On the other hand, the end-functionalized coil block can be employed as the macroinitiator to prepare rod–coil block copolymers. For example, Cloutet and coworkers synthesized a thiophene-terminated poly(tert-butylacrylate) (PtBA) and then copolymerized with 3-hexylthiophene by the oxidative polymerization (FeCl3 being the oxidant) to generate a P3AT-b-PtBA rod–coil block copolymers ( Scheme 4(a)) [68]. The successive coupling reaction between the functionalized coil blocks and rod segments was used to prepare rod–coil block copolymers. For example, the hydroxyl-terminated poly(propylene oxide) (PPO) was converted to 4-bromobenzoic acid terminated by a diisopropylcarbodiimide mediated esterification reaction. Then, rod–coil PPP-b-PPO copolymers were fabricated by the Suzuki coupling reaction [79] and [80]. In another example, methyl ketone-terminated of polystyrene (PS) or poly(methyl methacrylate) (PMMA) were prepared by the ATRP method and then coupled with 5-acetyl-2-aminobenzophenone monomer through a condensation polymerization to form rod–coil diblock PPQ-b-PS or PPQ-b-PMMA copolymers ( Scheme 4(b)) [56], [57] and [81].