A novel 4(8).6(7) topology metal organic material (MOM) platform of formula [M(bpe)(2)(M'O-4)] (M = Co or Ni; bpe = 1,2-bis(4-pyridyl)ethene; M' = Mo or Cr) has been synthesized and evaluated in the context of gas sorption. These MOMs have been assigned RCSR code mmo and are uninodal 6-connected nets. [Ni-(bpe)(2)(MoO4)], MOOFOUR-1-Ni, and its chromate analogue, CROFOUR-1-Ni, exhibit high CO2 affinity and selectivity, especially at low loading. This behavior can be attributed to exceptionally high isosteric heats of adsorption (Q(st)) of CO2 in MOOFOUR-1-Ni and CROFOUR-1-Ni of similar to 56 and similar to 50 kJ/mol, respectively, at zero loading. These results were validated by molecular simulations which indicate that the electrostatics of these inorganic anions affords attractions toward CO2 that are comparable to those of unsaturated metal centers.