Helical water chain mediated proton conductivity in homochiral metal-organic frameworks with unprecedented zeolitic unh-topology

Four new homochiral metal-organic framework (MOF) isomers, [Zn(l-L(Cl))(Cl)](H(2)O)(2) (1), [Zn(l-L(Br))(Br)](H(2)O)(2) (2), [Zn(d-L(Cl))(Cl)](H(2)O)(2) (3), and [Zn(d-L(Br))(Br)](H(2)O)(2) (4) [L = 3-methyl-2-(pyridin-4-ylmethylamino)butanoic acid], have been synthesized by using a derivative of L-/D-valine and Zn(CH(3)COO)(2)·2H(2)O. A three-periodic lattice with a parallel 1D helical channel was formed along the crystallographic c-axis. Molecular rearrangement results in an unprecedented zeolitic unh-topology in 1-4. In each case, two lattice water molecules (one H-bonded to halogen atoms) form a secondary helical continuous water chain inside the molecular helix. MOFs 1 and 2 shows different water adsorption properties and hence different water affinity. The arrangement of water molecules inside the channel was monitored by variable-temperature single-crystal X-ray diffraction, which indicated that MOF 1 has a higher water holding capacity than MOF 2. In MOF 1, water escapes at 80 °C, while in 2 the same happens at a much lower temperature (～40 °C). All the MOFs reported here shows reversible crystallization by readily reabsorbing moisture. In MOFs 1 and 2, the frameworks are stable after solvent removal, which is confirmed by a single-crystal to single-crystal transformation. MOFs 1 and 3 show high proton conductivity of 4.45 × 10(-5) and 4.42 × 10(-5) S cm(-1), respectively, while 2 and 4 shows zero proton conductivity. The above result is attributed to the fact that MOF 1 has a higher water holding capacity than MOF 2.     

Homo‐Helical Rod Packing as a Path Toward the Highest Density of Guest‐Binding Metal Sites in Metal–Organic Frameworks

In porous materials, metal sites with coordinate solvents offer opportunities for many applications, especially those promoted by host–guest chemistry, but such sites are especially hard to create for Li‐based materials, because unlike transition metals, lithium does not usually possess a high‐enough coordination number for both framework construction and guest binding. This challenge is addressed by mimicking the functional group ratio and metal‐to‐ligand charge ratio in MOF‐74. A family of rod‐packing lithium–organic frameworks (CPM‐47, CPM‐48, and CPM‐49) were obtained. These materials exhibit an extremely high density of guest‐binding lithium sites. Also unusual is the homo‐helical rod‐packing in the CPM series, as compared to the hetero‐helical rod packing by helices of opposite handedness in MOF‐74. This work demonstrates new chemical and structural possibilities in developing a record‐setting high density of guest‐binding metal sites in inorganic–organic porous materials.     

A chiral tetragonal magnesium-carboxylate framework with nanotubular channels

Reported here is a rare example of a highly symmetrical chiral Mg-based MOF (CPF-1) with nanotubular channels, built from 4(1) (or 4(3)) helical chains. It exhibits a high gas sorption capacity (ca. 1.29 wt% H(2) at 77 K, 1 atm; 84 cm(3) g(-1) of CO(2) at 273 K, 1 atm).     

Construction of Stable Helical Metal-Organic Frameworks with a Conformationally Rigid “Concave Ligand”

A helical metal-organic framework was prepared by using a conformationally rigid tetratopic benzoic acid ligand with binding units pointing toward each other (concave ligand). To avoid the obvious intramolecular interactions between binding units, matching spacing groups were applied to introduce atropic repulsion, thereby allowing the formation of extended frameworks for the first time. With this new ligand design, a helical-shaped MOF with significantly improved air and moisture stability was successfully prepared, thus providing a new strategy for ligand design toward porous material constructions.     

A Highly Energetic N‐Rich Metal–Organic Framework as a New High‐Energy‐Density Material

Metal–organic framework (MOF)‐based energetic material [Cu₃(MA)₂(N₃)₃] ( 1 ; MA=melamine) was synthesized and structurally characterized (47.55 % N). The structural analysis revealed the existence of unusual multiwalled tubular channels and interweaving of single and double helical units in 1 . The standard molar enthalpy of formation was found to be 1788.73 kJ mol^?1, which is the highest value among previously reported MOF‐based energetic materials. The calculated detonation properties showed that 1 can be used as a potential explosive. Sensitivity tests revealed that 1 is insensitive and thus can function as a high‐energy‐density material with a favorable level of safety.     

A new coordination polymer exhibiting unique 2D hydrogen-bonded (H2O)16 ring formation and water-dependent luminescence properties

A new coordination polymer, [Zn(dpe)(bdc)]·4H(2)O (ZndB; dpe=1,2-bis(4-pyridyl)ethane, bdc(2-)=dianion of benzenedicarboxylic acid), which possesses a 3D metal-organic framework (MOF) has been synthesized and structurally characterized. This 3D MOF is constructed by the assembly of helical channels filled with guest water molecules in both inner and outer regions of the channel. The resulting network also creates a 2D water layer containing hydrogen-bonded (H(2)O)(16) rings as the basic building units. Thermogravimetric and powder X-ray diffraction measurements of ZndB revealed a two-step weight loss of water molecules with a reversible water adsorption/desorption process in the inner channel for the first stage, and irreversible water desorption in the outer channel for the second stage. This spongelike property is manifested by the excimer emission originating from interaction between dpe (π*) and the other dpe (π) of the proximal helical channel, which is highly sensitive to the environmental perturbation. Powder X-ray analyses reveal that the dehydration process induces the readjustment of dpe π-π stacking distance/orientation, which results in dramatic luminescence changes from dim pale blue (λ(em)≈470 nm) upon hydration to bright white-light generation (broad, λ(em)≈500-550 nm) upon water depletion, accompanied by a ≈100-fold increase in the emission intensity.     

Metal-Carboxyl Helical Chain Secondary Units Supported Ion-Exchangeable Anionic Uranyl–Organic Framework

As a less explored avenue, actinide-based metal-organic frameworks (MOFs) are worth studying for the particularity of actinide nodes in coordination behaviour and assembly modes. In this work, an azobenzenetetracarboxylate-based anionic MOF supported by uranyl–carboxyl helical chain units was synthesized, incorporating linear uranyl as the metal centre. This kind of helical chain-type building unit is reported for the first time in uranyl-based MOFs. Structural analysis reveals that the formation of helical chain secondary units can be attributed to restricted equatorial coordination of rigid flat azobenzene ligand to uranyl centres. Meanwhile, this newly-synthesized anionic material has been used to remove Eu³⁺ ions, as a non-radioactive surrogate of Am³⁺ ion, through an ion-exchange process with [(CH₃)₂NH₂]⁺ ions in its open channels, as evidenced by a combination of ¹H NMR spectroscopy, EDS and PXRD.     

基于超分子构筑模块和酰胺插入的螺旋配体的PCN类型金属有机骨架的结构和选择性吸附CO2

首次实现了窗口缩小的小斜方六面体超分子构筑模块(SBB)和酰胺功能化螺旋配体5,5’-(((1,1’-biphenyl)-2,2’-dicarbonyl)bis(azanediyl))diisophthalic acid (H₄L)的链接,形成了一个pcu拓扑的微孔金属有机骨架[Cu₂(L)(H₂O)₂]·DMF·6H₂O(NTUniv-53),其在室温下展示了良好的二氧化碳吸附选择性。由于窗口缩小和酰胺的共同作用,该选择性基本不受温度变化的影响。     

金属-有机框架衍生中空超级结构的研究进展:合成与应用（英文）

金属-有机框架(MOF)衍生功能材料的合理设计对于其应用具有重要意义.以简单MOF衍生物为基本单元组装成中空超级结构(HSSs)是提升材料性能的有效策略.目前关于MOF衍生物的综合评述已有诸多报道,然而鲜少针对HSSs的构筑和应用.本文系统总结了MOF衍生HSSs相关研究的最新进展.首先,根据结构差异将MOF衍生HSSs分为5种类型;其次,总结了由MOF衍生物构建HSSs的策略,着重阐述如何设计MOF前驱体和选择转化条件;随后,展示了MOF衍生HSSs在能源和催化相关领域的一些应用;最后,提出了MOF衍生HSSs研究领域所面临的挑战和机遇,旨在为MOF衍生材料的结构设计和性能强化提供一些思路.     

MOF‐on‐MOF: Oriented Growth of Multiple Layered Thin Films of Metal–Organic Frameworks

The precise alignment of multiple layers of metal–organic framework (MOF) thin films, or MOF‐on‐MOF films, over macroscopic length scales is presented. The MOF‐on‐MOF films are fabricated by epitaxially matching the interface. The first MOF layer (Cu₂(BPDC)₂, BPDC=biphenyl‐4,4′‐dicarboxylate) is grown on an oriented Cu(OH)₂ film by a “one‐pot” approach. Aligned second (Cu₂(BDC)₂, BDC=benzene 1,4‐dicarboxylate, or Cu₂(BPYDC)₂, BPYDC=2,2′‐bipyridine‐5,5′‐dicarboxylate) MOF layers can be deposited using liquid‐phase epitaxy. The co‐orientation of the MOF films is confirmed by X‐ray diffraction. Importantly, our strategy allows for the synthesis of aligned MOF films, for example, Cu₂(BPYDC)₂, that cannot be grown on a Cu(OH)₂ surface. We show that aligned MOF films furnished with Ag nanoparticles show a unique anisotropic plasmon resonance. Our MOF‐on‐MOF approach expands the chemistry of heteroepitaxially oriented MOF films and provides a new toolbox for multifunctional porous coatings.     

Controllable Modular Growth of Hierarchical MOF‐on‐MOF Architectures

Fabrication of hybrid MOF‐on‐MOF heteroarchitectures can create novel and multifunctional platforms to achieve desired properties. However, only MOFs with similar crystallographic parameters can be hybridized by the classical epitaxial growth method (EGM), which largely suppressed its applications. A general strategy, called internal extended growth method (IEGM), is demonstrated for the feasible assembly of MOFs with distinct crystallographic parameters in an MOF matrix. Various MOFs with diverse functions could be introduced in a modular MOF matrix to form 3D core–satellite pluralistic hybrid system. The number of different MOF crystals interspersed could be varied on demand. More importantly, the different MOF crystals distributed in individual domains could be used to further incorporate functional units or enhance target functions.     

Integration of Plasmonic Effects and Schottky Junctions into Metal–Organic Framework Composites: Steering Charge Flow for Enhanced Visible‐Light Photocatalysis

A wide range of light absorption and rapid electron–hole separation are desired for efficient photocatalysis. Herein, on the basis of a semiconductor‐like metal–organic framework (MOF), a Pt@MOF/Au catalyst with two types of metal–MOF interfaces integrates the surface plasmon resonance excitation of Au nanorods with a Pt‐MOF Schottky junction, which not only extends the light absorption of the MOF from the UV to the visible region but also greatly accelerates charge transfer. The spatial separation of Pt and Au particles by the MOF further steers the formation of charge flow and expedites the charge migration. As a result, the Pt@MOF/Au presents an exceptionally high photocatalytic H₂ production rate by water splitting under visible light irradiation, far superior to Pt/MOF/Au, MOF/Au and other counterparts with similar Pt or Au contents, highlighting the important role of each component and the Pt location in the catalyst.     

Metal Organic Framework Glasses: A New Platform for Electrocatalysis?

Metal organic framework (MOF) glasses are a coordination network of metal nodes and organic ligands as an undercooled frozen-in liquid, and have therefore broadened the potential of MOF materials in the fundamental research and application scenarios. On the road to deploying MOF glasses as electrocatalysts, it remains several basic scientific hurdles although MOF glasses not only inherit the structural merits of MOFs but also endow with active catalytic features including concentrated defects, metal centers and disorder structure etc. The research on the ionic conductivity, catalytic stability and reactivity of MOF glasses has yielded scientific insights towards its electrocatalytic applications. Here, we first comb the history, definition and basic properties of MOF glasses. Then, we identify the main synthetic methods and characterization techniques. Finally, we advance the potentials and challenges of MOF glasses as electrocatalysts in furthering the understanding of these themes.     

An Ultrahydrophobic Fluorous Metal–Organic Framework Derived Recyclable Composite as a Promising Platform to Tackle Marine Oil Spills

Derived from a strategically chosen hexafluorinated dicarboxylate linker aimed at the designed synthesis of a superhydrophobic metal–organic framework (MOF), the fluorine‐rich nanospace of a water‐stable MOF ( UHMOF‐100 ) exhibits excellent water‐repellent features. It registered the highest water contact angle (≈176°) in the MOF domain, marking the first example of an ultrahydrophobic MOF. Various experimental and theoretical studies reinforce its distinctive water‐repellent characteristics, and the conjugation of superoleophilicity and unparalleled hydrophobicity of a MOF material has been coherently exploited to achieve real‐time oil/water separation in recyclable membrane form, with significant absorption capacity performance. This is also the first report of an oil/water separating fluorinated ultrahydrophobic MOF‐based membrane material, with potential promise for tackling marine oil spillages.     

Van der Waals Heterostructured MOF‐on‐MOF Thin Films: Cascading Functionality to Realize Advanced Chemiresistive Sensing

Heterostructured metal—organic framework (MOF)‐on‐MOF thin films have the potential to cascade the various properties of different MOF layers in a sequence to produce functions that cannot be achieved by single MOF layers. An integration method that relies on van der Waals interactions, and which overcomes the lattice‐matching limits of reported methods, has been developed. The method deposits molecular sieving Cu‐TCPP (TCPP=5,10,15,20‐tetrakis(4‐carboxyphenyl)porphyrin) layers onto semiconductive Cu‐HHTP (HHTP=2,3,6,7,10,11‐hexahydrotriphenylene) layers to obtain highly oriented MOF‐on‐MOF thin films. For the first time, the properties in different MOF layers were cascaded in sequence to synergistically produce an enhanced device function. Cu‐TCPP‐on‐Cu‐HHTP demonstrated excellent selectivity and the highest response to benzene of the reported recoverable chemiresistive sensing materials that are active at room temperature. This method allows integration of MOFs with cascading properties into advanced functional materials.     

Ruthenium Complexation in an Aluminium Metal–Organic Framework and Its Application in Alcohol Oxidation Catalysis

A ruthenium trichloride complex has been loaded into an aluminium metal–organic framework (MOF), MOF‐253, by post‐synthetic modification to give MOF‐253‐Ru. MOF‐253 contains open bipyridine sites that are available to bind with the ruthenium complex. MOF‐253‐Ru was characterised by elemental analysis, N₂ sorption and X‐ray powder diffraction. This is the first time that a Ru complex has been coordinated to a MOF through post‐synthetic modification and used as a heterogeneous catalyst. MOF‐253‐Ru catalysed the oxidation of primary and secondary alcohols, including allylic alcohols, with PhI(OAc)₂ as the oxidant under very mild reaction conditions (ambient temperature to 40 °C). High conversions (up to >99 %) were achieved in short reaction times (1–3 h) by using low catalyst loadings (0.5 mol % Ru). In addition, high selectivities (>90 %) for aldehydes were obtained at room temperature. MOF‐253‐Ru can be recycled up to six times with only a moderate decrease in substrate conversion.     

Lithographic Deposition of Patterned Metal–Organic Framework Coatings Using a Photobase Generator

A photobase generator was used to induce metal–organic framework (MOF) nucleation upon UV irradiation. This method was further developed into a simple, one‐step method for depositing patterned MOF films. Furthermore, the ability of our method to coat a single substrate with MOF films having different chemical compositions is illustrated. The method is an important step towards integrating MOF deposition with existing lithographic techniques and the incorporation of these materials into sensors and other electronic devices.     

MOF-on-MOF heteroepitaxy: perfectly oriented [Zn2(ndc)2(dabco)]n grown on [Cu2(ndc)2(dabco)]n thin films

We report the successful heteroepitaxial growth of perfectly oriented hybrid MOF thin films. By employing step-by-step liquid-phase epitaxy (LPE), [Zn(2)(ndc)(2)(dabco)](n) was grown on [Cu(2)(ndc)(2)(dabco)](n), thus demonstrating that the MOF-on-MOF deposition scheme developed for powdered microcrystalline MOF materials can also be applied in connection with LPE for MOF thin films or multilayers. The deposition was monitored by surface plasmon resonance (SPR) spectroscopy, the resulting MOF heterostructures were characterized using IR spectroscopy and different types of X-ray diffraction (XRD)-based techniques. The results suggest that the LPE method is a promising way to fabricate and grow MOF heterostructures, and also demonstrates the potential of [Cu(2)(ndc)(2)(dabco)](n) MOF thin films as substrates for the LPE-based growth of different MOFs on top.     

Metal-organic framework membranes: From synthesis to electrocatalytic applications

Metal-organic frameworks (MOFs), as an emerging family of porous inorganic-organic crystal materials, exhibit widely applications in gas storage and separation, drug release, sensing, and catalysis, owing to easily adjustable pore sizes, uniformly distributed metal centers, high surface areas, and tunable functionalities. However, MOF crystal powders are usually difficult to be directly applied into specific devices because of their brittleness, insolubility and low compatibility. Therefore, to expand versatile MOF membranes with robustness and operational flexibility is urgent to satisfy practical applications. Although numerous reports have reviewed the synthesis and applications of MOF membranes, relatively few reports the electrocatalytic properties based on MOF membranes. Herein, this mini-review provides an overview of preparation of MOF membranes, including directed synthesis, secondary growth and electrochemical deposition method. Meanwhile, fabrication of ultrathin 2D MOF nanosheets those can be also defined as a kind of nanoscale MOF membranes is also mentioned. Electrocatalytic performance of oxygen reduction reaction (ORR), oxygen evolution reaction (OER), hydrogen evolution reaction (HER) and CO₂ reduction reaction (CO₂RR) for diverse MOF membranes/nanosheets and their derivatives are introduced.     

Spray-Coating of Catalytically Active MOF–Polythiourea through Postsynthetic Polymerization

A UiO-66-NCS MOF was formed by postsynthetic modification of UiO-66-NH₂. The UiO-66-NCS MOFs displays a circa 20-fold increase in activity against the chemical warfare agent simulant dimethyl-4-nitrophenyl phosphate (DMNP) compared to UiO-66-NH₂, making it the most active MOF materials using a validated high-throughput screening. The −NCS functional groups provide reactive handles for postsynthetic polymerization of the MOFs into functional materials. These MOFs can be tethered to amine-terminated polypropylene polymers (Jeffamines) through a facile room-temperature synthesis with no byproducts. The MOFs are then crosslinked into a MOF–polythiourea (MOF–PTU) composite material, maintaining the catalytic properties of the MOF and the flexibility of the polymer. This MOF–PTU hybrid material was spray-coated onto Nyco textile fibers, displaying excellent adhesion to the fiber surface. The spray-coated fibers were screened for the degradation of DMNP and showed durable catalytic reactivity.