Infinite Twisted Polycatenanes

Abstract

Poly[n]catenanes have exceptional mechanical bonding properties that give them tremendous potential for use in the development of molecular machines and soft materials. Synthesizing these compounds has, however, proven to be a formidable challenge. Herein, we describe a concise method for the construction of twisted polycatenanes. Our approach involves using preorganized double helicates as templates, linked crosswise in a linear fashion by either silver ions or triple bonds. By using this approach, we successfully synthesized twisted polycatenanes with both coordination and covalent bonding employing Ag(I) ions and ethynylene units, respectively, as the linkages and leveraging the same Ag(I)‐templated double helicate in both cases. Synthesis with Ag(I) ions formed a single‐crystalline one‐dimensional (1D) coordination poly[n]catenane, and synthesis using ethynylene units generated 1D fibers which self‐assembled with solvents to form a gel. Our results confirm the potential of multi‐stranded metallohelicates for creating sophisticated mechanically interlocked molecules and polymers, which could pave the way for exploration in the realms of molecular nanotopology and materials design.