TY - JOUR

T1 - Inside information on xenon adsorption in porous organic cages by NMR

AU - Komulainen, Sanna

AU - Roukala, Juho

AU - Zhivonitko, Vladimir V.

AU - Javed, Muhammad Asadullah

AU - Chen, Linjiang

AU - Holden, Daniel

AU - Hasell, Tom

AU - Cooper, Andrew

AU - Lantto, Perttu

AU - Telkki, Ville Veikko

N1 - Publisher Copyright: © The Royal Society of Chemistry 2017.

PY - 2017/8/1

Y1 - 2017/8/1

N2 - 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.

AB - 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.

KW - BASIS-SETS

KW - CHEMICAL-SHIFT

KW - DIFFUSION

KW - EXCHANGE

KW - FRAMEWORK

KW - MAGNETIC-RESONANCE

KW - MOLECULES

KW - ORDER REGULAR APPROXIMATION

KW - STIMULATED ECHO

KW - ULTRASENSITIVE XE-129 NMR

UR - http://www.scopus.com/inward/record.url?scp=85026311002&partnerID=8YFLogxK

U2 - 10.1039/c7sc01990d

DO - 10.1039/c7sc01990d

M3 - Article

C2 - 28989612

AN - SCOPUS:85026311002

VL - 8

SP - 5721

EP - 5727

JO - Chemical Science

JF - Chemical Science

SN - 2041-6520

IS - 8

ER -