=DCP or TCP; x=0, 1 or 3] complexes were synthesised and characterised by analytical and spectroscopic methods using elemental analysis and FTIR. The electrochemical behavior of the complexes was studied by cyclic voltammetry in tetrabutylammoniumtetrafluoroborate-N,N-dimethylformamide electrolyte-sol vent couple. Cyclic voltammogram of the complexes displayed two-step oxidation processes under the nitrogen gas atmosphere. The polymerization of the complexes was accomplished in the same solvent-electrolyte couple by the constant potential electrolysis of NiL2(Ph)(2)(.)xH(2)O, synthesizing the poly(di- or monochlorophenylene oxide)s via free radical mechanism. The simultaneous polymerization of non-conducting polymer and conducting polymer (the conductivity of 0.7 S cm(-2)) were achieved by electroinitiated polymerization of Ni(DMPz)(2)(TCP)(2). The structural analysis of the polymers were performed using FTIR, H-1 NMR and C-13 NMR spectroscopic techniques and DSC for the thermal analysis. The kinetics of the polymerization was followed by in situ UV-vis spectrophotometer during the electrolysis. The low temperature ESR spectrum of the electrolysis solution also confirmed the formation of phenol radical (g=2.0028). One electron oxidation process of NiL2(DCP)(2)(.)xH(2)O produces a new Ni(II) complex, Ni(L-L)(DCP)(2)(S) by the rapid decomposition of (NiL2)-L-III(DCP)(2) into a ligand radical producing a singlet with the g value of 2.0015. Second electron oxidation process generates oligemers, which could not be isolated from the electrolyte solution. (c) 2005 Elsevier Ltd. All rights reserved.