Temperature‐Dependent Separation of CO2 from Light Hydrocarbons in a Porous Self‐Assembly of Vertexes Sharing Octahedra

Abstract Design of flexible porous materials where the diffusion of guest molecules is regulated by the dynamics of contracted pore aperture is challenging. Here, a flexible porous self‐assembly consisting of 1D channels with dynamic bottleneck gates is reported. The dynamic pendant naphthimidazolylmethyl moieties at the channel necks provide kinetic gate function, that enables unusual adsorption for light hydrocarbons. The adsorption for CO 2 is mainly dominated by thermodynamics with the uptakes decreasing with increasing temperature, whereas the adsorptions for larger hydrocarbons are controlled by both thermodynamics and kinetics resulting in an uptake maximum at a temperature threshold. Such an unusual adsorption enables temperature‐dependent separation of CO 2 from the corresponding hydrocarbons.