Pseudo-Gated Adsorption with Negligible Volume Change Evoked by Halogen-Bond Interaction in the Nanospace of MOFs

The enhancement of gas adsorption utilizing weak interactions in porous compounds is highly demanding for the design of energy-efficient storage materials. Here, we present a rational design for such an adsorption process by using synergistic functions between dynamic motion in a local module and weak but specific host–guest interactions, that is, halogen-bond (XB) interactions in metal–organic frameworks (MOFs). We designed a new porous coordination polymer (PCP), that is, Br-PCP, the pore surfaces of which are decorated with −CH₂Br groups and could be useful for interaction with CO₂ molecules. In accordance with our anticipation, in-situ studies suggest that the adsorption step at approximately 54 kPa during CO₂ adsorption is indeed facilitated by XB interactions with little change in the structural volume. This approach of integrating flexible XB modules in rigid PCPs is applicable for designing advanced gas storage systems.