Inside information on xenon adsorption in porous organic cages by NMR†

Abstract

In-depth experimental and computational ¹²⁹Xe NMR analysis of extraordinarily efficient adsorption of xenon in a porous organic cage.

Abstract

A solid porous molecular crystal formed from an organic cage, CC3, has unprecedented performance for the separation of rare gases. Here, xenon was used as an internal reporter providing extraordinarily versatile information about the gas adsorption phenomena in the cage and window cavities of the material. ¹²⁹Xe NMR measurements combined with state-of-the-art quantum chemical calculations allowed the determination of the occupancies of the cavities, binding constants, thermodynamic parameters as well as the exchange rates of Xe between the cavities. Chemical exchange saturation transfer (CEST) experiments revealed a minor window cavity site with a significantly lower exchange rate than other sites. Diffusion measurements showed significantly reduced mobility of xenon with loading. ¹²⁹Xe spectra also revealed that the cage cavity sites are preferred at lower loading levels, due to more favourable binding, whereas window sites come to dominate closer to saturation because of their greater prevalence.

Notes

†Electronic supplementary information (ESI) available: Additional details of experimental methods and results as well as computational modelling. See DOI: 10.1039/c7sc01990d