Pathway Dependence in Redox-Driven Metal–Organic Gels

Pathway dependence is common in self-assembly. Herein, the importance of pathway dependence for redox-driven gels is shown by constructing a Fe^II/Fe^III redox-based metal–organic gel system is shown. In situ oxidation of the Fe^II ions at different rates results in conversion of a Fe^II gel into a Fe^III organic gel, which controls the material properties, such as gel stiffness, gel strength, and an unusual swelling behaviour, is described. The rate of formation of Fe^III ions determines the extent of intermolecular interactions and so whether gelation or precipitation occurs.     

2D Semiconducting Metal–Organic Framework Thin Films for Organic Spin Valves

2D conductive metal–organic frameworks (2D c-MOFs) feature promising applications as chemiresistive sensors, electrode materials, electrocatalysts, and electronic devices. However, exploration of the spin-polarized transport in this emerging materials and development of the relevant spintronics have not yet been implemented. In this work, layer-by-layer assembly was applied to fabricate highly crystalline and oriented thin films of a 2D c-MOF, Cu₃(HHTP)₂, (HHTP: 2,3,6,7,10,11-hexahydroxytriphenylene), with tunable thicknesses on the La_0.67Sr_0.33MnO₃ (LSMO) ferromagnetic electrode. The magnetoresistance (MR) of the LSMO/Cu₃(HHTP)₂/Co organic spin valves (OSVs) reaches up to 25 % at 10 K. The MR can be retained with good film thickness adaptability varied from 30 to 100 nm and also at high temperatures (up to 200 K). This work demonstrates the first potential applications of 2D c-MOFs in spintronics.     

Enhancing Multicomponent Metal–Organic Frameworks for Low Pressure Liquid Organic Hydrogen Carrier Separations

The resurgence of interest in the hydrogen economy could hinge on the distribution of hydrogen in a safe and efficient manner. Whilst great progress has been made with cryogenic hydrogen storage or liquefied ammonia, liquid organic hydrogen carriers (LOHCs) remain attractive due to their lack of need for cryogenic temperatures or high pressures, most commonly a cycle between methylcyclohexane and toluene. Oxidation of methylcyclohexane to release hydrogen will be more efficient if the equilibrium limitations can be removed by separating the mixture. This report describes a family of six ternary and quaternary multicomponent metal–organic frameworks (MOFs) that contain the three-dimensional cubane-1,4-dicarboxylate (cdc) ligand. Of these MOFs, the most promising is a quaternary MOF (CUB-30), comprising cdc, 4,4′-biphenyldicarboxylate (bpdc) and tritopic truxene linkers. Contrary to conventional wisdom that adsorptive interactions with larger, hydrocarbon guests are dominated by π–π interactions, here we report that contoured aliphatic pore environments can exhibit high selectivity and capacity for LOHC separations at low pressures. This is the first time, to the best of our knowledge, where selective adsorption for cyclohexane over benzene is witnessed, underlining the unique adsorptive behavior afforded by the unconventional cubane moiety.     

Synthesis and Characterization of a Novel One-dimensional Metal Organic Compound

1 INTRODUCTION Metal-organic compounds with open-frameworks are of intense interest due to their potential appli- ciations in the fields of molecular sieving, optical materials, zeolitic catalyses and so forth[1～9]. Addi- tionally, their functionality can be modified by chan- ging either the inorganic species or the organic li- gands in the structures. In the past decade, one di- mensional (1-D) infinite sructure with specific topo- logies has been obtained by assembly of suitable metal …     

Coordination-Induced Band Gap Reduction in a Metal–Organic Framework

Herein, we report on the synthesis of a microporous, three-dimensional phosphonate metal–organic framework (MOF) with the composition Cu₃(H₅-MTPPA)₂ ⋅ 2 NMP (H₈-MTPPA=methane tetra-p-phenylphosphonic acid and NMP=N-methyl-2-pyrrolidone). This MOF, termed TUB1, has a unique one-dimensional inorganic building unit composed of square planar and distorted trigonal bipyramidal copper atoms. It possesses a (calculated) BET surface area of 766.2 m²/g after removal of the solvents from the voids. The Tauc plot for TUB1 yields indirect and direct band gaps of 2.4 eV and 2.7 eV, respectively. DFT calculations reveal the existence of two spin-dependent gaps of 2.60 eV and 0.48 eV for the alpha and beta spins, respectively, with the lowest unoccupied crystal orbital for both gaps predominantly residing on the square planar copper atoms. The projected density of states suggests that the presence of the square planar copper atoms reduces the overall band gap of TUB1, as the beta-gap for the trigonal bipyramidal copper atoms is 3.72 eV.     

Microscopic and Mesoscopic Dual Postsynthetic Modifications of Metal–Organic Frameworks

We report the dual postsynthetic modification (PSM) of a metal–organic framework (MOF) involving the microscopic conversion of C−H bonds into C−C bonds and the mesoscopic introduction of hierarchical porosity. MOF crystals underwent single-crystal-to-single-crystal transformations during the electrophilic aromatic substitution of Co₂(m-DOBDC) (m-DOBDC⁴⁻=4,6-dioxo-1,3-benzenedicarboxylate) with alkyl halides and formaldehyde. The steric hindrance caused by the proximity of the introduced functional groups to the coordination bonds reduced bond stability and facilitated the transformation into hierarchically porous mesostructures by etching with in situ generated protons (hydroniums) and halides. The numerous defect sites in the mesostructural MOFs are potential water-sorption sites. However, since the introduced functional groups are close to the main adsorption sites, even methyl groups are able to considerably decrease water adsorption, whereas hydroxy groups increase adsorption at low vapor pressures.     

Amorphization of Metal–Organic Framework MOF-5 by Electrical Discharge

Amorphization of various solid materials has attracted increasing attentions. We report here an amorphization of metal–organic framework-5 (MOF-5) of composition Zn₄O(BDC)₃ (BDC = 1,4-benzenedicarboxylate) using dielectric-barrier discharge (DBD) treatment at ambient pressure and low gas temperature (around 120°C). The irreversible amorphization was confirmed by x-ray diffraction (XRD) characterization. The result of N₂ adsorption–desorption measurements revealed a collapse of pores, which further supported the XRD results. The destroying of part of carboxylate groups might be the main reason resulting in the amorphization of MOF-5.     

Solvent-Vapor-Induced Reversible Single-Crystal-to-Single-Crystal Transformation of a Triphosphaazatriangulene-Based Metal–Organic Framework

A triphosphaazatriangulene (H₃L) was synthesized through an intramolecular triple phospha-Friedel–Crafts reaction. The H₃L triangulene contains three phosphinate groups and an extended π-conjugated framework, which enables the stimuli-responsive reversible transformation of [Cu(HL)(DMSO)⋅(MeOH)]_n, a 3D-MOF that exhibits reversible sorption characteristics, into (H₃L⋅0.5 [Cu₂(OH)₄⋅6 H₂O] ⋅4 H₂O), a 1D-columnar assembled proton-conducting material. The hydrophilic nature of the latter resulted in a proton conductivity of 5.5×10⁻³ S cm⁻¹ at 95 % relative humidity and 60 °C.     

Fabrication of Self-Expanding Metal–Organic Cages Using a Ring-Openable Ligand

Metal–organic cages (MOCs), which are formed via coordination-driven assembly, are being extensively developed for various applications owing to the utility of their accessible molecular-sized cavity. While MOC structures are uniquely and precisely predetermined by the metal coordination number and ligand configuration, tailoring MOCs to further modulate the size, shape, and chemical environment of the cavities has become intensively studied for a more efficient and adaptive molecular binding. Herein, we report self-expanding MOCs that exhibit remarkable structural variations in cage size and flexibility while maintaining their topology. A cyclic ligand with an oligomeric chain tethering the two benzene rings of stilbene was designed and mixed with Rh^II ions to obtain the parent MOCs. These MOCs were successfully transformed into expanded MOCs via the selective cleavage of the double bond in stilbene. The expanded MOCs could effectively trap multidentate N-donor molecules in their enlarged cavity, in contrast to the original MOCs with a narrow cavity. As the direct synthesis of expanded MOCs is impractical because of the entropically disfavored structures, self-expansion using ring-openable ligands is a promising approach that allows precision engineering and the production of functional MOCs that would otherwise be inaccessible.     

Imparting Multifunctionality by Utilizing Biporosity in a Zirconium-Based Metal–Organic Framework

In this work, we have synthesized nanocomposites made up of a metal–organic framework (MOF) and conducting polymers by polymerization of specialty monomers such as pyrrole (Py) and 3,4-ethylenedioxythiophene (EDOT) in the voids of a stable and biporous Zr-based MOF ( UiO-66 ). FTIR and Raman data confirmed the presence of polypyrrole ( PPy ) and poly3,4-ethylenedioxythiophene ( PEDOT ) in UiO-66-PPy and UiO-66-PEDOT nanocomposites, respectively, and PXRD data revealed successful retention of the structure of the MOF. HRTEM images showed successful incorporation of polymer fibers inside the voids of the framework. Owing to the intrinsic biporosity of UiO-66 , polymer chains were observed to selectively occupy only one of the voids. This resulted in a remarkable enhancement (million-fold) of the electrical conductivity while the nanocomposites retain 60–70 % of the porosity of the original MOF. These semiconducting yet significantly porous MOF nanocomposite systems exhibited ultralow thermal conductivity. Enhanced electrical conductivity with lowered thermal conductivity could qualify such MOF nanocomposites for thermoelectric applications.     

Rapid Generation of Hierarchically Porous Metal–Organic Frameworks through Laser Photolysis

Hierarchically porous metal–organic frameworks (HP-MOFs) facilitate mass transfer due to mesoporosity while preserving the advantage of microporosity. This unique feature endows HP-MOFs with remarkable application potential in multiple fields. Recently, new methods such as linker labilization for the construction of HP-MOFs have emerged. To further enrich the synthetic toolkit of MOFs, we report a controlled photolytic removal of linkers to create mesopores within microporous MOFs at tens of milliseconds. Ultraviolet (UV) laser has been applied to eliminate “photolabile” linkers without affecting the overall crystallinity and integrity of the original framework. Presumably, the creation of mesopores can be attributed to the missing-cluster defects, which can be tuned through varying the time of laser exposure and ratio of photolabile/robust linkers. Upon laser exposure, MOF crystals shrank while metal oxide nanoparticles formed giving rise to the HP-MOFs. In addition, photolysis can also be utilized for the fabrication of complicated patterns with high precision, paving the way towards MOF lithography, which has enormous potential in sensing and catalysis.     

Emergence of a Radical-Stabilizing Metal–Organic Framework as a Radio-photoluminescence Dosimeter

Radio-photoluminescence (RPL) materials display a distinct radiation-induced permanent luminescence center, and therefore find application in the detection of ionizing radiation. The current inventory of RPL materials, which were discovered by serendipity, has been limited to a small number of metal-ion-doped inorganic materials. Here we document the RPL of a metal–organic framework (MOF) for the first time: X-ray induced free radicals are accumulated on the organic linker and are subsequently stabilized in the conjugated fragment in the structure, while the metal center acts as the X-ray attenuator. These radicals afford new emission features in both UV-excited and X-ray excited luminescence spectra, making it possible to establish linear relationships between the radiation dose and the normalized intensity of the new emission feature. The MOF-based RPL materials exhibit advantages in terms of the dose detection range, reusability, emission stability, and energy threshold. Based on a comprehensive electronic structure and energy diagram study, the rational design and a substantial expansion of candidate RPL materials can be anticipated.     

Construction of Flexible-on-Rigid Hybrid-Phase Metal–Organic Frameworks for Controllable Multi-Drug Delivery

Multi-component MOFs contain multiple sets of unique and hierarchical pores, with different functions for different applications, distributed in their inter-linked domains. Herein, we report the construction of a class of precisely aligned flexible-on-rigid hybrid-phase MOFs with a unique rods-on-octahedron morphology. We demonstrated that hybrid-phase MOFs can be constructed based on two prerequisites: the partially matched topology at the interface of the two frameworks, and the structural flexibility of MOFs with acs topology, which can compensate for the differences in lattice parameters. Furthermore, we achieved domain selective loading of multiple guest molecules into the hybrid-phase MOF, as observed by scanning transmission electron microscopy–energy-dispersive X-ray spectrometry elemental mapping. Most importantly, we successfully applied the constructed hybrid-phase MOF to develop a dual-drug delivery system with controllable loading ratio and release kinetics.     

Stimuli-Responsive Luminescent Properties of Tetraphenylethene-Based Strontium and Cobalt Metal–Organic Frameworks

Herein we report two new TPE-based 3D MOFs, that is, Sr-ETTB and Co-ETTB (TPE=Tetraphenylethylene, H₈ETTB=4′,4′′′,4′′′′′,4′′′′′′′-(ethene-1,1,2,2-tetrayl)tetrakis(([1,1′-biphenyl]-3,5-dicarboxylic acid))). Through tailoring outer shell electron configurations of Sr^II and Co^II cations, the fluorescence intensity of the MOFs is tuned from high emission to complete non-emission. Sr-ETTB with strong blue fluorescence shows reversible fluorescence variations in response to pressure and temperature, which is directly related to the reversible deformation of the crystal structure. In addition, non-emissive Co-ETTB counterpart exhibits a turn-on fluorescent enhancement under the stimulation of analyte histidine. In the process, TPE-cored linkers in the MOFs are released through competitive coordination substitution and subsequently reassembled to perform aggregation-induced luminescence behavior originated from the organic linkers.     

Effective C4 Separation by Zeolite Metal–Organic Framework Composite Membranes

Inorganic zeolites have excellent molecular sieving properties, but they are difficult to process into macroscopic structures. In this work, we use metal–organic framework (MOF) glass as substrates to engineer the interface with inorganic zeolites, and then assemble the discrete crystalline zeolite powders into monolithic structures. The zeolites are well dispersed and stabilized within the MOF glass matrix, and the monolith has satisfactory mechanical stabilities for membrane applications. We demonstrate the effective separation performance of the membrane for 1,3-butadiene (C₄H₆) from other C₄ hydrocarbons, which is a crucial and challenging separation in the chemical industry. The membrane achieves a high permeance of C₄H₆ (693.00±21.83 GPU) and a high selectivity over n-butene, n-butane, isobutene, and isobutane (9.72, 9.94, 10.31, and 11.94, respectively). This strategy opens up new possibilities for developing advanced membrane materials for difficult hydrocarbon separations.     

Solid State Machinery of Multiple Dynamic Elements in a Metal–Organic Framework

Engineering coordinated rotational motion in porous architectures enables the fabrication of molecular machines in solids. A flexible two-fold interpenetrated pillared Metal-Organic Framework precisely organizes fast mobile elements such as bicyclopentane (BCP) (10⁷ Hz regime at 85 K), two distinct pyridyl rotors and E-azo group involved in pedal-like motion. Reciprocal sliding of the two sub-networks, switched by chemical stimuli, modulated the sizes of the channels and finally the overall dynamical machinery. Actually, iodine-vapor adsorption drives a dramatic structural rearrangement, displacing the two distinct subnets in a concerted piston-like motion. Unconventionally, BCP mobility increases, exploring ultra-fast dynamics (10⁷ Hz) at temperatures as low as 44 K, while the pyridyl rotors diverge into a faster and slower dynamical regime by symmetry lowering. Indeed, one pillar ring gained greater rotary freedom as carried by the azo-group in a crank-like motion. A peculiar behavior was stimulated by pressurized CO_2, which regulates BCP dynamics upon incremental site occupation. The rotary dynamics is intrinsically coupled to the framework flexibility as demonstrated by complementary experimental evidence (multinuclear solid-state NMR down to very low temperatures, synchrotron radiation XRD, gas sorption) and computational modelling, which helps elucidate the highly sophisticated rotor-structure interplay.     

Isoreticular Linker Substitution in Conductive Metal–Organic Frameworks with Through-Space Transport Pathways

The extension of reticular chemistry concepts to electrically conductive three-dimensional metal–organic frameworks (MOFs) has been challenging, particularly for cases in which strong interactions between electroactive linkers create the charge transport pathways. Here, we report the successful replacement of tetrathiafulvalene (TTF) with a nickel glyoximate core in a family of isostructural conductive MOFs with Mn²⁺, Zn²⁺, and Cd²⁺. Different coordination environments of the framework metals lead to variations in the linker stacking geometries and optical properties. Single-crystal conductivity data are consistent with charge transport along the linker stacking direction, with conductivity values only slightly lower than those reported for the analogous TTF materials. These results serve as a case study demonstrating how reticular chemistry design principles can be extended to conductive frameworks with significant intermolecular contacts.     

Encapsulation of a Porous Organic Cage into the Pores of a Metal–Organic Framework for Enhanced CO2 Separation

We present a facile approach to encapsulate functional porous organic cages (POCs) into a robust MOF by an incipient-wetness impregnation method. Porous cucurbit[6]uril (CB6) cages with high CO₂ affinity were successfully encapsulated into the nanospace of Cr-based MIL-101 while retaining the crystal framework, morphology, and high stability of MIL-101. The encapsulated CB6 amount is controllable. Importantly, as the CB6 molecule with intrinsic micropores is smaller than the inner mesopores of MIL-101, more affinity sites for CO₂ are created in the resulting CB6@MIL-101 composites, leading to enhanced CO₂ uptake capacity and CO₂/N₂, CO₂/CH₄ separation performance at low pressures. This POC@MOF encapsulation strategy provides a facile route to introduce functional POCs into stable MOFs for various potential applications.     

Metal–Organic Gels from Silver Nanoclusters with Aggregation-Induced Emission and Fluorescence-to-Phosphorescence Switching

Luminescent metal nanoclusters (NCs) are emerging as a new class of functional materials that have rich physicochemical properties and wide potential applications. In recent years, it has been found that some metal NCs undergo aggregation-induced emission (AIE) and an interesting fluorescence-to-phosphorescence (F-P) switching in solutions. However, insights of both the AIE and the F-P switching remain largely unknown. Now, gelation of water soluble, atomically precise Ag₉ NCs is achieved by the addition of antisolvent. Self-assembly of Ag₉ NCs into entangled fibers was confirmed, during which AIE was observed together with an F-P switching occurring within a narrow time scale. Structural evaluation indicates the fibers are highly ordered. The self-assembly of Ag₉ NCs and their photoluminescent property are thermally reversible, making the metal–organic gels good candidates for luminescent ratiometric thermometers.     

3D Chiral Nanoporous Metal–Organic Framework for Chromatographic Separation in GC

Metal–organic frameworks (MOFs) have received great attention as stationary phases in chromatographic separation technology because of their unusual properties such as high surface areas, fascinating structures, and excellent chemical and thermal stability. A chiral MOF, [(CH₃)₂NH₂][Cd(bpdc)_1.5]·2DMA, possesses a unique chiral nanotube motif built from the covalent linkage of homochiral nanotubes made up of octuple helices. Here, we report the fabrication of a three-dimensional (3D) chiral nanoporous MOF-coated capillary column (2 m long × 75 μm i.d.) for capillary gas chromatographic separation of racemates, Grob’s test mixture, normal alkanes, normal alcohols, and isomers. The MOF-coated capillary column offered good separation efficiency (2,180 plates m^?1), which was measured using n-dodecane as the analyte at 120 °C. The relative standard deviations of repeatability for citronellal on MOF-coated capillary column were 0.23 and 2.1 % for retention time and peak area, respectively. The results demonstrated that the capillary column exhibited excellent selectivity and separation ability toward Grob’s test mixture, normal alkanes, normal alcohols and isomers, especially for racemates.