Towards hybrid carbazole/pyrrole-based carboxylated monomers: chemical synthesis, characterisation and electro-oxidation properties

Six novel hybrid carbazole (Cbz)-pyrrole (Pyr)-based carboxylated monomers were synthesised and unambiguously characterised using common spectroscopic tools. Clauson-Kaas, amide coupling, LAH (lithium aluminium hydride)-mediated reduction, esterification and debenzylation reactions were used as key chemical reactions towards their multi-step synthesis. The electro-oxidation features of all these six hybrid Cbz/Pyr-monomers were investigated for the electro-deposition of corresponding polyCOOH conducting coatings. Quite interestingly, and due to the fact that such electro-oxidisable monomers contain both types of oxidisable heterocycles, that is, Pyr and Cbz species, it was found that the successful electro-polymerisation of these hybrid Cbz/Pyr-monomers was highly dependent on the relative number of Cbz versus Pyr unit(s) present in corresponding monomers. Indeed, a successful electro-deposition of the corresponding conducting polymeric films onto a working Pt electrode was observed only for hybrid monomers characterised by a Cbz/Pyr unit(s) ratio greater than or equal to 1. This result has been validated by systematically tuning the number of oxidisable Cbz and Pyr unit(s) present in monomers through proper chemical design and monomer multi-step synthesis. In that case, cyclic voltammogram analyses readily confirmed the exclusive electro-deposition of conducting polyCbz-films. (C) 2011 Elsevier Ltd. All rights reserved.