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Chiral Porous Metacrystals: Employing Liquid-Phase Epitaxy to Assemble Enantiopure Metal–Organic Nanoclusters into Molecular Framework Pores

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    Chiral Porous Metacrystals: Employing Liquid-Phase Epitaxy to Assemble Enantiopure Metal–Organic Nanoclusters into Molecular Framework Pores
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    † State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 350002 Fuzhou, P. R. China
    ‡ ‡Institute of Functional Interfaces (IFG), and §Institute of Nanotechnology (INT), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344, Eggenstein-Leopoldshafen, Germany
    *E-mail: [email protected] (J.Z.).
    *E-mail: [email protected] (L.Z.).
    *E-mail: [email protected] (C.W.).
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    ACS Nano

    Cite this: ACS Nano 2016, 10, 1, 977–983
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    https://doi.org/10.1021/acsnano.5b06230
    Published December 7, 2015
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    We describe the fabrication of hybrid yet well-ordered porous nanoparticle (NP) arrays with full three-dimensional periodicity by embedding nanometer-sized metal–organic clusters (MOCs) into metal–organic frameworks (MOFs). Although conventional NP@MOF encapsulation procedures failed for these fairly large (1.66 nm diameter) NPs, we achieved maximum loading efficiency (one NP per pore) by using a modified liquid phase epitaxy (LPE) layer-by-layer approach to grow and load the MOF. The preformed NPs, homochiral Ti4(OH)4(R/S-BINOL)6 clusters (Ti-MOC, BINOL = 1,1′-bi-2-naphthol), formed a regular lattice inside the pores of an achiral HKUST-1 (or Cu3(BTC)2, BTC = 1,3,5-benzenetricarboxylate) MOF thin film. Exposure to the different enantiomers of methyl lactate revealed that the NP@MOF metacrystal is quite efficient regarding enantiomer recognition and separation. The approach presented here is also suited for other MOF types and expected to provide a substantial stimulus for the fabrication of metacrystals, crystalline solids made from nanoparticles instead of atoms.

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    Cite this: ACS Nano 2016, 10, 1, 977–983
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    https://doi.org/10.1021/acsnano.5b06230
    Published December 7, 2015
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