Metal-ion redox cooperativity is commonly invoked in biological catalysis as a fundamental requirement for effecting multi-electron redox reactions under ambient conditions and at biologically accessible reduction potentials (e.g., N2 reduction). Synthetic systems employing base metals lag behind their biological counterparts to catalyze such reactions under similar conditions. Here, we detail our use multimetallic complexes of macrobicyclic ligands as templates for understanding and harnessing this biological cooperativity. Our recent results include catalytic N2 fixation and CO2 reduction, and highlight the effect of cluster design on accessing novel reactivity vis-à-vis the monometallic analogs.