Soft Porous Crystal Based upon Organic Cages That Exhibit Guest-Induced Breathing and Selective Gas Separation

Soft porous crystals (SPCs) that exhibit stimuli-responsive dynamic sorption behavior are attracting interest for gas storage/separation applications. However, the design and synthesis of SPCs is challenging. Herein, we report a new type of SPC based on a [2 + 3] imide-based organic cage (NKPOC-1) and find that it exhibits guest-induced breathing behavior. Various gases were found to induce activated NKPOC-1 crystals to reversibly switch from a closed nonporous phase (a) to two porous open phases (beta and gamma). The net effect is gate-opening behavior induced by CO2 and C3 hydrocarbons. Interestingly, NKPOC-1-alpha selectively adsorbs propyne over propylene and propane under ambient conditions. Thus, NKPOC-1-alpha has the potential to separate binary and ternary C3 hydrocarbon mixtures, and the performance was subsequently verified by fixed bed column breakthrough experiments. In addition, molecular dynamics calculations and in situ X-ray diffraction experiments indicate that the gate-opening effect is accompanied by reversible structural transformations. The adsorption energies from molecular dynamics simulations aid are consistent with the experimentally observed selective adsorption phenomena. The understanding gained from this study of NKPOC-1 supports the further development of SPCs for applications in gas separation/storage because SPCs do not inherently suffer from the recyclability problems often encountered with rigid materials.