Identifying Selective Host-Guest Interactions Based on Hydrogen Bond Donor-Acceptor Pattern in Functionalized Al-MIL-53 Metal-Organic Frameworks
authors Wack, J; Siegel, R; Ahnfeldt, T; Stock, N; Mafra, L; Senker, J
nationality International
journal JOURNAL OF PHYSICAL CHEMISTRY C
keywords SOLID-STATE NMR; NUCLEAR-MAGNETIC-RESONANCE; DIRECT SPECTRAL OPTIMIZATION; DISTANCE MEASUREMENTS; SENSITIVITY ENHANCEMENT; DECOUPLING SEQUENCES; PROTON SPECTROSCOPY; BREATHING BEHAVIOR; CARBON-DIOXIDE; POWERFUL TOOL
abstract We present a study analyzing the selectivity of host guest interactions in a series of functionalized Al-MIL-53-X metal organic frameworks with X = H, NH2, and NHCHO using acetone; ethanol, and water as probe molecules. While the amino group introduces additional hydrogen bond donor centers the NHCHO anchors function as donor and acceptor. The guests were chosen due to their ability to act solely as an acceptor in the case of acetone, whereas ethanol and water provide acceptor and donor qualities with a gradual decrease of the acceptor strength toward ethanol. The characterization of the host guest interactions includes a comprehensive solid-state NMR spectroscopic study based on a full assignment of H-1 and C-13 high-resolution spectra using CRAMPS decoupling schemes to enhance H-1 resolution combined with advanced 2D HETCOR (H-1-C-13, H-1-Al-27, and H-1-N-14) spectra at high magnetic fields. In spite of a pronounced dynamical disorder of the guests, we could identify a preferred binding of the acetone via a NH center dot center dot center dot OC hydrogen bond for the NH2 and the NHCHO anchor groups by analyzing trends in the C-13 isotropic chemical shifts. At the same time H-1-H-1 through space connectivities reveal a close vicinity of the acetone methyl groups to the benzene rings of the linkers. In contrast, for ethanol and water, the interaction with the anchor groups is too weak to compete with the thermal disorder at room temperature.
publisher AMER CHEMICAL SOC
issn 1932-7447
year published 2013
volume 117
issue 39
beginning page 19991
ending page 20001
digital object identifier (doi) 10.1021/jp4063252
web of science category Chemistry, Physical; Nanoscience & Nanotechnology; Materials Science, Multidisciplinary
subject category Chemistry; Science & Technology - Other Topics; Materials Science
unique article identifier WOS:000326300700023
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