One-Pot Synthesis, Circularly Polarized Luminescence, and Controlled Self-Assembly of Janus-Type Miktoarm Star Copolymers

With the aim of broadening the scope of Janus-type polymers with new functionalities, Janus-type miktoarm star copolymers comprising helical poly(phenyl isocyanide) (PPI) and a vinyl polymer were designed and synthesized via a combination of Pd(II)-initiated isocyanide polymerization and atom transfer radical polymerization (ATRP). A functional beta-cyclodextrin bearing 7 Pd(II) complexes at one side and 14 bromine groups at the other side ((Pd(II))(7)-CD-(Br)(14)) was prepared and used as an initiator for the one-pot polymerization of phenyl isocyanide and the ATRP of vinyl monomers in a living and controlled manner. A variety of Janus-type copolymers with different structures and tunable compositions were facilely obtained by using this method. Thus, Janus-type copolymers composed of helical PPIs and tetraphenylethylene-modified vinyl polymers exhibited a significant circularly polarized luminescence performance in both soluble and aggregated states. Meanwhile, Janus-type copolymers containing PPIs and hydrophilic vinyl polymers presented amphiphilicity and self-assembled into diverse morphologies.