Metallo-supramolecular complexes from mPEG/PDPA diblock copolymers and their self-assembled strip nanosheets

Herein we designed and synthesized mPEG/PDPA copolymers containing two 4-([2,2′:6′,2′′-terpyridin]-4′-yl) phenyl (Tpyp) groups at the junction point of the two blocks (mPEG(-b-Tpyp)(2)-b-PDPA(x), x = 23, 33, and 44). Interestingly, after a hierarchical pattern from the coordination of mPEG(-b-Tpyp)(2)-b-PDPA(x) with Ru(ii) ions followed by the self-assembly in water, 2D strip nanosheets with a monomolecular layer were obtained. In contrast, mPEG(-b-Tpyp)(2)-b-PDPA(x) without coordination self-assembled into spherical micelles in the similar condition. The formation of the rigid and charged ⋯Tpyp-Ru(ii)⋯ chain, the brush-shaped polymer architecture and the presence of the hexafluorophosphate (PF(6)(−)) counterions should be responsible for the unique self-assembly behavior of the metallo-supramolecular complexes. It is expected that the hierarchical self-assembly pattern can provide a new strategy for preparation of self-assemblies with different morphologies.