Identifying Selective Host–Guest Interactions Based on Hydrogen Bond Donor–Acceptor Pattern in Functionalized Al-MIL-53 Metal–Organic Frameworks
Identifying Selective Host–Guest Interactions Based on Hydrogen Bond Donor–Acceptor Pattern in Functionalized Al-MIL-53 Metal–Organic Frameworks
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DOI：
10.1021/jp4063252
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发表时间：
2013-09
影响因子：
3.7
通讯作者：
Julia S Wack;Renée Siegel;Tim Ahnfeldt;N. Stock;L. Mafra;J. Senker
中科院分区：
文献类型：
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作者：
Julia S Wack;Renée Siegel;Tim Ahnfeldt;N. Stock;L. Mafra;J. Senker
我们提出了一个研究分析一系列功能化的Al-MIL-53-X金属有机框架与X = H，NH 2，和NHCHO使用丙酮，乙醇和水作为探针分子的主客体相互作用的选择性。当氨基引入额外的氢键供体中心时，NHCHO锚作为供体和受体起作用。选择客体是因为它们在丙酮的情况下仅作为受体的能力，而乙醇和水提供受体和供体质量，其中受体强度朝向乙醇逐渐降低。主客体相互作用的表征包括基于1H和13 C高分辨率光谱的完整分配的全面固态NMR光谱研究，使用CRAMPS解耦方案结合高级2D HETCOR（1H-13 C，1H-27 Al和1H-14 N）光谱在高磁场下增强1H分辨率。尽管一个明显的动力学紊乱的客人，我们可以确定一个优先结合的丙酮通过NH··
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 1H and 13C high-resolution spectra using CRAMPS decoupling schemes to enhance 1H resolution combined with advanced 2D HETCOR (1H–13C, 1H–27Al, and 1H–14N) 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··...