Electrochemical Polymerization of Bis(3,4‐ethylenedioxythiophene)‐Substituted 1,4‐Diketo‐3,6‐diphenyl‐pyrrolo[3,4‐c]pyrrole (DPP) Derivative

Abstract

Synthesis and electropolymerization of the new bisthienyl‐substituted diketopyrrolopyrrole monomer 1,4‐diketo‐2,5‐di‐hexyl‐3,6‐bis{[2‐(3',4'‐ethylenedi‐oxy)thienyl]phenyl}pyrrolo[3,4‐c]pyrrole (EDOT‐DPP‐EDOT) is reported. EDOT‐DPP‐EDOT exhibits a low oxidation potential of 0.67 V versus ferrocene and can be electropolymerized to form a stable, well adherent polymer thin film at the ITO anode. The polymer film is insoluble in organic solvents, non‐fluorescent, but exhibits reversible electrochromic properties with color changes from deep blue in the neutral state via transparent gray to purple red in the oxidized state. The reversibility in air is excellent.

Electrochromic Behavior of Donor-Acceptor Polymers Containing Diketopyrrolopyrrole Unit

“…The excellent reversibility was previously reported for the anodic electrochromism of the DPP-thiophene copolymers [13][14][15][16][17][18]. Unfortunately, the DPPbased polymers with the fluorene or triphenylamine donors in this study did not show such a reversible electrochromism in the anodic direction.…”

“…On the other hand, as compared to the semiconducting applications, the electrochromic properties of the DPP-based polymers have rarely been investigated. Most of the reported electrochromic DPP-based polymers were the copolymers with thiophenebased comonomers, and accordingly, they showed only an anodic electrochromism [13][14][15][16][17][18].…”

Cyclic Voltammetric, Chronocoulometric, and Spectroelectrochemical Studies of Electropolymerized Films Based on (3,4-Ethylenedioxythiophene)-Substituted 3,6-Dithiophen-2-yl-2,5-dihydropyrrole[3,4-c]pyrrole-1,4-dione

“…Measurements of film thickness were made using an atomic force microscope (Bruker's Dimension Icon, Santa Barbara, CA) on modified ITO surfaces. 1 H NMR and 13 C NMR spectra were obtained using standard acquisition parameters and referenced to TMS. Infrared spectra were obtained with a single reflection diamond ATR.…”

“…This is advantageous because the covalently attached dye moiety will not leach from the electrode surface when the electopolymerized film is exposed to various environments. 13 Such leaching could occur if EDOT was simply electropolymerized in the presence of DTDPP.…”

Electrochemical Polymerisation of N‐Arylated and N‐Alkylated EDOT‐Substituted Pyrrolo[3,4‐c]pyrrole‐1,4‐dione (DPP) Derivatives: Influence of Substitution Pattern on Optical and Electronic Properties

“…Electropolymerisation represents an alternative route to prepare such polymers in a catalyst‐free approach 26–33. Up to now, only a single article appeared, in which electropolymerisation of a bis‐EDOT‐substituted N ‐alkylated DPP monomer was reported 34. An electrochromic polymer with low oxidation potential and reversible switching behaviour was obtained.…”