Stepwise self-assembly of a block copolymer–platinum(ii) complex hybrid in solvents of variable quality: from worm-like micelles to free-standing sheets to vesicle-like nanostructures

Abstract

The self-assembly process of formation of worm-like micelles of a block copolymer–platinum(II) complex hybrid is investigated with respect to the influence of solvent quality. When the solvent quality is moderately weakened, unilamellar free-standing sheets are achieved, in which the worm-like micelles snap off to form star micelles together with a few short worms. Extremely worsened solvent quality leads to unilamellar vesicle-like nanostructures, onto which only star micelles emerged. With the intermediate solvent quality, the sheets coexist with the vesicle-like nanostructures. This is well correlated with mechanistic insights regarding the morphological transition from sheet- to vesicle-like nanoassemblies. In these aggregates, short worms and star micelles still hold their core–shell structures. Furthermore, these unconventional superstructures are well interrelated with their luminescence properties. This result challenges the conventional paradigm of the amphiphilic self-assembly of surfactants and block copolymers in selective solvents, where they form bilayered nanostructures and are required universally to be rearranged during the morphological transition from micelles to vesicles.