Supramolecular complexes of poly(3‐Hexylthiophene)‐block (and random)‐poly[3‐(2‐(6‐carboxyhexyl)methyl)thiophene] copolymers with perylene bisimide

Block and random copolymers of poly(3‐hexylthiophene) and poly3‐(2‐(6‐carboxyhexyl)methyl)thiophene] with side‐chain carboxylic functionality ((P3HT‐b‐P3COOH) and (P3HT‐r‐P3COOH) were developed by Grignard Metathesis (GRIM) polymerization. The carboxylic functionality was introduced in the side chain via the oxazoline route. Both the block and random polythiophene copolymers were complexed with pyridine functionalized perylene bisimide to obtain supramolecular block and random polymer complexes. The complex formation in both systems was confirmed by ¹H NMR, WXRD and SAXS studies. An expansion of d spacing upon complex formation was observed in both the block and random copolymer, which could be traced by WXRD. Hole and electron mobilities measured for the supramolecular complexes indicated values which were higher by an order of magnitude for the supramolecular block complex (μ_h ≈ 2.9 × 10^?4 cm²/Vs; μ_e ≈ 3.1 × 10^?6 cm²/Vs) as compared to the random (μ_h ≈ 1.4 × 10^?5 cm²/Vs; μ_e ≈ 4.7 × 10^?7 cm²/Vs) copolymer. These results are indicative of the higher degree of disorder prevailing in the films of random copolymer system compared to the block copolymer. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1574–1583