CO, ethylene, and H2 demonstrate divergent adsorption enthalpies upon interaction with a series of anion-exchanged Ni2X2BTDD materials (X = OH, F, Cl, Br; H2BTDD = bis(1H-1,2,3-triazolo[4,5-b][4',5'-i])dibenzo[1,4]dioxin)). The dissimilar responses of these conventional π-acceptor gaseous ligands are in contrast with the typical behavior that may be expected for gas sorption in metal-organic frameworks (MOFs), which generally follows similar periodic trends for a given set of systematic changes to the host MOF structure. A combination of computational and spectroscopic data reveals that the divergent behavior, especially between CO and ethylene, stems from a predominantly σ-donor interaction between the former and Ni2+ and a π-acceptor interaction for the latter. These findings will facilitate further deliberate postsynthetic modifications of MOFs with open metal sites to control the equilibrium selectivity of gas sorption.