Metal-ligand coordinating polymers utilize labile bonds between polymer-bound ligands and free cations to delocalize and conduct mono and multivalent metal ions in the solid state. These interactions simultaneously act as reversible cross-links, leading to delayed terminal relaxation as measured by oscillatory rheology. Well-controlled poly(methyl acrylate)s with imidazole chain ends are synthesized as model polymers to obtain metal-ligand bond lifetimes and to investigate design rules for solid polymer electrolytes. Through changes in identity of the metal species, metal-ligand bond lifetimes are varied over nearly two orders of magnitude. Scaling analysis demonstrates a correlation between the bond lifetime and the ionic conductivity, suggesting a hierarchical conduction mechanism that involves interplay of polymer segmental motion with the dissociation of metal-ligand bonds. This suggests an alternative means to enhance long-range ionic transport that is partially decoupled from efforts to enhance the segmental mobility of ion-conducting polymers.