Construction and selective gas adsorption properties of two heteroSBU MOFs based on unsymmetrical tetracarboxylate linkers

By employing the strategy of positional isomerism, we designed and synthesized two unsymmetrical biphenyl tetracarboxylate ligands, and used them to successfully construct two novel copper-based MOFs. Structural determinations show that the resulting MOFs are three-dimensional networks, each incorporating two different kinds of discrete copper-carboxylate clusters, including the typical dicopper Cu2(COO)4(H2O)2 paddlewheel, as inorganic SBUs, and they display distinctly different topologies, highlighting the significant effect of ligand desymmetrization. ZJNU-9 is a neutral coordination network composed of one typical dicopper paddlewheel and a new dicopper cluster Cu2(COO)4(DMF)2(H2O)2 connected by the organic ligands, while ZJNU-10 is based on one typical dicopper paddlewheel and a new tetracopper cluster Cu4(COO)4(OH)2Cl(H2O)4 linked by the organic ligands to a cationic framework containing three types of cages. The two novel copper-containing clusters discovered in the two compounds greatly enrich the diversity and complexity of inorganic copper-carboxylate SBUs and thus MOF structures. Furthermore, a systematical investigation of their selective adsorption properties with respect to C2H2, CO2, and CH4 through pure-component isotherm measurements and IAST predictions revealed their promising potential for C2H2 recovery and CO2 removal from CH4 under ambient conditions. This work represents a rare example of homometallic pure-carboxylate hetero-SBU MOFs exhibiting highly selective adsorption of C2H2 and CO2 over CH4.

[1]  Shu’ni Li,et al.  Tailoring the Pore Environment of a Robust Ga-MOF by Deformed [Ga3O(COO)6] Cluster for Boosting C2H2 Uptake and Separation. , 2020, Inorganic chemistry.

[2]  R. Krishna,et al.  Rational design of microporous MOFs with anionic boron cluster functionality and cooperative dihydrogen binding sites for highly selective capture of acetylene. , 2020, Angewandte Chemie.

[3]  Huiyan Liu,et al.  Insight into the Construction of (3,6)-Connected rtl, ant, and Chiral anh Nets Based on Structural Investigation of Several MOFs via Steric Tuning of Linkers. , 2020, Inorganic chemistry.

[4]  Falu Hu,et al.  Building a robust 3D Ca-MOF by a new square Ca4O SBU for purification of natural gas. , 2020, Dalton transactions.

[5]  Tingting Xu,et al.  Immobilization of N-oxide functionality into NbO-type MOFs for significantly enhanced C2H2/CH4 and CO2/CH4 separations. , 2020, Dalton transactions.

[6]  S. Deng,et al.  Optimizing Pore Space for Flexible-Robust Metal-Organic Framework to Boost Trace Acetylene Removal. , 2020, Journal of the American Chemical Society.

[7]  Yaoyu Wang,et al.  Two Robust In(III)-Based Metal-Organic Frameworks with Higher Gas Separation, Efficient Carbon Dioxide Conversion, and Rapid Detection of Antibiotics. , 2020, Inorganic chemistry.

[8]  Tingting Xu,et al.  A hydrostable cage-based MOF with open metal sites and Lewis basic sites immobilized in the pore surface for efficient separation and purification of natural gas and C2H2. , 2020, Dalton transactions.

[9]  Libo Li,et al.  Immobilization of Oxygen Atoms in the Pores of Microporous Metal–Organic Frameworks for C2H2 Separation and Purification , 2020 .

[10]  Sihui Zhan,et al.  C2H2/CH4 and CO2/CH4 separations on a ethoxyl-functionalized Cobalt(II)–Organic framework with open metal sites , 2020 .

[11]  S. Xiang,et al.  A metal-organic framework with double interpenetrated frameworks for effective C2H2/CO2 separation , 2020 .

[12]  R. Krishna,et al.  Pore-Space-Partition-Enabled Exceptional Ethane Uptake and Ethane-Selective Ethane-Ethylene Separation. , 2020, Journal of the American Chemical Society.

[13]  Guanghua Li,et al.  Selective Acetylene Adsorption within an Imino Functionalized Nanocage-Based Metal-Organic Framework. , 2020, ACS applied materials & interfaces.

[14]  Yuchuan Liu,et al.  Two zinc metal-organic framework isomers based on pyrazine tetracarboxylic acid and dipyridinylbenzene for adsorption and separation of CO2 and light hydrocarbons. , 2020, Dalton transactions.

[15]  Tingting Xu,et al.  Tailoring the structures and gas adsorption properties of copper–bent diisophthalate frameworks by a substituent-driven ligand conformation regulation strategy , 2019, CrystEngComm.

[16]  J. Long,et al.  Thermodynamic Separation of 1-Butene from 2-Butene in Metal-Organic Frameworks with Open Metal Sites. , 2019, Journal of the American Chemical Society.

[17]  Tingting Xu,et al.  Effect of arrangement of functional groups on stability and gas adsorption properties in two regioisomeric copper bent diisophthalate frameworks , 2019, CrystEngComm.

[18]  T. Ding,et al.  Highly selective C2H2 and CO2 capture and magnetic properties of a robust Co-chain based metal-organic framework. , 2019, Dalton transactions.

[19]  Ming-Hua He,et al.  Incorporation of bifunctional aminopyridine into an NbO-type MOF for the markedly enhanced adsorption of CO2 and C2H2 over CH4 , 2019, Inorganic Chemistry Frontiers.

[20]  M. Zaworotko,et al.  Highly Selective, High-Capacity Separation of o-Xylene from C8 Aromatics by a Switching Adsorbent Layered Material. , 2019, Angewandte Chemie.

[21]  Arun Pal,et al.  Three Co(II) Metal-Organic Frameworks with Diverse Architectures for Selective Gas Sorption and Magnetic Studies. , 2019, Inorganic chemistry.

[22]  Xinsheng Zhao,et al.  Microwave-assisted synthesis of urea-containing zirconium metal–organic frameworks for heterogeneous catalysis of Henry reactions , 2019, CrystEngComm.

[23]  Guanghua Li,et al.  Two unique copper cluster-based metal–organic frameworks with high performance for CO2 adsorption and separation , 2019, Inorganic Chemistry Frontiers.

[24]  Yao Wang,et al.  A ligand conformation preorganization approach to construct a copper–hexacarboxylate framework with a novel topology for selective gas adsorption , 2019, Inorganic Chemistry Frontiers.

[25]  Yaoyu Wang,et al.  Stable Indium-Pyridylcarboxylate Framework: Selective Gas Capture and Sensing of Fe3+ Ion in Water. , 2018, Inorganic chemistry.

[26]  T. He,et al.  Two interpenetrated metal–organic frameworks with a slim ethynyl-based ligand: designed for selective gas adsorption and structural tuning , 2018 .

[27]  Shu’ni Li,et al.  Assembly of [Cu2(COO)4] and [M3(μ3-O)(COO)6] (M = Sc, Fe, Ga, and In) building blocks into porous frameworks towards ultra-high C2H2/CO2 and C2H2/CH4 separation performance. , 2018, Chemical communications.

[28]  Christina T. Lollar,et al.  Control the Structure of Zr-Tetracarboxylate Frameworks through Steric Tuning. , 2017, Journal of the American Chemical Society.

[29]  Angelo Kirchon,et al.  An Amino-Functionalized Metal-Organic Framework, Based on a Rare Ba12 (COO)18 (NO3 )2 Cluster, for Efficient C3 /C2 /C1 Separation and Preferential Catalytic Performance. , 2017, Chemistry.

[30]  Yabing He,et al.  A rare Pb9 cluster-organic framework constructed from a flexible cyclotriphosphazene-functionalized hexacarboxylate exhibiting selective gas separation , 2017 .

[31]  T. Yildirim,et al.  Fine Tuning of MOF-505 Analogues To Reduce Low-Pressure Methane Uptake and Enhance Methane Working Capacity. , 2017, Angewandte Chemie.

[32]  Jing Li,et al.  Metal-organic frameworks: functional luminescent and photonic materials for sensing applications. , 2017, Chemical Society reviews.

[33]  A. J. Blake,et al.  Tailoring porosity and rotational dynamics in a series of octacarboxylate metal-organic frameworks , 2017, Proceedings of the National Academy of Sciences.

[34]  Sihai Yang,et al.  Unravelling exceptional acetylene and carbon dioxide adsorption within a tetra-amide functionalized metal-organic framework , 2017, Nature Communications.

[35]  Yanxi Tan,et al.  Rational design of a flu-type heterometallic cluster-based Zr-MOF. , 2016, Chemical communications.

[36]  R. Krishna,et al.  A Porous Zirconium-Based Metal-Organic Framework with the Potential for the Separation of Butene Isomers. , 2016, Chemistry.

[37]  G. Zhu,et al.  Reticular Synthesis of a Series of HKUST-like MOFs with Carbon Dioxide Capture and Separation. , 2016, Inorganic chemistry.

[38]  X. You,et al.  Finely tuning MOFs towards high performance in C2H2 storage: synthesis and properties of a new MOF-505 analogue with an inserted amide functional group. , 2016, Chemical communications.

[39]  Zu-Jin Lin,et al.  Water-Stable Anionic Metal-Organic Framework for Highly Selective Separation of Methane from Natural Gas and Pyrolysis Gas. , 2016, ACS applied materials & interfaces.

[40]  Daqiang Yuan,et al.  De Novo Tailoring Pore Morphologies and Sizes for Different Substrates in a Urea-Containing MOFs Catalytic Platform , 2016 .

[41]  Mingyan Wu,et al.  A porous metal-organic framework with ultrahigh acetylene uptake capacity under ambient conditions , 2015, Nature Communications.

[42]  T. Yildirim,et al.  A NbO-type metal-organic framework exhibiting high deliverable capacity for methane storage. , 2015, Chemical communications.

[43]  M. Zhan,et al.  Syntheses, crystal structures, photoluminescent/magnetic properties of four new coordination polymers based on 2,3′,4,5′-biphenyltetracarboxylic acid , 2014 .

[44]  R. Krishna,et al.  A new MOF-5 homologue for selective separation of methane from C2 hydrocarbons at room temperature , 2014 .

[45]  A. J. Blake,et al.  Studies on metal-organic frameworks of Cu(II) with isophthalate linkers for hydrogen storage. , 2014, Accounts of chemical research.

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

[47]  Hong‐Cai Zhou,et al.  Isostructural metal-organic frameworks assembled from functionalized diisophthalate ligands through a ligand-truncation strategy. , 2013, Chemistry.

[48]  W. Zhou,et al.  Microporous metal-organic frameworks for storage and separation of small hydrocarbons. , 2012, Chemical communications.

[49]  Rajamani Krishna,et al.  Metal–organic frameworks with potential for energy-efficient adsorptive separation of light hydrocarbons , 2012 .

[50]  Omar K Farha,et al.  Metal-organic framework materials with ultrahigh surface areas: is the sky the limit? , 2012, Journal of the American Chemical Society.

[51]  P. Thallapally,et al.  Switching Kr/Xe selectivity with temperature in a metal-organic framework. , 2012, Journal of the American Chemical Society.

[52]  V. Blatov.  Nanocluster analysis of intermetallic structures with the program package TOPOS , 2012, Structural Chemistry.

[53]  Hong-Cai Zhou,et al.  A highly porous and robust (3,3,4)-connected metal-organic framework assembled with a 90° bridging-angle embedded octacarboxylate ligand. , 2012, Angewandte Chemie.

[54]  Gérard Férey,et al.  Metal-organic frameworks in biomedicine. , 2012, Chemical reviews.

[55]  Hong-Cai Zhou,et al.  Metal-organic frameworks for separations. , 2012, Chemical reviews.

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

[57]  Yanfeng Yue,et al.  Luminescent functional metal-organic frameworks. , 2012, Chemical Reviews.

[58]  Zhiyu Wang,et al.  A Zn4O-containing doubly interpenetrated porous metal-organic framework for photocatalytic decomposition of methyl orange. , 2011, Chemical communications.

[59]  Sihai Yang,et al.  A mesoporous metal-organic framework constructed from a nanosized C3-symmetric linker and [Cu24(isophthalate)24] cuboctahedra. , 2011, Chemical communications.

[60]  Jingui Duan,et al.  Enhanced CO2 binding affinity of a high-uptake rht-type metal-organic framework decorated with acylamide groups. , 2011, Journal of the American Chemical Society.

[61]  S. Nguyen,et al.  De novo synthesis of a metal-organic framework material featuring ultrahigh surface area and gas storage capacities. , 2010, Nature chemistry.

[62]  W. Zhou,et al.  Open metal sites within isostructural metal-organic frameworks for differential recognition of acetylene and extraordinarily high acetylene storage capacity at room temperature. , 2010, Angewandte Chemie.

[63]  J. Simmons,et al.  An unusual case of symmetry-preserving isomerism. , 2010, Chemical communications.

[64]  Wei Zhou,et al.  Exceptionally high acetylene uptake in a microporous metal-organic framework with open metal sites. , 2009, Journal of the American Chemical Society.

[65]  Dan Zhao,et al.  Stabilization of metal-organic frameworks with high surface areas by the incorporation of mesocavities with microwindows. , 2009, Journal of the American Chemical Society.

[66]  Jie‐Peng Zhang,et al.  Optimized acetylene/carbon dioxide sorption in a dynamic porous crystal. , 2009, Journal of the American Chemical Society.

[67]  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.

[68]  S. Kitagawa,et al.  Storage and sorption properties of acetylene in jungle-gym-like open frameworks. , 2008, Chemistry, an Asian journal.

[69]  A. Matzger,et al.  Porous crystal derived from a tricarboxylate linker with two distinct binding motifs. , 2007, Journal of the American Chemical Society.

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

[71]  Bin Chen,et al.  Interwoven Metal-Organic Framework on a Periodic Minimal Surface with Extra-Large Pores , 2001, Science.

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

[73]  A. Spek.  PLATON SQUEEZE: a tool for the calculation of the disordered solvent contribution to the calculated structure factors. , 2015, Acta crystallographica. Section C, Structural chemistry.

[74]  P. Llewellyn,et al.  Is the bet equation applicable to microporous adsorbents , 2007 .

[75]  Alan L. Myers,et al.  Thermodynamics of mixed‐gas adsorption , 1965 .