title: Chiral Porous Metacrystals: Employing Liquid-Phase Epitaxy to Assemble Enantiopure Metal-Organic Nanoclusters into Molecular Framework Pores.
abstract: 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.
authors.affiliation: State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences , 350002 Fuzhou, P. R. China.
authors.forename: Zhi-Gang
authors.initials: ZG
authors.lastname: Gu
authors.affiliation: State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences , 350002 Fuzhou, P. R. China.
authors.forename: Hao
authors.initials: H
authors.lastname: Fu
authors.forename: Tobias
authors.initials: T
authors.lastname: Neumann
authors.affiliation: State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences , 350002 Fuzhou, P. R. China.
authors.forename: Zong-Xiong
authors.initials: ZX
authors.lastname: Xu
authors.affiliation: State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences , 350002 Fuzhou, P. R. China.
authors.forename: Wen-Qiang
authors.initials: WQ
authors.lastname: Fu
authors.forename: Wolfgang
authors.initials: W
authors.lastname: Wenzel
authors.affiliation: State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences , 350002 Fuzhou, P. R. China.
authors.forename: Lei
authors.initials: L
authors.lastname: Zhang
authors.affiliation: State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences , 350002 Fuzhou, P. R. China.
authors.forename: Jian
authors.initials: J
authors.lastname: Zhang
authors.forename: Christof
authors.initials: C
authors.lastname: Wöll
keywords: homochirality; metacrystals; metal−organic framework; nanocluster