Electrogenerated poly(thiophenes) derivatized by bipyridine ligands and metal complexes

Abstract

The synthesis of a series of bithiophenic precursors of electrogenerated conjugated polymers functionalized by bipyridine ligands is described. The precursor structure involves two polymerizable groups attached at both ends of a bipyridine ligand and fixed at an internal b-position of thiophene via an alkylsulfanyl or alkoxy spacer. Electrochemical and optical data show that the low polymerization potential resulting from the association of 3,4-ethylenedioxythiophene (EDOT) and alkylsulfanyl or alkoxy thiophene combined with the multi-site polymerization approach allows a straightforward electrosynthesis of extensively conjugated and stable functionalized polymers. On the basis of these results, iron and ruthenium complexes of these precursors have been synthesized and electropolymerized. The analysis of the electrochemical behavior of the resulting polymers shows that they exhibit the typical electrochemical signature of both the conjugated polythiophene backbone and the immobilized metal complex.{ Electronic supplementary information (ESI) available: synthetic procedures and analytical detail for all compounds. See

Electrosynthesis of a functional conducting polymer incorporating ferrocene unit from an EDOT-based bithiophenic precursor

“…Furthermore, the independence of the anodic/ cathodic peak separation (DE p ) on scan rate indicates a fast charge transfer. This result can be explained by the fact that the electroactivity of Fc is located in a potential region where the supporting conjugated backbone is highly conductive [16,17].…”

“…Silica gel (240-400 mesh) from Merck. 2-(3 0 ,4 0 -ethylenedioxythienyl)-3-(2-cyanoethylsulfanyl)thiophene 4 and ethyl 3-ferrocenylpropanoate 7 were prepared according to the literature methods [16][17][18].…”

Functional Oligothiophenes: Molecular Design for Multidimensional Nanoarchitectures and Their Applications

“…377 The precursor ligand contained a polymerizable bithiophene, consisting of a thiophene and an EDOT unit, which was attached to the bipyridine ligand through an alkylsulfanyl linker. The electrochemical polymerization of the complexes formed three-dimensional networks which exhibited the typical signature of both the π-conjugated polythiophene backbone and the immobilized metal complex.…”

Design, synthesis and electrochemical properties of a thiophene derivative functionalized with a siderophore-like chelator

“…Recently, a two-site precursor combining an EDOT moiety with a thiophene ring on which a functional group is attached at the internal b-position via a sulphide linkage was designed to allow efficient electropolymerization at low potential [2]. Indeed, the versatility of this electroactive EDOT-thiophene precursor was demonstrated by the facile electropolymerization of a series of derivatives containing bipyridyl ligands, metal complexes, fullerene C 60, different flexible linkers or ferrocene [2][3][4][5][6]. On the basis of these previous results we have undertaken the synthesis of new systems containing EDOT-thiophene units connected to hydroxypyridinone.…”