We report MPM-1-TIFSIX, a molecular porous material (MPM) based upon the neutral metal complex [Cu2(adenine)4(TiF6)2], that self-assembles through a hydrogen-bonding network. This MPM is amenable to room-temperature synthesis and activation. Gas adsorption measurements and ideal adsorbed solution theory selectivity predictions at 298 K revealed enhanced CO2 separation performance relative to a previously known variant as well as the highest CO2 uptake and isosteric heat of adsorption yet reported for an MPM. MPM-1-TIFSIX is thermally stable to 568 K and retains porosity and capacity even after immersion in water for 24 h.