Synthesis and charge-transport properties of polymers derived from the oxidation of 1-hydro-1'-(6-(pyrrol-1-yl)hexyl)-4,4'-bipyridinium bis(hexafluorophosphate) and demonstration of a pH-sensitive microelectrochemical transistor derived from the redox properties of a conventional redox center

Abstract

This article describes the synthesis and electrochemical properties of redox polymers, having a polypyrrole backbone and viologen subunits, derived from oxidative electropolymerization of 1-methyl-1'-(6-(pyrrol-1-yl)hexyl)-4,4'-bipyridinium (P-V-Me/sup 2 +/) and 1-hydro-1'-(6-(pyrrol-1-yl)hexyl)-4,4'-bipyridinium (P-V-H/sup 2 +/). Closely spaced (approx. 1.5 ..mu..M) Au microelectrode arrays (approx. 2.5 ..mu..m wide /times/ 50 ..mu..m long /times/ 0.1 ..mu..m high) modified with the polymers can be used to study aspects of the charge-transport behavior of the viologen redox system. Poly(P-V-Me/sup 2 +/) have been used to investigate the characteristics of microelectrochemical transistors based on a viologen redox center and a similar redox center, protonated, monoquaternized bipyridinium, which is pH dependent. The interesting properties from poly(P-V-Me/sup 2 +/) and poly(P-V-H/sup 2 +/) stem from behavior of the pendant viologen redox centers. The device based on poly(P-V-Me/sup 2 +/) has a narrow region (approx. 200 mV) of gate voltage, V/sub G/, where the source-drain current, I/sub D/, is nonzero and has a sharp, pH-independent peak in the I/sub D/-V/sub G/ plot at approx. 0.53 V versus SCE associated with the reversible, one-electron reduction of viologen. This result is consistent with electron self-exchange between redox centers being the mechanism for charge transport. The device based on poly(P-V-H/sup 2 +/) shows amore » pH-dependent I/sub D/ at fixed V/sub G/, as expected from the electrochemical behavior from reversible protonation of the terminal N of the bipyridinium group of poly(P-V-H/sup 2 +/). The microelectrochemical transistor based on poly(P-V-H/sup 2 +/) illustrates the design of chemically sensitive, molecule-based devices using conventional redox materials.« less