A Family of Chiral Metal–Organic Frameworks

Gedrich, Kristina; Heitbaum, Maja; Notzon, Andreas; Senkovska, Irena; Fröhlich, Roland; Getzschmann, Jürgen; Muêller, U.; Glorius, Frank; Kaskel, Stefan

doi:10.1002/chem.201002568

Cited by 130 publications

(73 citation statements)

References 65 publications

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“…Similarly, in this case a porous, solvent-free framework could not be produced. [27] These findings reinforce the role of 4,4'-bipyridine in directing a non-interpenetrated, robust pto-like, highly porous structure. The axial positions of paddle-wheels in DUT-34 in the absence of bipy are accessible for potential catalytic applications, and because most catalytic reactions occur in the liquid phase, the accessibility of the pore system of DUT-34 was proven by liquid-phase adsorption of ethyl cinnamate in n-heptane.…”

supporting

confidence: 71%

Route to a Family of Robust, Non‐interpenetrated Metal–Organic Frameworks with pto‐like Topology

Klein

Senkovska

Baburin

et al. 2011

Chemistry A European J

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A combination of topological rules and quantum chemical calculations has facilitated the development of a rational metal-organic framework (MOF) synthetic strategy using the tritopic benzene-1,3,5-tribenzoate (btb) linker and a neutral cross-linker 4,4'-bipyridine (bipy). A series of new compounds, namely [M(2)(bipy)](3)(btb)(4) (DUT-23(M), M = Zn, Co, Cu, Ni), [Cu(2)(bisqui)(0.5)](3)(btb)(4) (DUT-24, bisqui = diethyl (R,S)-4,4'-biquinoline-3,3'-dicarboxylate), [Cu(2)(py)(1.5)(H(2)O)(0.5)](3)(btb)(4) (DUT-33, py = pyridine), and [Cu(2)(H(2)O)(2)](3)(btb)(4) (DUT-34), with high specific surface areas and pore volumes (up to 2.03 m(3) g(-1) for DUT-23(Co)) were synthesized. For DUT-23(Co), excess storage capacities were determined for methane (268 mg g(-1) at 100 bar and 298 K), hydrogen (74 mg g(-1) at 40 bar and 77 K), and n-butane (99 mg g(-1) at 293 K). DUT-34 is a non-cross-linked version of DUT-23 (non-interpenetrated pendant to MOF-14) that possesses open metal sites and can therefore be used as a catalyst. The accessibility of the pores in DUT-34 to potential substrate molecules was proven by liquid phase adsorption. By exchanging the N,N donor 4,4'-bipyridine with a substituted racemic biquinoline, DUT-24 was obtained. This opens a route to the synthesis of a chiral compound, which could be interesting for enantioselective separation.

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supporting

confidence: 71%

Route to a Family of Robust, Non‐interpenetrated Metal–Organic Frameworks with pto‐like Topology

Klein

Senkovska

Baburin

et al. 2011

Chemistry A European J

Self Cite

131

108

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“…In particular, chiral MOFs are highly promising for the separation of enantiomers and for chiral catalysis, as a result of their high porosity, functional diversity, flexibility and size and shape selectivity, surpassing traditional inorganic and organic porous materials [16][17][18][19][20] . Chiral MOF catalysts with uniform active sites for enantioselective reactions have been developed based on functionalized chiral molecular (pre)catalysts [21][22][23][24][25][26][27][28][29][30] . In a handful of latest studies, the resolution of enantiomers (racemic alcohols and sulphoxides) with chiral MOFs via chromatography [31][32][33][34] , crystallization [35][36][37][38][39][40] and membrane 41,42 has been reported, but only few exhibit good chiral separation performance.…”

mentioning

confidence: 99%

Engineering chiral porous metal-organic frameworks for enantioselective adsorption and separation

et al. 2014

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The separation of racemic molecules is of substantial significance not only for basic science but also for technical applications, such as fine chemicals and drug development. Here we report two isostructural chiral metal-organic frameworks decorated with chiral dihydroxy or -methoxy auxiliares from enantiopure tetracarboxylate-bridging ligands of 1,1 0 -biphenol and a manganese carboxylate chain. The framework bearing dihydroxy groups functions as a solid-state host capable of adsorbing and separating mixtures of a range of chiral aromatic and aliphatic amines, with high enantioselectivity. The host material can be readily recycled and reused without any apparent loss of performance. The utility of the present adsorption separation is demonstrated in the large-scale resolution of racemic 1-phenylethylamine. Control experiments and molecular simulations suggest that the chiral recognition and separation are attributed to the different orientations and specific binding energies of the enantiomers in the microenvironment of the framework.

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“…These open metal sites can act as catalytic sites for asymmetric reactions. Kaskel and coworkers reported [Zn 3 (ChirBTB-1) 2 ]·3DEF with Zn 2+ and 1,3,5-tri{4-[2-(4-isopropyl-2-oxooxazolidin-3-yl)] benzoate}benzene, which acted as a highly active Lewis acid catalyst for the Mukaiyama enantioselective aldol reaction [84]. Kim et al developed a mixed linker homochiral MOFs [Zn 2 (bdc)(L-lac)-(dmf)]·0.9DMF·0.1H 2 O as enantioselective guest-sorption materials, which also exhibited high catalytic activity in the oxidation of thioethers to sulfoxides with size-and chemo-selectivity [85].…”

Section: Chiral Reactions Over Mofsmentioning

confidence: 98%

Metal–Organic Frameworks for Catalysis

et al. 2015

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Metal-organic frameworks (MOFs) are a relatively new class of porous material, which are comprised of metal ions or clusters linked with poly-functional organic molecules. MOFs have been studied increasingly for heterogeneous catalysis applications because these hybrid materials have well-ordered tunable porous structures with exceptional textural properties and introduction of additional active sites can be carried out easily by relatively simple post-synthesis functionalization. This short review focuses on recent works on liquid phase catalytic reactions carried out over selected MOFs. The MOF membranes for catalysis and the potential of functionalized MOF materials for chiral reactions are also mentioned briefly.

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A Family of Chiral Metal–Organic Frameworks

Cited by 130 publications

References 65 publications

Route to a Family of Robust, Non‐interpenetrated Metal–Organic Frameworks with pto‐like Topology

Route to a Family of Robust, Non‐interpenetrated Metal–Organic Frameworks with pto‐like Topology

Engineering chiral porous metal-organic frameworks for enantioselective adsorption and separation

Metal–Organic Frameworks for Catalysis

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