Mixed alkylthiophene-based heterocyclic polymers containing oxadiazole units via electrochemical polymerisation: spectroscopic, electrochemical and spectroelectrochemical properties

Abstract

Symmetric alkylthiophene-based mixed heterocyclic trimer and pentamer, containing central oxadiazole units, have been prepared. Because of the electron-withdrawing properties of oxadiazole, the trimer cannot be electropolymerised and undergoes an oxidative-type destruction at high potentials. In contrast, the pentamer readily polymerises, giving a short chain polymer. Both trimer and pentamer exhibit strong photoluminescence with a maximum at 399 nm (13% quantum yield) and 467 nm (46% quantum yield), respectively. The polymer resulting from the electropolymerisation of the pentamer is also luminescent with the maximum of the excitation band at 528 nm (33% quantum yield). The polymer can be oxidatively doped as demonstrated by cyclic voltammetry, showing a clear anodic peak at 0.62 V versus Ag/Ag⁺ and its cathodic counterpart at 0.56 V, associated with the undoping process. The significantly higher potential of the oxidative doping of the prepared mixed heterocyclic polymer, as compared to the poly(alkylthiophene) homopolymer of similar molecular weight, is caused by the presence of the oxadiazole unit, which lowers the electron density in the π-electron system of the oligothiophene subunit and makes its oxidation more difficult. The spectroelectrochemical investigation of the polymer is consistent with its voltammetric behaviour, exhibiting doping-induced bleaching of the band originating from the π-π* transition and simultaneous growth of the bipolaron bands. The observed clear and reversible spectroelectrochemical behaviour makes the developed polymer a promising candidate for applications in electrochromic devices or electrochemical sensors.