Journal
JOURNAL OF PHYSICAL CHEMISTRY A
Volume 113, Issue 49, Pages 13675-13684Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jp903452k
Keywords
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Funding
- National Research Agency (ANR program)
- Cluster Recherche Chimie, Region Rhone-Alpes
- Fulbright Scholar Program
- NSF IRFP [0502393]
- NSF [CHE-0349255]
- Office Of Internatl Science &Engineering
- Office Of The Director [0502393] Funding Source: National Science Foundation
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The reversible trapping of small hydrocarbons and other gases by cryptophane-111 (1) in organic solution was characterized with variable-temperature H-1 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, similar to 42 angstrom(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 H-1 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.
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