Solid-state synthesis of poly(3′,4'-dimethoxy-2,2′:5′, 2′-terthiophene): Comparison with poly(terthiophene) and poly(3′,4′-ethylenedioxy-2,2′:5′,2′- terthiophene)

Abstract

A new terthiophene monomer: 3',4'-dimethoxy-2,2':5',2"-terthiophene (TMT) was synthesized and characterized by 1H-NMR, 13C-NMR and FTIR. The solid-state oxidative polymerizations of TMT were performed in various ratios of oxidant (FeCl3) to monomer (TMT). The resulting polymers were characterized by 1H-NMR, FTIR, UV-vis-NIR, GPC, X-ray diffraction, CV, as well as TGA and conductivity measurements. The structure and properties of poly (TMT) were compared with those of polyterthiophene [poly(TT)] and poly (3′,4′- ethylenedioxy-2,2′:5′,2′-terthiophene) [poly(TET)] prepared under the same polymerization conditions. After comparative analysis with poly(TT) and poly(TET), the effects of the dimethoxy substituent and FeCl3 on the structural and physicochemical properties of the poly(TMT)s were discussed in depth. The comparison suggested that the dimethoxy-substituted polymer did not display higher crystallinity, thermal stability, conductivity and electrochemical activity than ethylenedioxy substituted one. The results also showed that the effect of FeCl 3 on poly(TMT) was similar that seen with the poly(TT), in which the oxidation degree, electrochemical activity and conductivity increased steadily with increasing [FeCl 3]/[TT] ratio. Furthermore, the poly(TMT) and poly(TT) are mostly made up of dimers with a small amount of higher molecular weight components. © 2012 by the authors.