Electrochimica Acta, Vol.56, No.24, 8108-8114, 2011
An electrochromic diquat-quaterthiophene alternating copolymer: A polythiophene with a viologen-like moiety in the main chain
A bis-bithiophenyl derivative of diquat, 3,10-bis(2,2'-bithiophene-5-yl)-6,7-dihydropyrido[1,2-a:2',1'-c]pyrazino diynium hexafluorophosphate (bt2dq), was synthesized by quaternization of 5,5 ''-bis(2,2'-bithiophene-5-yl)-2,2'-bipyridine with 1,2-dibromoethane. Its UV-vis absorption spectrum is explained by TD-DFT calculations. It shows the electrochemical properties characteristic for bipyridinium salts (viologens and diquats) and can be electropolymerized to form a conjugated polymer composed of alternating quaterthiophene and diquat blocks. The polymer has been characterised by cyclic voltammetry and UV-vis spectroelectrochemistry: it can be reversibly oxidized, with spectral signs of p-doping of the oligothiophene blocks, and reversibly reduced, with formation of viologen-like cation radicals, which dimerize or form pi-stacks. (C) 2011 Elsevier Ltd. All rights reserved.