Topological architectures enriched by cooperative acetylene coordination

Abstract

Material chemists have utilized acetylene as a robust, flexible, and easily processable building unit, and such properties could be further extended upon the formation of coordination bonds with metals represented by coinage metal ions (Au(I), Ag(I), and Cu(I)). Furthermore, the simultaneous formation of acetylene coordination and other coordination bonds on the same or adjacent metal centers has been shown to result in unprecedented nanostructures. This review highlights the progress of strategies to construct molecular architectures based on acetylene coordination, including our recent work. Initially, relatively simple supramolecules were reported as heralding the advent of something more complex than conventional unimolecular complexes with acetylene coordination. Learning from their design principles, highly complex molecular topologies have recently emerged as fascinating elements in infinite coordination networks and discrete entangled complexes that exploit the diversity of cooperative acetylene coordination. Our study also demonstrated the self-assembly of coordination polyhedra containing highly entangled three-dimensional (3D) topologies, showing extension to co-crystals, controlled topological chirality, and sequence interconversion of 5-nm class porous architectures regulated by counter anion exchange and side chain effects. The application of cooperative acetylene coordination is still in its infancy but holds promise as a fruitful strategy for the creation of diverse coordination nanomaterials.