ELECTROCHROMIC METALLOPOLYMER FILM PREPARED BY OXIDATIVE ELECTROPOLYMERIZATION OF THE FE(Ⅱ)-TERPYRIDINE COMPLEX WITH TRIPHENYLAMINE MODIFIED GROUPS

摘要

A functionalized complex [Fe(L)_2](PF_6)_2 {L = 4'-[p-(diphenylamino)phenyl)]-2,2':6',2''-terpyridine} has been synthesized and confirmed successfully. Its oxidative electropolymerization has been conducted by continuous cycling of the working electrode potential from 0 to 1.8 V in 0.1 mol·L~(-1) Bu_4NClO_4/CH_3CN solution containing 5.0×10~(-4) molL~(-1) monomer. The purple hybrid polymer film exhibits a non-diffusional charge transfer behavior of Fe(Ⅲ)/Fe(Ⅱ) couple and an irreversible redox process of phenylamine moiety on the Pt working electrode, as well as high stability in monomer-free electrolytic solution. The film thickness is easily tuned by controlling the number of potential sweeping cycle, and the AC impedance of as-formed film increases with cycling number. The donor-acceptor (D-A) polymer film on ITO shows a broad and red-shifted ~1MLCT wave in the UV-vis spectrum and a clearly electrochromic behavior from purple to pale yellow with the times of 0.9 s for the coloration step and 1.7 s for the bleaching step, the optical contrast of 26.4 % and the coloration efficiency of 223 C~(-1)· cm~2. This work is supported by the Natural Science Foundation of Henan Province (No: 102300410221) and the Project supported by the Young Core Instructor from the Education Commission of Henan Province.