Functionalized branched EDOT-terthiophene copolymer films by electropolymerization and post-polymerization “click”-reactions

Abstract

SummaryThe electrocopolymerization of 3,4-ethylenedioxythiophene (EDOT) with the branched thiophene building block 2,2′:3′,2″-terthiophene (3T) is presented as a versatile route to functional polymer films. Comparisons to blend systems of the respective homopolymers PEDOT and P3T by in situ spectroelectrochemistry and Raman spectroscopy prove the successful copolymer formation and the access to tailored redox properties and energy levels. The use of EDOT-N3 as co-monomer furthermore allows modifications of the films by polymer analogous reactions. Here, we exemplarily describe the post-functionalization with ionic moieties by 1,3-dipolar cycloaddition (“click”-chemistry) which allows to tune the surface polarity of the copolymer films from water contact angles of 140° down to 40°.

Electrochemical Characterization of Redox Probes Confined in 3D Conducting Polymer Networks

“…[38,39] The Ludwigs group reported on branched electropolymerized and chemically polymerized EDOT-N 3 /2,2':3',2''-terthiophene (3T) copolymer films to introduce ion functionality. [40] The branched amorphous architectures are inherently suitable for fast counterion exchange reactions upon electrochemical doping. [41] In the case of solution-processable conjugated polymers Venkataraman et al proposed to use copolymers of 3-alkylth-iophenes and side-chain functionalized (4-(thiophen-3-yl)-but-1inyl)-triisopropylsilane (3TBT) as linear copolymer systems.…”

“…With (MeCN) 4 Cu(I)PF 6 as a preformed catalyst which stabilizes ions in polar solvents and elemental copper protecting the catalytic system from external oxidation, redox‐active and electron‐donating ferrocene units could be successfully attached to PEDOT films [38,39] . The Ludwigs group reported on branched electropolymerized and chemically polymerized EDOT‐N 3 /2,2’:3’,2’’‐terthiophene (3T) copolymer films to introduce ion functionality [40] . The branched amorphous architectures are inherently suitable for fast counterion exchange reactions upon electrochemical doping [41] …”

Poly(3,4-ethylenedioxythiophene) (PEDOT) Derivatives: Innovative Conductive Polymers for Bioelectronics

“… Most representative functional EDOT monomers synthesized from azidomethyl-EDOT using click chemistry: ( a ) aliphatic, ferrocene phtalamide [ 50 , 52 ], ( b ) fluorinated ester, substituted xantene [ 51 ], ( c ) sugar, bipyridine, naphtalenediimide, substituted fullerene [ 63 ], ( d ) plain aliphatic chains [ 49 , 64 ], ( e ) plain aromatic groups [ 65 ], ( f ) fluorinated ester [ 64 ], ( g ) fluorinated aromatic, primary alcohol [ 53 ], and ( h ) sulfonate salt, have all been connected to the EDOT scaffold via a triazole spacer [ 66 ]. …”

Dynamics of polarons in branched conducting polymers

“…Such polymers attracted certain attention over the past decade. A considerable number of papers have been published in the literature during past two decades on the synthesis of different branched polymers and study of their optical, electronic and mechanical properties (see, e.g., [12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29]). A review of the chemistry and physics of hyperbranched polymers is presented in [15].…”