Polyallene-block-polythiophene-block-polyallene Copolymers: One-Pot Synthesis, Helical Assembly, and Multiresponsiveness

A family of coil-rod-coil ABA triblock copolymers containing poly(3-hexylthiophene) (P3HT) and poly(hexadecyloxyallene) (PHA) were facilely synthesized in one-pot via three sequential living polymerizations of hexadecyloxyallene, 2-bromo-3-hexyl-5-chloromagnesiothiophene, and hexadecyloxyallene using the pi-allylnickel complex as a single catalyst. Although the different monomers were polymerized under distinct polymerization mechanisms, the one-pot block copolymerization were revealed to proceed in a living/controlled chain-growth manner, affording well-defined PHA-b-P3HT-b-PHA triblock copolymers in high yields with controlled molecular weights and tunable compositions. The isolated triblock copolymers were found to self-assemble into well-defined supramolecular helical polymers with equivalent of right- and left-handedness. The helicity of the assemblies can be facilely tuned through the induction of chiral cholesteryl pendants introduced on the polyallene segments. Moreover, by using this synthetic method, amphiphilic P3HT triblock copolymers containing hydrophobic P3HT and hydrophilic poly(triethylene glycol allene) (PTA) were readily prepared. Such water-soluble PTA-b-P3HT-b-PTA triblock copolymer exhibited multiresponsiveness including solvent, pH, and temperature.