TANGLED 3-FUNCTIONALIZED POLYPYRROLE DERIVATIVES BUILT AROUND CU(DPP)(2)(-DIPHENYL-1,10-PHENANTHROLINE)() (DPP = 2,9)

The rrol-3-yl)-octan-1-oxy)phenyl]-1,10-phenanthroline ligand L was sy nthesized by condensation of 2,9-di(p-hydroxyphenyl)-1,10-phenanthroli ne with the mesylate derivative of 1-triiso-propylsilyl)-3-(1-octan-8- ol)-pyrrole in dimethylformamide+K2CO3 medium followed by N-deprotecti on using CsF. The entwined complex of Cu+, (CuL2)+, is characterized b y NMR and cyclic voltammetry. Electropolymerization of this complex ge nerates a film. The electrode modified in this way exhibits electroact ivity of both the copper complex (E(CuII/CuI) = 0.4 V; E(CuI/Cu0) = - 1.6 V) and the polypyrrolic matrix (3-PPy) (E3PPy - -0.4 V vs. Ag/10(- 2) mol l-1 Ag+). Compared with the N-pyrrole (E(N-PPy) - E(CuII/CuI)) and 3-thiophene (E3-PT > E(CuII/CuI)) substituted series, the relative location of the potential values (E3-PPy < E(CuII/CuI)) is the most f avourable for the electrical wiring of the Cu(II)/Cu(I) couple. The do ping level of the poly(Cu(L)2)+ film is 0.2.