High‐Quality Electrochromic Polythiophenes via BF₃·Et₂O Electropolymerization

Abstract Electrochemical polymerization in the strong Lewis acid, boron trifluoride ethylether (BFEE), has been used to prepare electrochromic polythiophene (PTh) and its derivatives: poly(3‐methylthiophene) (PMeTh), poly(3‐bromothiophene) (PBrTh), and poly(3,4‐dibromothiophene) (PDBrTh). The polymerization processes and properties of the resultant films are compared, where possible, to those carried out in traditional organic electrochemical solvents. The polymerization of these high oxidation potential thiophene monomers in BFEE yielded good‐quality, homogenous, and smooth electroactive and electrochromic films that could be repeatedly switched in common electrochemical solvents up to 240, 1380, 560, and 420 cycles for PTh, PMeTh, PBrTh, and PDBrTh, respectively, for 50 % retention of electroactivity. A colorimetric study of these films showed distinctive color changes between red and blue as they were switched between reduced and oxidized states. These findings allow the use of commercially available high oxidation potential thiophene monomers to provide electrochromic polymers, avoiding the use of other custom‐synthesized monomers.