Expanding the stoichiometric window for metal cross-linked gel assembly using competition.

Polymer networks with dynamic cross-links have generated widespread interest as tunable and responsive viscoelastic materials. However, narrow stoichiometric limits in cross-link compositions are typically imposed in the assembly of these materials to prevent excess free cross-linker from dissolving the resulting polymer networks. Here we demonstrate how the presence of molecular competition allows for vast expansion of the previously limited range of cross-linker concentrations that result in robust network assembly. Specifically, we use metal-coordinate cross-linked gels to verify that stoichiometric excessive metal ion cross-linker concentrations can still result in robust gelation when in the presence of free ion competing ligands, and we offer a theoretical framework to describe the coupled dynamic equilibria that result in this effect. We believe the insights presented here can be generally applied to advance engineering of the broadening class of polymer materials with dynamic cross-links.