Understanding Carbon Monoxide Binding and Interactions in M-MOF-74 (M = Mg, Mn, Ni, Zn)

)) with various structural constraints ranging from geometrically constrained adsorbent and adsorbate ions to fully optimized geometries to deconvolute the relative contributions of various structural effects to the adsorption energetics and binding distances observed. Our data indicate that the most significant structural changes during adsorption correlate with the greatest π-backbonding behaviors and commensurately result in a sizable binding energy change observed for CO adsorption. The insights built from this work are relevant to two longstanding research challenges within the MOF community: rational design of materials for separations and the design of force fields capable of accurately modeling adsorption.