Anion-driven supramolecular polymers come and go under dissipative chemistry

Dynamic and non-equilibrium polymerizations seen across biology provide inspiration for artificial systems. These have been explored in the context of various classes of well-described linkage chemistries, e.g., metal coordination and H-bonding, but only rarely with anion-driven recognition chemistries. We present examples using ditopic monomers bearing phosphate headgroups. These phosphates link up as anion-anion dimers forming anti-electrostatic hydrogen bonds inside the central cavities of cyanostar macrocycles with remarkably high stabilities. Recent demonstrations include concentration driven polymerization in solution, as well as stoichiometry controlled homopolymers and alternating copolymers that form tunable and thermally reversible adhesives. We will present new work expanding the scope of linkage chemistries to organic cations. Looking ahead, we will lay out very recent work to use dissipative, aka fueled, chemistry to create cycles of polymerization and depolymerization.