An In Situ One-Pot Synthetic Approach towards Multivariate Zirconium MOFs.

Chemically highly stable MOFs incorporating multiple functionalities are of great interest for applications under harsh environments. Herein, we presented a facile one-pot synthetic strategy to incorporate multiple functionalities into stable Zr-MOFs from mixed ligands of different geometry and connectivity. Via our strategy, tetratopic tetrakis(4-carboxyphenyl)porphyrin (TCPP) ligands were successfully integrated into UiO-66 while maintaining the crystal structure, morphology, and ultrahigh chemical stability of UiO-66. The amount of incorporated TCPP is controllable. Through various combinations of BDC derivatives and TCPP, 49 MOFs with multiple functionalities were obtained. Among them, MOFs modified with FeTCPPCl were demonstrated to be catalytically active for the oxidation of ABTS. We anticipate our strategy to provide a facile route to introduce multiple functionalities into stable Zr-MOFs for a wide variety of potential applications.

[1]  P. Silva,et al.  Multifunctional metal-organic frameworks: from academia to industrial applications. , 2015, Chemical Society reviews.

[2]  Bongsoo Kim,et al.  Superprotonic conductivity of a UiO-66 framework functionalized with sulfonic acid groups by facile postsynthetic oxidation. , 2015, Angewandte Chemie.

[3]  U. Müller,et al.  “Heterogenität innerhalb von Ordnung” in Metall‐organischen Gerüsten , 2015 .

[4]  H. Furukawa,et al.  "Heterogeneity within order" in metal-organic frameworks. , 2015, Angewandte Chemie.

[5]  Weihong Zhu,et al.  Fluorescent and colorimetric ion probes based on conjugated oligopyrroles. , 2015, Chemical Society reviews.

[6]  J. Hupp,et al.  MOF functionalization via solvent-assisted ligand incorporation: phosphonates vs carboxylates. , 2015, Inorganic chemistry.

[7]  J. Barth,et al.  Porphyrins at interfaces. , 2015, Nature chemistry.

[8]  Jie Su,et al.  A highly stable zeotype mesoporous zirconium metal-organic framework with ultralarge pores. , 2015, Angewandte Chemie.

[9]  M. Grätzel,et al.  Meso-substituted porphyrins for dye-sensitized solar cells. , 2014, Chemical reviews.

[10]  Wenbin Lin,et al.  Nanoscale Metal–Organic Framework for Highly Effective Photodynamic Therapy of Resistant Head and Neck Cancer , 2014, Journal of the American Chemical Society.

[11]  Shuhong Yu,et al.  MIL-101-SO3H: a highly efficient Brønsted acid catalyst for heterogeneous alcoholysis of epoxides under ambient conditions. , 2014, Chemistry.

[12]  K. Lillerud,et al.  Synthesis and characterization of amine-functionalized mixed-ligand metal-organic frameworks of UiO-66 topology. , 2014, Inorganic chemistry.

[13]  Omar K Farha,et al.  Beyond post-synthesis modification: evolution of metal-organic frameworks via building block replacement. , 2014, Chemical Society reviews.

[14]  Jack D. Evans,et al.  Post-synthetic metalation of metal-organic frameworks. , 2014, Chemical Society reviews.

[15]  Qiang Zhang,et al.  Tuning the structure and function of metal-organic frameworks via linker design. , 2014, Chemical Society reviews.

[16]  Wenbin Lin,et al.  Metal-organic frameworks for artificial photosynthesis and photocatalysis. , 2014, Chemical Society reviews.

[17]  Sachin Chavan,et al.  Tuned to Perfection: Ironing Out the Defects in Metal–Organic Framework UiO-66 , 2014 .

[18]  François-Xavier Coudert,et al.  Correlated Defect Nano-Regions in a Metal–Organic Framework , 2014, Nature Communications.

[19]  Ruliang Liu,et al.  Conversion of fructose into 5-hydroxymethylfurfural catalyzed by recyclable sulfonic acid-functionalized metal–organic frameworks , 2014 .

[20]  Chuande Wu,et al.  Porous metal-organic frameworks for heterogeneous biomimetic catalysis. , 2014, Accounts of chemical research.

[21]  Omar K Farha,et al.  Versatile functionalization of the NU-1000 platform by solvent-assisted ligand incorporation. , 2014, Chemical communications.

[22]  Hong‐Cai Zhou,et al.  Metal-organic frameworks based on previously unknown Zr8/Hf8 cubic clusters. , 2013, Inorganic chemistry.

[23]  Banglin Chen,et al.  Highly efficient C-H oxidative activation by a porous Mn(III) -porphyrin metal-organic framework under mild conditions. , 2013, Chemistry.

[24]  Michael O’Keeffe,et al.  The Chemistry and Applications of Metal-Organic Frameworks , 2013, Science.

[25]  Ping Chen,et al.  Unusual and highly tunable missing-linker defects in zirconium metal-organic framework UiO-66 and their important effects on gas adsorption. , 2013, Journal of the American Chemical Society.

[26]  E. Wang,et al.  Nanomaterials with enzyme-like characteristics (nanozymes): next-generation artificial enzymes. , 2013, Chemical Society reviews.

[27]  Christian Wolf,et al.  Chirality sensing using stereodynamic probes with distinct electronic circular dichroism output. , 2013, Chemical Society reviews.

[28]  C. Malliakas,et al.  A straight forward route for the development of metal-organic frameworks functionalized with aromatic -OH groups: synthesis, characterization, and gas (N2, Ar, H2, CO2, CH4, NH3) sorption properties. , 2013, Inorganic chemistry.

[29]  Eric Wei-Guang Diau,et al.  Porphyrin-sensitized solar cells. , 2013, Chemical Society reviews.

[30]  G. Wiederrecht,et al.  Light-harvesting and ultrafast energy migration in porphyrin-based metal-organic frameworks. , 2013, Journal of the American Chemical Society.

[31]  Jinhee Park,et al.  Introduction of functionalized mesopores to metal-organic frameworks via metal-ligand-fragment coassembly. , 2012, Journal of the American Chemical Society.

[32]  Nathaniel L. Rosi,et al.  Strain-promoted "click" modification of a mesoporous metal-organic framework. , 2012, Journal of the American Chemical Society.

[33]  Dawei Feng,et al.  Zirconium-metalloporphyrin PCN-222: mesoporous metal-organic frameworks with ultrahigh stability as biomimetic catalysts. , 2012, Angewandte Chemie.

[34]  Christian Serre,et al.  A series of isoreticular, highly stable, porous zirconium oxide based metal-organic frameworks. , 2012, Angewandte Chemie.

[35]  Stefan Kaskel,et al.  Zr(IV) and Hf(IV) based metal-organic frameworks with reo-topology. , 2012, Chemical communications.

[36]  Duilio Cascio,et al.  Synthesis, structure, and metalation of two new highly porous zirconium metal-organic frameworks. , 2012, Inorganic chemistry.

[37]  M. Pera‐Titus,et al.  Homogeneity of flexible metal–organic frameworks containing mixed linkers , 2012 .

[38]  D. Astruc Electron-transfer processes in dendrimers and their implication in biology, catalysis, sensing and nanotechnology. , 2012, Nature chemistry.

[39]  Kenji Sumida,et al.  Carbon dioxide capture in metal-organic frameworks. , 2012, Chemical reviews.

[40]  Mohamed Eddaoudi,et al.  Template-directed synthesis of nets based upon octahemioctahedral cages that encapsulate catalytically active metalloporphyrins. , 2012, Journal of the American Chemical Society.

[41]  Jian Zhang,et al.  High and selective CO2 uptake, H2storage and methanol sensing on the amine-decorated 12-connected MOF CAU-1 , 2011 .

[42]  Bong Jin Hong,et al.  Light-harvesting metal-organic frameworks (MOFs): efficient strut-to-strut energy transfer in bodipy and porphyrin-based MOFs. , 2011, Journal of the American Chemical Society.

[43]  Peter Behrens,et al.  Porous interpenetrated zirconium-organic frameworks (PIZOFs): a chemically versatile family of metal-organic frameworks. , 2011, Chemistry.

[44]  Zhigang Xie,et al.  Doping metal-organic frameworks for water oxidation, carbon dioxide reduction, and organic photocatalysis. , 2011, Journal of the American Chemical Society.

[45]  Peter Behrens,et al.  Modulated synthesis of Zr-based metal-organic frameworks: from nano to single crystals. , 2011, Chemistry.

[46]  Andrew D. Burrows,et al.  Mixed-component metal–organic frameworks (MC-MOFs): enhancing functionality through solid solution formation and surface modifications , 2011 .

[47]  T. Dingemans,et al.  Methyl modified MOF-5: a water stable hydrogen storage material. , 2011, Chemical communications.

[48]  Bartolomeo Civalleri,et al.  Disclosing the Complex Structure of UiO-66 Metal Organic Framework: A Synergic Combination of Experiment and Theory , 2011 .

[49]  Elsje Alessandra Quadrelli,et al.  Synthesis and Stability of Tagged UiO-66 Zr-MOFs , 2010 .

[50]  Seth M Cohen,et al.  Isoreticular synthesis and modification of frameworks with the UiO-66 topology. , 2010, Chemical communications.

[51]  Matthias I. J. Stich,et al.  Multiple fluorescent chemical sensing and imaging. , 2010, Chemical Society reviews.

[52]  C. Pinel,et al.  Generic postfunctionalization route from amino-derived metal-organic frameworks. , 2010, Journal of the American Chemical Society.

[53]  Christian J. Doonan,et al.  Multiple Functional Groups of Varying Ratios in Metal-Organic Frameworks , 2010, Science.

[54]  T. Moore,et al.  Solar fuels via artificial photosynthesis. , 2009, Accounts of chemical research.

[55]  S. Nguyen,et al.  Selective bifunctional modification of a non-catenated metal-organic framework material via "click" chemistry. , 2009, Journal of the American Chemical Society.

[56]  John S. O. Evans,et al.  Chemically blockable transformation and ultraselective low-pressure gas adsorption in a non-porous metal organic framework. , 2009, Nature chemistry.

[57]  C. Serre,et al.  Porous Chromium Terephthalate MIL‐101 with Coordinatively Unsaturated Sites: Surface Functionalization, Encapsulation, Sorption and Catalysis , 2009 .

[58]  Seigo Ito,et al.  Large pi-aromatic molecules as potential sensitizers for highly efficient dye-sensitized solar cells. , 2009, Accounts of chemical research.

[59]  Seth M. Cohen,et al.  Postsynthetic modification of metal-organic frameworks. , 2009, Chemical Society reviews.

[60]  M. Allendorf,et al.  Luminescent metal-organic frameworks. , 2009, Chemical Society reviews.

[61]  Freek Kapteijn,et al.  An amine-functionalized MIL-53 metal-organic framework with large separation power for CO2 and CH4. , 2009, Journal of the American Chemical Society.

[62]  D. Vos,et al.  Separation of CO2/CH4 mixtures with the MIL-53(Al) metal–organic framework , 2009 .

[63]  Michael O'Keeffe,et al.  Control of pore size and functionality in isoreticular zeolitic imidazolate frameworks and their carbon dioxide selective capture properties. , 2009, Journal of the American Chemical Society.

[64]  C. Hu,et al.  Pillared porphyrin homologous series: intergrowth in metal-organic frameworks. , 2009, Inorganic chemistry.

[65]  S. Shinkai,et al.  "Clickable" metal-organic framework. , 2008, Journal of the American Chemical Society.

[66]  Carlo Lamberti,et al.  A new zirconium inorganic building brick forming metal organic frameworks with exceptional stability. , 2008, Journal of the American Chemical Society.

[67]  Bjørnar Arstad,et al.  Amine functionalised metal organic frameworks (MOFs) as adsorbents for carbon dioxide , 2008 .

[68]  Patrick Ryan,et al.  Separation of CO2 from CH4 using mixed-ligand metal-organic frameworks. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[69]  Michael O'Keeffe,et al.  Three-periodic nets and tilings: semiregular nets. , 2003, Acta crystallographica. Section A, Foundations of crystallography.