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An optically active, amphiphilic meta -phenylene ethynylene ( m -PE) bearing a chiral amide pendant was designed and synthesized. Living polymerization of m -PE using alkyne-Pd(II) as the initiator afforded well-defined poly( meta -phenylene ethynylene) ( m -PPE). These m -PPEs were found to have a stable helical conformation in THF, 1,4-dioxane, and CH₃CN and showed split Cotton effects over the range of 245⁻400 nm. The positive first Cotton effect was observed at a wavelength of approximately 308 nm, and the negative second Cotton effect was observed at a wavelength of approximately 289 nm. The m -PPEs exhibited helical conformational changes in different mixed solvents and showed effective solvent-dependent helix inversion in CHCl₃/THF solutions. The sign of the Cotton effect of m -PPE was inverted at 25 °C by varying the mixing ratio of THF and CHCl₃. Finally, amphiphilic poly( meta -phenylene ethynylene)- block -polyisocyanide containing hydrophilic PPE and hydrophobic PPI segments were facilely prepared using Pd(II)-terminated m -PPE as the macroinitiator. This block copolymer can self-assemble into well-defined spherical nanostructures in a selective THF/CH₃OH solution. This efficient polymerization will open up enormous opportunities for the preparation of functional amphiphilic block copolymers in a wide variety of fields.

polymers

A Facile Synthetic Route to Amphiphilic Poly(Meta-Phenylene Ethynylene) and Poly(Meta-Phenylene Ethynylene)-Block-Polyisocyanide Using a Single Catalyst