Dendronized Organoplatinum(II) Metallacyclic Polymers Constructed by Hierarchical Coordination-Driven Self-Assembly and Hydrogen-Bonding Interfaces

We describe the efficient preparation of rhomboidal metallacycles that self-assemble upon mixing a donor decorated with 2-ureido-4-pyrimidinone (UPy) with acceptors containing pendant [G1]-[G3] dendrons. The formed rhomboids subsequently polymerize into dendronized organoplatinum(II) metallacyclic polymers through H-bonding UPy interfaces, which possess the structural features of conventional dendronized polymers as well as the dynamic reversibility of supramolecular polymers. Preservation of both properties in a single material is achieved by exploiting hierarchical self-assembly, namely the unification of coordination-driven self-assembly with H-bonding, which provides facile routes to dendronized metallacycles and subsequent high ordering. The supramolecular polymerization defined here represents a novel method to deliver architecturally complex and ordered polymeric materials with adaptive properties.