A series of isoreticular chiral metal-organic frameworks as a tunable platform for asymmetric catalysis.

Metal-organic frameworks, built by bridging metal ions with organic linkers, represent a new class of porous hybrid materials with attractive tunability in compositions, structures and functions. In particular, the mild conditions typically employed for their synthesis allow for the functionalization of their building blocks, and thus the rational design of novel materials. Here we demonstrate the systematic design of eight mesoporous chiral metal-organic frameworks, with the framework formula [LCu2(solvent)2] (where L is a chiral tetracarboxylate ligand derived from 1,1'-bi-2-naphthol), that have the same structures but channels of different sizes. Chiral Lewis acid catalysts were generated by postsynthesis functionalization with Ti(OiPr)4, and the resulting materials proved to be highly active asymmetric catalysts for diethylzinc and alkynylzinc additions, which converted aromatic aldehydes into chiral secondary alcohols. The enantioselectivities of these reactions can be modified by tuning the size of the channels, which alters the diffusion rates of the organic substrates.

[1]  Wenbin Lin,et al.  Chirality-controlled and solvent-templated catenation isomerism in metal-organic frameworks. , 2008, Journal of the American Chemical Society.

[2]  Kimoon Kim,et al.  Postsynthetic Modification Switches an Achiral Framework to Catalytically Active Homochiral Metal—Organic Porous Materials. , 2009 .

[3]  Seth M. Cohen,et al.  Postsynthetic Modification of Metal-Organic Frameworks. , 2009, Inorganic chemistry.

[4]  L. Pu,et al.  Catalytic asymmetric organozinc additions to carbonyl compounds. , 2001, Chemical reviews.

[5]  L. Long,et al.  Three-dimensional metal-organic frameworks based on functionalized tetracarboxylate linkers: synthesis, structures, and gas sorption studies. , 2009, Inorganic chemistry.

[6]  Wenbin Lin,et al.  Surfactant-assisted synthesis of nanoscale gadolinium metal-organic frameworks for potential multimodal imaging. , 2008, Angewandte Chemie.

[7]  Jeong Yong Lee,et al.  3D metal-organic frameworks based on elongated tetracarboxylate building blocks for hydrogen storage. , 2008, Inorganic chemistry.

[8]  A. J. Blake,et al.  High H2 adsorption by coordination-framework materials. , 2006, Angewandte Chemie.

[9]  Omar K Farha,et al.  Metal-organic framework materials as catalysts. , 2009, Chemical Society reviews.

[10]  A. Fletcher,et al.  Hysteretic Adsorption and Desorption of Hydrogen by Nanoporous Metal-Organic Frameworks , 2004, Science.

[11]  Chuan-De Wu,et al.  A homochiral porous metal-organic framework for highly enantioselective heterogeneous asymmetric catalysis. , 2005, Journal of the American Chemical Society.

[12]  Krista S. Walton,et al.  Applicability of the BET method for determining surface areas of microporous metal-organic frameworks. , 2007, Journal of the American Chemical Society.

[13]  Wenbin Lin,et al.  Nanoscale coordination polymers for platinum-based anticancer drug delivery. , 2008, Journal of the American Chemical Society.

[14]  Michael O'Keeffe,et al.  A route to high surface area, porosity and inclusion of large molecules in crystals , 2004, Nature.

[15]  Zhenqiang Wang,et al.  Postsynthetic covalent modification of a neutral metal-organic framework. , 2007, Journal of the American Chemical Society.

[16]  Michael O'Keeffe,et al.  Reticular synthesis and the design of new materials , 2003, Nature.

[17]  Zhengtao Xu,et al.  Variable Pore Size, Variable Chemical Functionality, and an Example of Reactivity within Porous Phenylacetylene Silver Salts , 1999 .

[18]  A. Matzger,et al.  A crystalline mesoporous coordination copolymer with high microporosity. , 2008, Angewandte Chemie.

[19]  J. Long,et al.  Hydrogen storage in microporous metal-organic frameworks with exposed metal sites. , 2008, Angewandte Chemie.

[20]  Wenbin Lin,et al.  Manganese-based nanoscale metal-organic frameworks for magnetic resonance imaging. , 2008, Journal of the American Chemical Society.

[21]  Wenbin Lin,et al.  Crystal Engineering of NLO Materials Based on Metal—Organic Coordination Networks , 2010 .

[22]  Anthony L. Spek,et al.  Journal of , 1993 .

[23]  J. Hupp,et al.  An example of node-based postassembly elaboration of a hydrogen-sorbing, metal-organic framework material. , 2008, Inorganic chemistry.

[24]  Wenbin Lin,et al.  Enantioselective catalysis with homochiral metal-organic frameworks. , 2009, Chemical Society reviews.

[25]  A Alec Talin,et al.  Stress-induced chemical detection using flexible metal-organic frameworks. , 2008, Journal of the American Chemical Society.

[26]  S. Nguyen,et al.  A metal-organic framework material that functions as an enantioselective catalyst for olefin epoxidation. , 2006, Chemical communications.

[27]  Omar M Yaghi,et al.  Strategies for hydrogen storage in metal--organic frameworks. , 2005, Angewandte Chemie.

[28]  Omar K Farha,et al.  Supercritical processing as a route to high internal surface areas and permanent microporosity in metal-organic framework materials. , 2009, Journal of the American Chemical Society.

[29]  D. Olson,et al.  A luminescent microporous metal-organic framework for the fast and reversible detection of high explosives. , 2009, Angewandte Chemie.

[30]  Kunlun Hong,et al.  Surface interactions and quantum kinetic molecular sieving for H2 and D2 adsorption on a mixed metal-organic framework material. , 2008, Journal of the American Chemical Society.

[31]  Wenbin Lin,et al.  Heterogeneous asymmetric catalysis with homochiral metal-organic frameworks: network-structure-dependent catalytic activity. , 2007, Angewandte Chemie.

[32]  Alexander J. Blake,et al.  High capacity hydrogen adsorption in Cu(II) tetracarboxylate framework materials: the role of pore size, ligand functionalization, and exposed metal sites. , 2009, Journal of the American Chemical Society.

[33]  C. Serre,et al.  A Chromium Terephthalate-Based Solid with Unusually Large Pore Volumes and Surface Area , 2005, Science.

[34]  Zhigang Xie,et al.  Freeze drying significantly increases permanent porosity and hydrogen uptake in 4,4-connected metal-organic frameworks. , 2009, Angewandte Chemie.

[35]  Wenbin Lin.  Metal-Organic Frameworks for Asymmetric Catalysis and Chiral Separations , 2007 .

[36]  Jinho Oh,et al.  A homochiral metal–organic porous material for enantioselective separation and catalysis , 2000, Nature.

[37]  Yuanjing Cui,et al.  A luminescent metal-organic framework with Lewis basic pyridyl sites for the sensing of metal ions. , 2009, Angewandte Chemie.

[38]  Michael O'Keeffe,et al.  Systematic Design of Pore Size and Functionality in Isoreticular MOFs and Their Application in Methane Storage , 2002, Science.

[39]  C. Serre,et al.  Role of Solvent-Host Interactions That Lead to Very Large Swelling of Hybrid Frameworks , 2007, Science.

[40]  Y. Kawazoe,et al.  Highly controlled acetylene accommodation in a metal–organic microporous material , 2005, Nature.

[41]  Gérard Férey,et al.  Flexible porous metal-organic frameworks for a controlled drug delivery. , 2008, Journal of the American Chemical Society.

[42]  Weili Lin,et al.  Nanoscale metal-organic frameworks as potential multimodal contrast enhancing agents. , 2006, Journal of the American Chemical Society.

[43]  C. Serre,et al.  Prediction of the conditions for breathing of metal organic framework materials using a combination of X-ray powder diffraction, microcalorimetry, and molecular simulation. , 2008, Journal of the American Chemical Society.

[44]  Ian D. Williams,et al.  A chemically functionalizable nanoporous material (Cu3(TMA)2(H2O)3)n , 1999 .

[45]  Wenbin Lin,et al.  Chiral porous solids based on lamellar lanthanide phosphonates. , 2001, Journal of the American Chemical Society.