Light hydrocarbon separation is considered one of the most industrially challenging and desired chemical separation processes and is highly essential in polymer and chemical industries. Among them, separating ethylene (C2H4)...

Adsorptive chemical separation is at the forefront of future technologies,f or use in chemical and petrochemical industries.Inthis process,aporous adsorbent selectively allows asingle component from amixture of three or more chemical components to be adsorbed or permeate.T os eparate the unsorted chemicals,adifferent adsorbent is needed. Aunique adsorbent which can recognizea nd separate each of the chemicals from am ixture of three or more components is the necessity for the next generation porous materials.I nt his regard, we demonstrate a"dynamic chemical clip" in asupramolecular framework capable of thermodynamic and kineticsbased chemical separation. The dynamic space,f eaturing as trong preference for aromatic guests through p-p and C-H•••p interactions and adaptability,c an recognizet he individual chemical isomers from mixtures and separate those based on thermodynamic and kinetic factors.The liquid-phase selectivity and separation of the aromatic isomers are possible by the adaptability of the "chemical clip" and here we elucidate the prime factors in ac ombinatorial approach involving crystallographic evidence and detailed computational studies.

Mechanism of higher gas adsorption at higher temperature is revealed using analysis of free energy barrier for gas diffusion across gated pore channels.

Three halogenated metal–organic frameworks (MOFs) reported recently exhibited a second step in their CO2 gas adsorption isotherms. The emergence of halogen-bonding interactions beyond a threshold gas pressure between the framework halogen and the CO2 guest was conjectured to be the underlying reason for the additional step in the isotherm. Our investigation employing periodic density functional theory calculations did not show significant interactions between the halogen and CO2 molecules. Further, using a combination of DFT-based ab initio molecular dynamics and grand canonical Monte Carlo simulations, we find that the increased separation of framework nitrate pairs facing each other across the pore channel enables the accommodation of an additional CO2 molecule which is further stabilized by cooperative interactionsan observation that facilely explains the second isotherm step. The increased separation between the nitrate groups can occur without any lattice expansion, consistent with experiments. The results point to a structural feature to achieve this isotherm step in MOFs that neither possess large pores nor exhibit large-scale structural changes such as breathing.

Adsorptive chemical separation is at the forefront of future technologies, for use in chemical and petrochemical industries. In this process, a porous adsorbent selectively allows a single component from a mixture of three or more chemical components to be adsorbed or permeate. To separate the unsorted chemicals, a different adsorbent is needed. A unique adsorbent which can recognize and separate each of the chemicals from a mixture of three or more components is the necessity for the next generation porous materials. In this regard, we demonstrate a “dynamic chemical clip” in a supramolecular framework capable of thermodynamic and kinetics‐based chemical separation. The dynamic space, featuring a strong preference for aromatic guests through π‐π and C‐H⋅⋅⋅π interactions and adaptability, can recognize the individual chemical isomers from mixtures and separate those based on thermodynamic and kinetic factors. The liquid‐phase selectivity and separation of the aromatic isomers are possible by the adaptability of the “chemical clip” and here we elucidate the prime factors in a combinatorial approach involving crystallographic evidence and detailed computational studies.