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Abstract: A highly cross-linked polyviologen film was prepared by reductive electropolymerization of a trifunctional monomer with three 4-cyanopyridinium moieties. The him was deposited on an ITO-deposited glass electrode at higher current efficiency than in the case of a linear polyviologen from a bifunctional monomer. The resulting polymer film shows a clear electrochromism characteristic of a viologen redox process. The him exhibits typical redox waves in a monomer-free electrolytic solution containing a smaller electrolyte anion than the anion used in electropolymerization. On the contrary, the film behaves as electrochemically inactive in a solution containing a larger electrolyte anion due to its reduced mobility through the cavity in the cross-linked polymer structure. This anion- controlled redox behavior suggested that the cavity size in the cross-linked polymer may be determined by the template effect of the electrolyte anion used in electropolymerization, called anion-imprinted electropolymerization. These features can be regarded as a new voltammetric anion recognition of the highly cross-linked polyviologen film. (C) 1999 Elsevier Science S.A. All rights reserved