Exploring the supramolecular chemistry of cyclopropeniums: halogen-bonding-induced electrostatic assembly of polymers

Exploring new noncovalent synthons for supramolecular assembly is essential for material innovation. Accordingly, we herein report a unique type of cyclopropenium-based supramolecular motif and demonstrate its applications to polymer self-assembly. Because of the "ion pair strain" effect, trisaminocyclopropenium iodides complex strongly with fluoroiodobenzene derivatives, forming stable adducts. Crystal structure analysis reveals that halogen-bonding between the iodide anion and the iodo substituent of the fluoroiodobenzene is the driving force for the formation of these electrostatically complexed adducts. Such halogen-bonding-induced electrostatic interactions were further successfully applied to drive the assembly of polymers in solution, on surfaces, and in bulk, demonstrating their potential for constructing supramolecular polymeric materials. Exploring new noncovalent synthons for supramolecular assembly is essential for material innovation. We herein report a unique type of cyclopropenium-based supramolecular motif and demonstrate its applications to polymer self-assembly.