Manipulation of Nanostructures in the Co-assembly of Platinum(II) Complexes and Block Copolymers

We report on the formation and manipulation of crystalline nanostructures in two-component supramolecular co-assembly systems of platinum(II) complexes and block copolymers in aqueous solution. Poly(ethylene glycol)-b-poly(acrylic acid) (PEG-b-PAA) is used to interact with the platinum(II) complexes via electrostatic attractions to trigger the stacking and growth of the platinum(II) complexes directed by non-covalent metal-metal and p-p interactions to form water-soluble core-shell nanofibers. The cylindrical core of the nanofiber is formed by PAA blocks and hexagonally packed molecular columns of platinum(II) complexes, and the shell of the nanofiber consists of solvated PEG blocks. 1D nanostructures of platinum(II) complexes with diverse compositions and intriguing spectroscopic and luminescence properties were obtained. Moreover, sonication of the core-shell nanofibers led to formation of short patchy nanofibers with tunable side and end patches, and controlled 1D and 2D self-assembly of the patchy nanofibers was achieved by modulation of PEG steric protection on the nanofiber surface.