Single-Crystalline Ultrathin 2D Porous Nanosheets of Chiral Metal–Organic Frameworks

金属有机骨架 等结构 化学 超分子化学 镧系元素 高分辨率透射电子显微镜 纳米技术 材料科学 化学工程 分子 介孔材料 吸附 催化作用 结晶学 有机化学 透射电子显微镜 离子 晶体结构 工程类
作者
Yuhao Liu,Lingmei Liu,Xu Chen,Yan Liu,Yu Han,Yong Cui
出处
期刊:Journal of the American Chemical Society [American Chemical Society]
卷期号:143 (9): 3509-3518 被引量:114
标识
DOI:10.1021/jacs.0c13005
摘要

Two-dimensional (2D) materials with highly ordered in-plane nanopores are crucial for numerous applications, but their rational synthesis and local structural characterization remain two grand challenges. We illustrate here that single-crystalline ultrathin 2D MOF nanosheets (MONs) with intrinsic porosity can be prepared by exfoliating layered metal–organic frameworks (MOFs), whose layers are stabilized by sterically bulky groups. As a result, three three-dimensional (3D) isostructural lanthanide MOFs possessing porous layer structures are constructed by coordinating metal ions with an angular dicarboxylate linker derived from chiral 1,1′-biphenyl phosphoric acid with pendant mesityl groups. The Eu-MOF is readily ultrasonic exfoliated into single-crystalline nanosheets with a thickness of ca. 6.0 nm (2 layers) and a lateral size of 1.5 × 3.0 μm2. The detailed structural information, i.e., the pore channels and individual organic and inorganic building units in the framework, is clearly visualized by a low-dose high-resolution transmission electron microscopy (HRTEM) technique. Benefiting from their ultrathin feature, the nanosheets are well embedded into the polymer matrix to form free-standing mixed-matrix membranes. In both the solution and membrane phase, the fluorescence of the MONs can be effectively quenched by a total of 17 chiral terpenes and terpenoids through supramolecular interactions with uncoordinated chiral phosphoric acids, leading to a chiral optical sensor for detecting vapor enantiomers, which is among the most challenging molecular recognition tasks.
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