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Two porous metal–organic frameworks (1 and 2) with a fsc topology based on mixed ligands have been assembled and characterized. The different pillared ligands (pyrazine for 1 and 4,4′-bipyridine for 2) significantly influence the pore size of the frameworks. Gas uptake measurements reveal that complex 1 possesses higher H2, CO2, and CH4 uptake capacities than 2, although the surface area of 1 is lower than that of complex 2. These results further experimentally prove that the pore size plays an important role in gas uptake in porous MOFs, and the slit pore with a size of ∼6 Å exhibits stronger interactions with gas molecules. [ABSTRACT FROM AUTHOR]

A 2D wave-like layered framework based on benzotriazole-5-carboxylic acid (H2btca), 2,2′-bipy and zinc ions – [Zn(btca)(2,2′-bipy)]n (1) – has been resoundingly designed and synthesized by a solvothermal method. By changing the solvent from DMF to DMA, a 3D porous framework – [Zn2(btca)2(bpy)(H2O)]n·n(DMA) (2) – was obtained. Complexes 1 and 2 have been determined by single-crystal X-ray diffraction analysis and further characterized by powder X-ray diffraction (PXRD), elemental analysis, IR spectroscopy, and thermogravimetric (TG) analysis. Complex 1 shows an AA packing 2D layered structure and complex 2 displays a 3D open honeycomb framework with a (3,4)-connected 2-nodal fsc topology. Moreover, gas adsorption of 2a (the activated form of 2) and the luminescence properties of 1, 2 and 2a have also been investigated intensively. [ABSTRACT FROM AUTHOR]

The separation of ethylene (C2H4) from a mixture of ethane (C2H6), ethylene (C2H4), and acetylene (C2H2) at normal temperature and pressure is a significant challenge. The sieving effect of pores is powerless due to the similar molecular size and kinetic diameter of these molecules. We report a new modification method based on a stable ftw topological Zr‐MOF platform (MOF‐525). Introduction of a cyclopentadiene cobalt functional group led to new ftw‐type MOFs materials (UPC‐612 and UPC‐613), which increase the host‐guest interaction and achieve efficient ethylene purification from the mixture of hydrocarbon gases. The high performance of UPC‐612 and UPC‐613 for C2H2/C2H4/C2H6 separation has been verified by gas sorption isotherms, density functional theory (DFT), and experimentally determined breakthrough curves. This work provides a one‐step separation of the ternary gas mixture and can further serve as a blueprint for the design and construction of function‐oriented porous structures for such applications. [ABSTRACT FROM AUTHOR]

The separation of ethylene (C2H4) from a mixture of ethane (C2H6), ethylene (C2H4), and acetylene (C2H2) at normal temperature and pressure is a significant challenge. The sieving effect of pores is powerless due to the similar molecular size and kinetic diameter of these molecules. We report a new modification method based on a stable ftw topological Zr‐MOF platform (MOF‐525). Introduction of a cyclopentadiene cobalt functional group led to new ftw‐type MOFs materials (UPC‐612 and UPC‐613), which increase the host‐guest interaction and achieve efficient ethylene purification from the mixture of hydrocarbon gases. The high performance of UPC‐612 and UPC‐613 for C2H2/C2H4/C2H6 separation has been verified by gas sorption isotherms, density functional theory (DFT), and experimentally determined breakthrough curves. This work provides a one‐step separation of the ternary gas mixture and can further serve as a blueprint for the design and construction of function‐oriented porous structures for such applications. [ABSTRACT FROM AUTHOR]

Four novel 3D Co(II)-containing metal–organic frameworks (MOFs), namely [Co(ADDA)] (1), [Co(ADDA)(bipy)]·1.5H 2 O (2), [Co 0.5 (HADDA)(bipy) 0.5 ] (3) and [Co(ADDA)(bipy) 0.5 ] (4) (H 2 ADDA = 3,3'-(anthracene-9,10-diyl)diacrylic acid, bipy = 4,4′-bipyridine), have been successfully obtained based on reasonable synthetic strategies. N-donor auxiliary ligand, reaction medium and reaction temperature jointly induce interesting transformation of secondary building unit (SBU), resulting in structure diversities and topology variations. Notably, by increasing the reaction temperature in the mother liquid, 4 with {Co 2 (COO) 4 } paddle-wheel SBU can be generated by the single-crystal to single-crystal transformation of 3 with mononuclear {CoO 4 } SBU. Furthermore, the magnetic properties and electrocatalytic activities of these four Co-MOFs are also investigated in detail. • Four novel 3D Co(II)-containing metal–organic frameworks have been successfully synthesized. • N-donor auxiliary ligand, reaction medium and reaction temperature induce transformation of secondary building unit. • It offers insights into construction of new MOFs with SBU transformation for magnetic technology and electrocatalysis. [ABSTRACT FROM AUTHOR]

Linker desymmetrization has been witnessed as a powerful design strategy for the discovery of highly connected metal–organic frameworks (MOFs) with unprecedented topologies. Herein, we introduce molecular pivot‐hinge installation as a linker desymmetrization strategy to evolve the topology of highly connected rare‐earth (RE) MOFs, where a pivot group is placed in the center of a linker similar to a hinge. By tuning the composition of pivot groups and steric hindrances of the substituents on various linker rotamers, MOFs with various topologies can be obtained. The combination of L‐SO2 with C2v symmetry and 12‐connected RE9 clusters leads to the formation of a fascinating (4,12)‐c dfs new topology. Interestingly, when replacing L‐SO2 with a tetrahedra linker L‐O, the stacking behaviors of RE‐organic layers switch from an eclipsed mode to a staggered stacking mode, leading to the discovery of an intriguing hjz topology. Additionally, the combination of the RE cluster and a linker [(L‐(CH3)6)] with more bulky groups gives rise to a flu topology with a new 8‐c inorganic cluster. The diversity of these RE‐MOFs was further enhanced through post‐synthetic installation of linkers with various functional groups. Functionalization of each linker with acidic and basic units in the mesoporous RE‐based PCN‐905‐SO2 allows for efficient cascade catalytic transformation within the functionalized channels. [ABSTRACT FROM AUTHOR]

Linker desymmetrization has been witnessed as a powerful design strategy for the discovery of highly connected metal–organic frameworks (MOFs) with unprecedented topologies. Herein, we introduce molecular pivot‐hinge installation as a linker desymmetrization strategy to evolve the topology of highly connected rare‐earth (RE) MOFs, where a pivot group is placed in the center of a linker similar to a hinge. By tuning the composition of pivot groups and steric hindrances of the substituents on various linker rotamers, MOFs with various topologies can be obtained. The combination of L‐SO2 with C2v symmetry and 12‐connected RE9 clusters leads to the formation of a fascinating (4,12)‐c dfs new topology. Interestingly, when replacing L‐SO2 with a tetrahedra linker L‐O, the stacking behaviors of RE‐organic layers switch from an eclipsed mode to a staggered stacking mode, leading to the discovery of an intriguing hjz topology. Additionally, the combination of the RE cluster and a linker [(L‐(CH3)6)] with more bulky groups gives rise to a flu topology with a new 8‐c inorganic cluster. The diversity of these RE‐MOFs was further enhanced through post‐synthetic installation of linkers with various functional groups. Functionalization of each linker with acidic and basic units in the mesoporous RE‐based PCN‐905‐SO2 allows for efficient cascade catalytic transformation within the functionalized channels. [ABSTRACT FROM AUTHOR]

Al-MOFs have diverse chemical structures and tunable properties for potential applications in adsorption, separation, catalysis, proton conduction, chirality, and superhydrophobicity fields. [Display omitted] • Systematically summarized the similarities between secondary building units and linkers from the structural aspect of Al-MOFs, the structurally-led approach is distinctive and helps to better understand the crystal chemistry of Al-MOFs. • Introduced the research progress and highlighted several exciting discoveries of studying Al-MOFs. • Demonstrated the development trends, emerging challenges, and opportunities primarily oriented to their scalable production, and aimed at exploring the future application prospects of Al-MOFs from academic research to industrial production. It is essential to explore metal–organic frameworks (MOFs) with high durabilities and versatile properties for practical applications. Multiple metal ions have been utilized to construct MOFs, among which the aluminum ion (Al3+) has drawn intensive attention due to its low toxicity, abundant reserves in the earth, low cost, and sustainability. As an attractive MOF family in virtue of its diverse structures and functions, Al-MOFs exhibit high physicochemical stability and have wide applications in many scientific and engineering fields, due to the diverse secondary building units (SBUs) of Al3+ and the strong Al-O bond. In this review, we systematically summarize the SBUs and linkers from a structural perspective. We also highlight the research progress of Al-MOFs with novel topologies and structures. According to the composition of Al-metal nodes, Al-MOFs can be divided into Al3+-ions, Al3+-chains, or Al3+-clusters. In addition, the potential applications of Al-MOFs in various fields, including adsorption, separation, photocatalysis, electrochemistry, chirality, and superhydrophobicity are discussed. From the perspective of Al-MOF structures, the relationship between the structure and performances of Al-MOFs is reviewed, and the future application prospects of Al-MOFs are discussed. [ABSTRACT FROM AUTHOR]

Abstract: A barium(II) metal‐organic framework (MOF) based on a predesigned amino‐functionalized ligand, namely [Ba2(L)(DMF)(H2O)(NO3)1/3]⋅DMF⋅EtOH⋅2 H2O (UPC‐33) [H3L=4,4′‐((2‐amino‐5‐carboxy‐1,3‐phenylene)bis(ethyne‐2,1‐diyl))dibenzoic acid] has been synthesized. UPC‐33 is a 3‐dimensional 3,18‐connected network with fcu topology with a rare twelve‐nuclear Ba12(COO)18(NO3)2 cluster. UPC‐33 shows permanent porosity and a high adsorption heat of CO2 (49.92 kJ mol−1), which can be used as a platform for selective adsorption of CO2/CH4 (8.09). In addition, UPC‐33 exhibits high separation selectivity for C3 light hydrocarbons with respect to CH4 (228.34, 151.40 for C3H6/CH4, C3H8/CH4 at 273k and 1 bar), as shown by single component gas sorption and selectivity calculations. Due to the existence of −NH2 groups in the channels, UPC‐33 can effectively catalyze Knoevenagel condensation reactions with high yield, and substrate size and electron dependency. [ABSTRACT FROM AUTHOR]

This work presents the construction of a porous lead-organic framework (UPC-10) with large channels of ∼24 Å. UPC-10 shows efficient adsorption of I2 and selective adsorption of some dyes containing the SO3− group. After the adsorption of dyes, UPC-10 exhibits a CO2 gas uptake ability. Furthermore, UPC-10 could be transformed into PbS in a H2S atmosphere, and the derived PbS manifests N2 and CO2 uptake abilities. [ABSTRACT FROM AUTHOR]

The surface wettability switching of JUC-150 Metal-Organic Framework (MOF) mesh from hydrophilicity to hydrophobicity was achieved by a facial polydimethylsiloxane (PDMS) modification method. The PDMS modified JUC-150 mesh (JUC-150@PDMS mesh) exhibited high oil-water separation efficiency and flux attributed to the porous structure of the nickel mesh substrate. The passing phase (water or oil) through the MOF mesh can be determined according to the demand, which is of vital importance for industrial applications. Furthermore, this method is universal for other MOF meshes, films and membranes that will be applied in the field of water purification and gas mixture separation with steam. [ABSTRACT FROM AUTHOR]

Two lanthanide MOFs based on 3,3′-((2,3,6,7-tetramethoxyanthracene-9,10-diyl)bis(4,1-phenylene))diacrylic acid (H2LOMe), [Eu(LOMe)1.5(H2O)2]·3.5DMA·2H2O (1) and [Pr(LOMe)(H2O)4]·2.5DMA·3H2O (2) were synthesized under solvothermal conditions. Complex 1 displayed a 2D net with single nodal 44-sql topology, which further formed a 3D supramolecular architecture by strong π…π interaction. Complex 2 featured a 3D open framework with {42·84}-PtS topology. The PL spectrum results showed that 2 has potential application not only in the sensing of small organic molecules, such as DMF and NB, but also in detecting Al3+ and nitroaromatic derivatives. Furthermore, 2 also showed the selective adsorption of CO2 over CH4 and high catalytic activities with the cyanosilylation reaction. [ABSTRACT FROM AUTHOR]

An anionic metal-organic framework, H3[(Mn4Cl)3 L8]⋅30 H2O⋅2.5 DMF⋅5 Diox ( UPC-15), was successfully prepared by the reaction of MnCl2 with tris( p-carboxylic acid)tridurylborane (H3 L) under solvothermal conditions. UPC-15 with wide-open pores (∼18.8 Å) is constructed by packing of octahedral and cuboctahedral cages, and exhibits high gas-sorption capabilities. Notably, UPC-15 shows selective adsorption of cationic dyes due to the anion framework. Moreover, the catalytic and magnetic properties were investigated, and UPC-15 can highly catalyze the cyanosilylation of aromatic aldehydes. UPC-15 exhibits the exchange of metal ions from Mn to Cu in a single-crystal-to-single-crystal manner to generate UPC-16, which could not be obtained by the direct solvothermal reaction of CuCl2 and H3 L. UPC-16 exhibits similar properties for gas sorption, dye separation, and catalytic activity. However, the magnetic behaviors for UPC-15 and UPC-16 are distinct due to the metal-specific properties. Below 47 K, UPC-15 exhibits a ferromagnetic coupling but UPC-16 shows a dominant antiferromagnetic behavior. [ABSTRACT FROM AUTHOR]

Through a pillar-ligand extension strategy, a rare breathing behavior in polycatenated 2D→3D nets has been achieved. Three variants exhibit interesting sorption properties that range from non-breathing to breathing behaviors, which is influenced by the angles between the pillars and the single honeycomb layers. The increase in pillar length does not lead to an increase in polycatenation multiplicity, which is controlled by the length of intralayer tripodal carboxylate. It also does not induce obviously expanded interlayer separations but occupies much more the free voids, and as a consequence, a smaller pore volume is obtained. This suggests that in 2D→3D polycatenated bilayer metal-organic frameworks, the porosity is not always enhanced by increasing the length of the interlayer pillars with the intralayer linker remaining unchanged. [ABSTRACT FROM AUTHOR]

Twoisomorphous lanthanide–organic frameworks, Ln(BDC)1.5(DMF)(H2O) (Ln = Er (1), Tm (2)) have been synthesized based on 1,4-benzenedicarboxylicacid (H2BDC). Because of the 2-fold interpenetration, thepores are partly blocked and there are no significant gas adsorptionsfor these two interpenetrating nets. Through control over interpenetrationby applying an organic ligand with hindrance groups or replacing coordinatedsolvent molecules with a chelating ligand, three non-interpenetratinglanthanide–organic frameworks, Er2(BDC)3(phen)2·3H2O (3), Tm(TBDC)1.5(DMF)(H2O)·2H2O (4), Er2(TBDC)3(phen)2·4DMF·2H2O (5), possessing the same topology with 1and 2, have been synthesized and characterized.Further changing reaction conditions, three other porous lanthanide–organicframeworks with different structures with 1–5, Tm(BDC)1.5(H2O)·0.5DMF·C2H5OH·2H2O (6), Tm4(BDC)6(H2O)2(DMF)(C2H5OH)·2DMF·2H2O (7),and Sm(TBDC)1.5(phen)(H2O)·DMF·H2O (8), have been constructed. Gas sorption measurementsfor 5, 6, 7, and 8have been carried out and revealed that these materials possesspermanent porosity. The catalytic property for complex 6has also been studied. [ABSTRACT FROM AUTHOR]

[Display omitted] • New 3D bulk MOF and 2D ultrathin MOF nanosheets are synthesized. • The planar micro-supercapacitors with the interdigital microelectrodes are achieved based on MOF bulk and MOF nanosheets. • The MOF-nanosheets for micro-supercapacitors displays enhanced performance than MOF bulk. Due to the advantages of ultrahigh power density, long lifespan and easy integration with wearable and microscale electronics, micro-supercapacitors (MSCs) have attracted great interest in recent years. However, new high-performance electrode materials for such micro-electrochemical energy storage devices require deep excavation. Herein, we precisely synthesized a new 3D bulk MOF and new 2D ultrathin MOF nanosheets with a thickness of less than 10 nm, and utilized them as high-capacitance microelectrode materials for sophisticated all-solid-state MSC devices respectively. Notably, the MSCs based on MOF nanosheets displayed a high areal capacitance of 28.3 mF·cm−2, and a volumetric capacitance of 15.7 F·cm−3 at 0.2 mA·cm−2. Especially, our MSCs exhibited remarkable energy density of 8.7 mWh·cm−3 at a power density of 110.3 mW·cm−3, and excellent cycling lifespans with retention of 96.0% after 10,000 cycles, and all performances are better than the MSCs based on MOF bulks. This work provides a new way to further explore the inherent advantages of MOFs and stimulates the synthesis of advanced MOFs materials for application in microscale energy storage. [ABSTRACT FROM AUTHOR]

Keywords: cobalt; ethylene purification; metal-organic frameworks (MOFs); one-step purification; ternary gas mixture EN cobalt ethylene purification metal-organic frameworks (MOFs) one-step purification ternary gas mixture 11532 11532 1 05/06/21 20210510 NES 210510 B A CpCo group b was introduced in a cubic cage to generate a sphere-like force surface, thus dividing the cubic cage into two parts. Back Cover: One-step Ethylene Purification from an Acetylene/Ethylene/Ethane Ternary Mixture by Cyclopentadiene Cobalt-Functionalized Metal-Organic Frameworks (Angew. Based on the high selectivity of the CpCo group, high-purity ethylene is obtained from an acetylene/ethylene/ethane ternary mixture, as reported by Daofeng Sun et al. in their Research Article on page 11350. [Extracted from the article]

Cobalt, ethylene purification, metal-organic frameworks (MOFs), one-step purification, ternary gas mixture Keywords: cobalt; ethylene purification; metal-organic frameworks (MOFs); one-step purification; ternary gas mixture EN cobalt ethylene purification metal-organic frameworks (MOFs) one-step purification ternary gas mixture 11636 11636 1 05/06/21 20210510 NES 210510 B Eine CpCo-Einheit b wurde in einen kubischen Käfig eingeführt, um eine sphärische Kraftfläche zu erzeugen, wodurch der kubische Käfig in zwei Teile geteilt wird. Rücktitelbild: One-step Ethylene Purification from an Acetylene/Ethylene/Ethane Ternary Mixture by Cyclopentadiene Cobalt-Functionalized Metal-Organic Frameworks (Angew. [Extracted from the article]

Membranes with well-defined pore structure which have thin active layers may be promising materials for efficient gas separation. Graphene oxide (GO) materials have potential applications in the field of membrane separation. Here we describe a strategy for the construction of ultra-thin and flexible HKUST-1@GO intercalated membranes, where HKUST-1 is a copper-based metal–organic framework with coordinatively unsaturated metal sites, with simultaneous and synergistic modulation of permeance and selectivity to achieve high H2/CO2 separation. CuO nanosheets@GO membranes are fabricated layer-by-layer via repeated filtration cycles, then transformed to HKUST-1@GO membranes upon in situ reaction with linkers. The HKUST-1@GO membranes show enhanced performance for gas separation of H2/CO2 mixture. The number of filtration cycles is optimized to obtain H2 permeance of 5.77 × 10−7 mol m−2 s−1 Pa−1 and H2/CO2 selectivity of 73.2. Our work provides a facile strategy for the construction of membranes based on metal–organic frameworks and GO, which may be applied in the preparation of flexible membranes for gas separation applications. Graphene oxide membranes are promising materials for the separation of low molecular weight gases. Here, composite membranes comprising metal organic frameworks and graphene oxide show improved selectivity for the separation of hydrogen and carbon dioxide over graphene oxide alone. [ABSTRACT FROM AUTHOR]