Postpolymerization Grafting of Aniline Tetramer on Polythiophene Chain:  Structural Organization of the Product and Its Electrochemical and Spectroelectrochemical Properties

Abstract

We describe the preparation of solution-processible hybrid polymers, consisting of a polythiophene main chain and randomly distributed alkyl and oligoaniline side groups. The proposed procedure involves three steps: copolymerization of alkyl- and ester-group-substituted thiophenes to give the precursor polymer, followed by the hydrolysis of the pendant ester groups and aniline tetramer grafting through an amidation reaction. The proposed method is more versatile than previously used copolymerization procedures because higher tetraaniline grafting levels can be obtained. The postfunctionalized polymer is electrochemically active both in its oligoaniline part and in its conjugated polythiophene main chain. As shown by complementary voltammeric and UV−vis−NIR and Raman spectroelectrochemical studies, the polymer can be electrochemically doped selectively in its side oligoaniline chains or globally in the main chain as well as in the side chains. Selective side-chain doping can also be achieved chemically through protonation of the grafted oligoaniline groups in their semi-oxidized state. Doping with FeCl3 is global and involves the oxidation of the main chain and Lewis acid complexation of the side chains, as shown by Mössbauer spectroscopy.

Novel Copolymer with Oligoaniline and Anthracene Units in the Main Chain: Synthesis, Characterization, and Optical Properties

“…Another strategy is the incorporation of well-defined oligoanilines into polymers. Up to now, some graft, [10] alternating, [11][12][13][14] and block-like [15] copolymer have been synthesized.…”

Nanostructured Interpenetrating Polymer Network (IPN) Precursor Ultrathin Films

“…This peak also corresponded the p-p à transition band of the neutral polythiophene. [21] At a potential of 1.2 V, a new peak appears at 677 nm. This peak is attributed to the formation of a copolymer of thiophene and carbazole under potentiostatic conditions.…”

Installation of a reactive site for covalent wiring onto an intrinsically conductive poly(ionic liquid)

“…Post-polymerization modification offers a simple strategy for the creation of a functional interface, allowing the introduction of a unique functional group that may otherwise not be compatible with polymerization chemistry [9]. Several post-functionalization strategies have been reported for both conducting [10][11][12][13][14][15] and non-conducting polymers [16,17]. For example, a wide range of reactive groups, including carboxylic acids [10,13,14], amides [14], amines [10], thiols [10,12,15] and halides [12][13][14][15] have been introduced on polythiophene.…”

“…Several post-functionalization strategies have been reported for both conducting [10][11][12][13][14][15] and non-conducting polymers [16,17]. For example, a wide range of reactive groups, including carboxylic acids [10,13,14], amides [14], amines [10], thiols [10,12,15] and halides [12][13][14][15] have been introduced on polythiophene. Approaches applicable to the coupling of conductive systems to biomolecules include the activation of carbon nanotube surface hydroxyls or amines with 1,4-carbonyldiimidazole followed by reaction with amine-containing glucose oxidase [18].…”