Synthesis and electrochemical polymerization of D-A-D type monomers with thieno[3,4-c]pyrrole-4,6-dione acceptor unit

Abstract

In this study, three new donor-acceptor-donor type monomers bearing 1,3-dibromo-5-(2-ethylhexyl)-4H-thieno[3,4-c]pyrrole- 4,6(5H)-dione (A) as an acceptor unit and thiophene, 3,4-ethylenedioxythiophene (EDOT) and 3,3-didecyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine (didecyl-ProDOT) as donor units were synthesized via Stille cross-coupling reaction and their electrochemical polymerization by repetitive cycling was reported. The electrochemical and optical properties of the monomers ((5-(2-ethylhexyl)-1,3-di(thienyl-2-yl)-4H-thieno[3,4-c]pyrrole-4,6(5H)-dione(TAT), 1,3-bis(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-5-(2-ethylhexyl)-4H-thieno[3,4-c]pyrrole-4,6(5H)-dione (EAE) and 1,3-bis(3,3-didecyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-6-yl)-5-(2-ethylhexyl)-4H-thieno[3,4-c]pyrrole-4,6(5H)-dione (PAP)) and their corresponding polymers called PTAT, PEAE and PPAP were investigated and it was found that EDOT units containing monomer and polymer (EAE and PEAE) have lower oxidation potentials and lower band gap value as compared to didecyl-ProDOT and thiophene units containing monomers and polymers (PAP, TAT and PPAP, PTAT). Spectroelectrochemical investigations conducted on electrochemically obtained polymer films revealed that polymer films exhibited electrochromic behaviors: brick red to gray for PTAT, blue/violet to highly sky blue for PEAE and blue to highly light blue for PPAP in their neutral and oxidized states, respectively. Moreover, PAP was also polymerized chemically using FeCl3 as an oxidizing agent. Both chemically and electrochemically obtained PPAP were found to be soluble in some organic solvents and their dichloromethane solutions can be reversibly oxidized and reduced using antimony pentachloride and hydrazine hydrate solutions, respectively.