Engineering orthogonality in the construction of an alternating rhomboidal copolymer with high fidelity via integrative self-sorting

Abstract

Microtubules play versatile roles in vital movements due to their unique structures in which the subunits α-tubulin and β-tubulin show a strictly alternating arrangement. The synthesis of artificial copolymers with an alternating arrangement has drawn much research attention. However, as far as we know, an alternating copolymer constructed from monomers with complicated self-assembled structures is still rarely reported. Herein, an alternating rhomboidal copolymer (ARC) with high fidelity was prepared by multicomponent self-assembly in one pot based on metal-coordination and host–guest interactions. The delicate structure of the copolymer benefits from the combination of orthogonal self-assembly and integrative self-sorting strategies. Orthogonal self-assembly guarantees the copolymer with a hierarchical structure that rhomboidal metallacycles maintain their structure by metal–ligand coordination and link to each other through host–guest interactions. Meanwhile, integrative self-sorting endows the copolymer with an alternating arrangement based on different host–guest sites on the two rhomboidal metallacyclic cores. This work not only leads to an alternating rhomboidal copolymer having an intricate structure but also develops a strategy to construct novel supramolecular polymers with hierarchical complexity.