Synthesis and hierarchical self-assembly of luminescent platinum(ii)-containing telechelic metallopolymers

Telechelic polymers that contain a central polymer chain and two metal complex terminals would represent a novel class of functional metallopolymers. In this work, a series of telechelic polystyrenes end-difunctionalized with planar platinum(II) complexes have been successfully synthesized and characterized in detail. These metallopolymers are found to show metal–metal-to-ligand charge-transfer or excimeric phosphorescence emissions in solution arising from Pt(II)⋯Pt(II) and/or π–π stacking interactions between the planar platinum(II) units. Upon dispersion in the chloroform/methanol mixture solvent, they can self-assemble to form flowerlike micelles, wherein the micellar cores are filled with the solvophilic platinum(II) complexes, while the solvophobic polystyrene chains loop back to the same micellar core to generate coronas. The resulting flower micelles can further self-assemble into vesicle-like architectures, and the flowers still retain their original core–corona nanostructures. Such unconventional self-assembled behaviors are presumably due to strong Pt(II)⋯Pt(II) and/or π–π stacking interactions there. The present work of grafting telechelic polymers together with luminescent platinum(II) complexes presents a new way to explore functional metallopolymer materials.