Encapsulation of small gas molecules by cryptophane-111 in organic solution. 1. Size- and shape-selective complexation of simple hydrocarbons.
The reversible trapping of small hydrocarbons and other gases by cryptophane-111 (1) in organic solution was characterized with variable-temperature (1)H NMR spectroscopy. Characteristic spectral changes observed upon guest binding allowed kinetic and thermodynamic data to be readily extracted, permitting quantification and comparison of different host-guest interactions. Previous work (J. Am. Chem. Soc. 2007, 129, 10332) demonstrated that 1, the smallest cryptophane to date, forms a complex with xenon with remarkably high affinity. Presently, it is shown that 1 also exhibits slow exchange dynamics with methane at reduced temperatures (delta(bound) = -5.2 ppm) with an association constant K(a) = 148 M(-1) at 298 K. In contrast, ethane and ethylene are poorly recognized by 1 with K(a) values of only 2 M(-1) and 22 M(-1), respectively; moreover, chloromethane (whose molecular volume is similar to that of xenon, approximately 42 A(3)) is not observed to bind to 1. Separately, molecular hydrogen (H(2)) gas is observed to bind 1, but in contrast to other ligands presently studied, H(2) complexation is spectrally manifested by fast exchange throughout virtually the entire range of available conditions, as well as by a complex dependence of the guest (1)H resonance frequency upon temperature and host concentration. Taken together, these results establish 1 as a selective host for small gases, with implications for the design of size- and geometry-selective sensors targeted for various gas molecules.
Chaffee
Kathleen E
KE
Department of Chemistry and Biochemistry, 113 Neckers Building, Southern Illinois University, Carbondale, Illinois 62901, USA.
Fogarty
Heather A
HA
Brotin
Thierry
T
Goodson
Boyd M
BM
Dutasta
Jean-Pierre
JP