Metal-organic Frameworks Structures Research Articles

Scalable Approach for Grafting Qubit Candidates onto The Surface of MOF-808 Framework

The development of quantum bits (qubits) is crucial for the progress of quantum technologies. Among various approaches, the qubits based on paramagnetic centers have decent advantages, including their diversity and possibilities of regular ordering, for example, within the structure of metal-organic frameworks (MOFs). In the present work a simple and scalable approach to obtain qubit candidates based on stable organic radical 3-carboxy-proxyl and MOF-808 framework has been demonstrated. Investigation of the obtained compounds with different radical amounts using electron paramagnetic resonance (EPR) demonstrates the presence of two fractions of radicals, which is supported by simulations. Sufficiently long phase memory time at room temperature for the radicals adsorbed into MOF (0.39 μs), as well as the observed Rabi nutations, allow considering this material as a platform for qubits design. The developed approach is capable of incorporating various amounts of paramagnetic centers into the MOF structure and can be employed to obtain other spin qubit candidates.

Metal-Organic Frameworks of Cobalt(II) with 4,7-Di(1,2,4-triazol-1-yl)-2,1,3-benzothiadiazole and Aromatic Dicarboxylic Acids: Synthesis, Crystal Structures, and Magnetic Properties

The reactions of cobalt(II) nitrate with 4,7-di(1,2,4-triazol-1-yl)-2,1,3-benzothiadiazole (Tr2btd) and aromatic dicarboxylic acids (terephthalic (H2bdc), 2,6-naphthalenedicarboxylic (2,6-H2Ndc), and 2,5-furandicarboxylic (2,5-H2Fdc) acids) afford metal-organic frameworks [Co(Tr2btd)(bdc)]n (I) and {[Co2(Tr2btd)(Dmf)(2,6-Ndc)2]·Dmf}n (II) with the layered structures and chain metal-organic framework [Co(Tr2btd)2(H2O)(2,5-Fdc)]n (III). Compounds I and III are paramagnetic in a temperature range of 1.77–300 K without exchange interactions between the Co2+ cations, and compound II exhibits the antiferromagnetic interaction between the Co2+ cations in the binuclear building blocks with the exchange interaction constant J ≈ −100 K. Single crystals of the phase of compound IIIa with the identical composition but different structure are found when taking samples for X-ray diffraction (XRD) analysis. The molecular structures of metal-organic frameworks I, II, III, and IIIa are determined by XRD (CIF files CCDC nos. 2343141 (I), 2343297 (II), 2343296 (III), and 2343140 (IIIa)).

Multifunctional Magnetic Chiral HKUST MOF Decorated by Triazine, Fe3O4, and Cu(l-Proline)2 Complex for Green and Mild Asymmetric Catalysis.

A multifunctional magnetic chiral metal-organic framework (MOF) was developed for asymmetric applications by utilizing strategies of chiralization and multifunctionalization. Cu(l-proline)2-Triazine/Fe3O4@SiO2-NH2 was employed as a chiral secondary agent to synthesize a chiral hybrid nanocomposite within a MOF. The use of a chiral secondary agent efficiently induces chirality in an achiral MOF structure that cannot be directly chiralized. The HKUST-1@Cu(l-proline)2-Triazine/Fe3O4@SiO2-NH2 nanocomposite was afforded by first anchoring chiral Cu(l-proline)2 on the Triazine/Fe3O4@SiO2-NH2 surface and then encapsulating the Cu(l-proline)2-Triazine/Fe3O4@SiO2-NH2 nanoparticles with HKUST-1 via in situ ultrasonication synthesis. In the synthesis of the HKUST-1@Cu(l-proline)2-Triazine/Fe3O4@SiO2-NH2 nanocomposite, Cu(l-proline)2 was used as a chiral complex due to its Lewis acidic/basic hydroxyl groups, carboxylate carbonyl functional groups acting as Lewis bases, an active Cu site functioning as a Lewis acid center, and azine groups of TCT acting as Lewis bases, all synergistically interacting with the Lewis acidity of the Cu centers in HKUST-1. To assess these synergic effects, HKUST-1@Cu(l-proline)2-Triazine/Fe3O4@SiO2-NH2 was used in the formation of an asymmetric C-C bond in nitroaldol condensation and asymmetric cycloaddition of CO2 to epoxides. The findings demonstrated that under mild and green conditions, in both the asymmetric nitroalcohol condensation and the asymmetric cycloaddition of CO2, HKUST-1@Cu(l-proline)2-Triazine/Fe3O4@SiO2-NH2 had better enantioselectivity than the Cu(l-proline)2-Triazine/Fe3O4@SiO2-NH2 nanoparticles and a higher selectivity toward β-nitroalcohol and cyclic carbonate over the pure HKUST-1. Despite its simple and easy synthesis, HKUST-1@Cu(l-proline)2-Triazine/Fe3O4@SiO2-NH2 exhibited exceptional performance in the asymmetric nitroaldol condensation and asymmetric cycloaddition of CO2 to epoxides. Additionally, the mechanism of the reactions was depicted with reference to the total energy of the reactants, intermediates, and products.

Selective Electrocatalytic Production of Formic Acid from Plastic Waste Using a Ni Metal Organic Framework Constructed from a Biomass‐Derived Ligand

A novel nickel‐based metal organic framework (MOF) [Ni(FDC)(CH3OH)1.5(H2O)0.5](H2O)0.35 (UOW‐6) utilizing biomass‐derived 2,5‐furan dicarboxylate (FDC) as a ligand is reported as an electrocatalyst for anodic ethylene glycol oxidation with cathodic hydrogen evolution. The MOF structure was analyzed using single crystal X‐ray‐diffraction, TGA and thermodiffractometry, to establish its structure and verify phase purity. The material was dropcast on carbon fiber paper as a catalyst, and by using a three‐electrode system, UOW‐6 requires only 1.47 V to attain a current density of 50 mAcm‐2. During oxidation of the ethylene glycol (EG), UOW‐6 shows unprecedented selectivity towards formic acid with a Faradaic efficiency of 94% and remarkable stability over 20 days. The combination of electrochemical measurements and in situ Raman confirmed in situ formed NiOOH at the surface of UOW‐6 as the catalytically active sites for EG oxidation. This work not only presents a pioneering application of FDC‐based MOFs for polyethylene terephthalate (PET) upcycling but also underscores the potential of electrocatalysis in advancing sustainable plastic valorization strategies.

Simultaneous structure and surface engineering of metal-organic framework derived LiNi0.5-xFe2xMn1.5-xO4 cathode material for improving high voltage performance of lithium-ion batteries

This study presents a novel material synthesis approach utilizing a terephthalic acid-based metal-organic framework as a precursor and employing an ethanol-assisted hydrothermal treatment to produce high-performance Fe-doped LiNi0.5Mn1.5O4 (LNMO) cathode material. This strategy yields a well-crystallized spinel structure with uniformly distributed transition metal ions. Additionally, the appropriate quantity of Fe dopant can achieve the desired Mn3+/Mn4+ ratio, level of structural disordering, and crystal phase purity for Fe-doped LNMO. The synthesis process also aids in forming an amorphous Li2CO3 surface layer, approximately 1 nm thick, which protects the active material from excessive reaction with electrolyte. The typical Fe-doped LNMO cathode (S-05) exhibits superior performance compared to a commercialized LNMO counterpart. It delivers an initial discharge capacity of 135 mAh g-1 at 1 C with exceptional cycling stability over 500 cycles (capacity retention of 90%) under high voltage (5.0 V vs. Li+/Li). Furthermore, its rate capability significantly improves, with a capacity retention of 85% (5 C/0.2 C). This enhanced performance aligns with evidence of activated Ni2+/Ni3+/Ni4+ redox reactions and suppressed cathode electrolyte interphase resistance, leading to promoted Li+ diffusion. Moreover, it is found the cathode helps alleviate electrolyte degradation at high voltages by inhibiting the formation of singlet oxygen in the electrolyte.

Closing the Loop in the Carbon Cycle: Enzymatic Reactions Housed in Metal-Organic Frameworks for CO2 Conversion to Methanol.

The preparation of value-added chemicals from carbon dioxide (CO2) can act as a way of reducing the greenhouse gas from the atmosphere. Industrially significant C1 chemicals like methanol (CH3OH), formic acid (HCOOH), and formaldehyde (HCHO) can be formed from CO2. One sustainable way of achieving this is by connecting the reactions catalyzed by the enzymes formate dehydrogenase (FDH), formaldehyde dehydrogenase (FALDH), and alcohol dehydrogenase (ADH) into a single cascade reaction where CO2 is hydrogenated to CH3OH. For this to be adaptable for industrial use, the enzymes should be immobilized in materials that are extraordinarily protective of the enzymes, inexpensive, stable, and of ultra-large surface area. Metal-organic frameworks (MOFs) meet these criteria and are expected to usher in the much-awaited dispensation of industrial biocatalysis. Unfortunately, little is known about the molecular behaviour of MOF-immobilized FDH, FALDH, and ADH. It is also yet not known which MOFs are most promising for industrial enzyme-immobilization since the field of reticular chemistry is growing exponentially with millions of hypothetical and synthesized MOF structures reported at present. This review initially discusses the properties of the key enzymes required for CO2 hydrogenation to methanol including available cofactor regeneration strategies. Later, the characterization techniques of enzyme-MOF composites and the successes or lack thereof of enzyme-MOF-mediated CO2 conversion to CH3OH and intermediate products are discussed. We also discuss reported multi-enzyme-MOF systems for CO2 conversion cognizant of the fact that at present, these systems are the only chance of housing cascade-type biochemical reactions where strict substrate channelling and operational conditions are required. Finally, we delve into future perspectives.

Preparation and Electrocatalytic Properties of One-Dimensional Nanorod-Shaped N, S Co-Doped Bimetallic Catalysts of FeCuS-N-C

Metal air batteries have gradually attracted public attention due to their advantages such as high power density, high energy density, high energy conversion efficiency, and clean and green products. Reasonable design of oxygen reduction reaction (ORR) catalysts with high cost-effectiveness, high activity, and high stability is of great significance. Metal organic frameworks (MOFs) have the advantages of large specific surface area, high porosity, and designability, which make them widely used in many fields, especially in catalysis. This paper starts with regulating and optimizing the composition and structure of MOFs. A series of N, S co-doped electrocatalysts FeCuS-N-C were prepared by two high-temperature pyrolysis processes using N-doped carbon hollow nanorods derived from ZIF-8 as the substrate. The one-dimensional nanorod material derived from this MOF exhibits excellent electrocatalytic ORR performance (Eonset = 0.998 V, E1/2 = 0.874 V). When used as the air cathode catalyst for zinc air batteries and assembled into liquid ZABs, the battery discharge curve was calculated and found to have a maximum power density of 142.7 mW cm−2, a specific capacity of 817.1 mAh gZn−1, and a cycling stability test of over 400 h. This study provides an innovative approach for designing and optimizing non-precious metal catalysts for zinc air batteries.

Influence of MIL-53 on the catalytic performance of metallocene in propylene polymerization

In this study, we investigate the application of metal-organic frameworks (MOFs) as a support for metallocene catalysts in the polymerization of propylene. MOFs such as MIL-53 and other conventional supports, SBA-15 and SiO2, were employed to immobilize the Me2Si(2-Me-4-PhInd)2ZrCl2 catalyst activated with methylaluminoxane (MAO). The effects of the physicochemical properties of these supports on catalytic performance and polymer properties were investigated. MIL-53, characterized by its channel structure, facilitated higher molecular weight polypropylene production and exhibited double the catalytic activity of SBA-15 and SiO2 supports. The MIL-53/MAO/Me2Si(2-Me-4-PhInd)2ZrCl2 catalyst also demonstrated higher comonomer incorporation and lower polymer melting points. The higher activity, elevated molecular weight, and increased reactivity towards 1-hexene of the MIL-53/MAO/Me2Si(2-Me-4-PhInd)2ZrCl2 catalyst are attributed to the electronic and steric effects of MIL-53. This study underscores the significant role of MOF structure in influencing polymerization behavior and highlights the potential of MOF-supported catalysts for tailored polymer properties.

Nanoelectronic Detection of Acetone with MIL-53(Al)-NH2 Metal-Organic Framework on Single-Walled Carbon Nanotubes.

A new composite material has been synthesized by incorporating an amine-functionalized MIL-53 (Al) metal-organic framework (MOF) and single-walled carbon nanotubes (SWCNT) under hydrothermal conditions. This hybrid material combines the porosity of the MOF with the electrical conductivity of SWCNT. The preservation of MIL-53(Al)-NH2 MOF structure and morphology in the composite with SWCNT was verified by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, and Brunauer-Emmett-Teller surface area analysis. A characteristic current-voltage (I-V) curve showed the electrical conductivity of this composite and gave a linear response in the chemiresistive sensor with increasing concentrations of acetone. The MIL-53(Al)-NH2/SWCNT composite also displayed fluorescence quenching tendencies across various acetone concentrations, likely attributable to the impact of guest molecules influencing the framework. An alternative approach utilizing layer-by-layer sensor device fabrication was employed for growing this MOF on carbon nanotubes directly onto a silicon chip, demonstrating its potential for versatile on-chip-sensing applications.

Effect of Protein Loading Density on the Structure and Biopreservation Efficacy of Metal-Organic Frameworks

Effect of Protein Loading Density on the Structure and Biopreservation Efficacy of Metal-Organic Frameworks

Efficient Implementation of Monte Carlo Algorithms on Graphical Processing Units for Simulation of Adsorption in Porous Materials.

We present enhancements in Monte Carlo simulation speed and functionality within an open-source code, gRASPA, which uses graphical processing units (GPUs) to achieve significant performance improvements compared to serial, CPU implementations of Monte Carlo. The code supports a wide range of Monte Carlo simulations, including canonical ensemble (NVT), grand canonical, NVT Gibbs, Widom test particle insertions, and continuous-fractional component Monte Carlo. Implementation of grand canonical transition matrix Monte Carlo (GC-TMMC) and a novel feature to allow different moves for the different components of metal-organic framework (MOF) structures exemplify the capabilities of gRASPA for precise free energy calculations and enhanced adsorption studies, respectively. The introduction of a High-Throughput Computing (HTC) mode permits many Monte Carlo simulations on a single GPU device for accelerated materials discovery. The code can incorporate machine learning (ML) potentials, and this is illustrated with grand canonical Monte Carlo simulations of CO2 adsorption in Mg-MOF-74 that show much better agreement with experiment than simulations using a traditional force field. The open-source nature of gRASPA promotes reproducibility and openness in science, and users may add features to the code and optimize it for their own purposes. The code is written in CUDA/C++ and SYCL/C++ to support different GPU vendors. The gRASPA code is publicly available at https://github.com/snurr-group/gRASPA.

Electropolymerization of an Ultra-thin Film on bimetallic nanocomposite: Enhanced performance, perfect stability for supercapacitors

This research focused on synthesizing nanocomposites from vanadium-1.3.5-benzene tricarboxylic acid (V-BTC), vanadium-molibden-1.3.5-benzene tricarboxylic acid (V-BTC-Mo), and vanadium-molibden-1.3.5-benzene tricarboxylic acid/poly-orto-aminophenol (V-BTC-Mo/POAP) using chemical and electrochemical methods. The materials were analyzed using various analytical techniques such as XRD, FT-IR, FE-SEM, Elemental Mapping, and Edx. The SEM images revealed a nanorod structure of metal-organic framework (MOF) with a high specific surface area (SSA) of 131.13 m2.g−1 determined by nitrogen adsorption-desorption analysis. Electrochemical techniques including galvanostatic charge-discharge (GCD), electrochemical impedance spectroscopy (EIS), and cyclic voltammetry (CV) were employed to assess the supercapacitor (SC) properties. The results indicated that the V-BTC-MO/POAP composite exhibited a high specific capacitance (Cs) of 420.2 F g−1, with a high energy density of 38.1 Wh kg−1 at a power density of 236.2 W kg−1. Also, the V-BTC-Mo/POAP electrode demonstrated a good performance in structural stability by maintaining 97.3 % of the initial capacitance after 5000 continuous charge-discharge. Overall, the research aimed to develop a new methodology for synthesizing bimetallic nanocomposites and enhancing the performance of SCs in a three and two-electrode system, particularly focusing on vanadium and MOF-based electrodes.

SYNTHESIS AND CHARACTERIZATION OF ADVANCED METAL-ORGANIC FRAMEWORKS (MOFS)

Objective: This study aims to summarize, compare, and discuss the structure, synthesis techniques, and novel applications of Metal-Organic Frameworks (MOFs) as sensing materials. Specifically, it focuses on their use in sensors for detecting pharmaceuticals, pesticides, heavy metals, food additives, and other contaminants. Additionally, the study explores the antibacterial applications of MOFs due to their unique physical properties. Methods: The solvothermal process for synthesizing MOF-199 was investigated by varying the ethanol-to-water solvent ratio (1:1 to 1:2), solvothermal temperatures (85°C to 100°C), and synthesis times (24 to 48 hours). Characterization of the synthesized materials was conducted using X-ray diffraction (XRD), scanning electron microscopy (SEM), and Brunauer-Emmett-Teller (BET) surface area analysis to assess the structure, surface area, and pore characteristics. Results: The results indicate that MOF-199 synthesized under the optimal conditions (100°C for 48 hours with a 1:1 ethanol-to-water ratio) exhibited a specific volume of 0.693 cm³/g, a pore volume of 11.8 Å, a BET surface area of 5518 m²/g, and crystallinity of 103%. These properties are crucial for enhancing the performance of MOFs in electrochemical sensing applications. Novelty: This paper provides a detailed overview of the antibacterial applications of MOFs and their nanocomposite forms, offering new insights into their potential for sensing a wide range of chemicals and their enhanced selectivity for electrochemical analysis. The study introduces the solvothermal synthesis of MOF-199 and presents optimized parameters for its production, contributing to the development of more sensitive, cost-effective, and versatile electrochemical sensors for detecting contaminants.

Mn-MOF based electrochemical sensor for highly detection of poisonous rat bait (Bromadiolone)

Bromadiolone is a potent rodenticide used to control rat and mouse populations. Because of its anticoagulant properties, it prevents blood clots by interfering with the vitamin K cycle. While effective in pest control, its impact extends beyond the targeted species. Bromadiolone poses significant risks to non-target wildlife, particularly predators and scavengers that may consume poisoned rodents, leading to secondary poisoning. Metal-organic frameworks (MOFs) are a significant class of porous materials that have garnered substantial attention in recent years due to their unique properties and potential applications. Using the sonochemical approach, a novel metal–organic framework (MOF) combining manganese and ligand generated from 2-carboxy-benzaldehyde and 4-aminobenzoic acid has been synthesized. The resulting crystalline material were examined using a range of analytical methods, including thermal analysis, scanning electron microscope (SEM), energy dispersive Xray (EDX), powder X-ray diffraction (PXRD), Fourier-Transform infrared spectroscopy (FT-IR) and (BET) surface area. The findings of the BET study showed that the surface area was 1106.65 m2 g−1. The computed total pore volume was 1.81 cm3 g−1, with an average pore size of 3.27 nm. The newly synthesized Mn-MOF is used in the electrochemical detection of a potent anticoagulant rodenticide bromadiolone, which represented a significant advancement in chemistry. The existence of Mn in the MOF structure enhanced its electrochemical properties, allowing for the sensitive detection of bromadiolone in oats and maize samples.

Fine-Tuning Porous Structure of Zirconium-Based Metal-Organic Frameworks for Efficient Separation and Purification of Astaxanthin by Defect Engineering.

Efficient separation of bioactive compounds from nature source, particularly that of astaxanthin (AXT), remains challenging due to their low content in complicated matrix and readily degradable structure. Herein, a modulator-induced defect engineering is presented on the stable zirconium-based metal-organic frameworks (Zr-MOFs) to optimize pore size and pore chemistry for the efficient separation and purification of AXT for the first time. High adsorption capacity of 26.21mgg-1 is achieved on the best-performing defect Zr-MOF (d-UiO-67-4), superior over the other reported adsorbent for AXT. Meanwhile, d-UiO-67-4 exhibits the selective adsorption of AXT over other carotenoids analogues with similar structure and properties. This is attributed to the preferential non-covalent interactions between defect framework and AXT revealed by the spectroscopy analysis and density functional theory (DFT) calculations. High purity of AXT with 89.0%±2.3% extraction efficiency can be realized after the purification of AXT by d-UiO-67-4. The practical separation performance of d-UiO-67-4 for AXT extracted from Haematococcus pluvialis is demonstrated by fixed-bed column-based dynamic adsorption and desorption experiments. This work broadens the preparation methods for thermosensitive active substances and provided new research ideas for the controlled adsorption of functional food factors.

A Sodium Metal-Organic Framework with Deep Blue Room-Temperature Phosphorescence.

It is a great challenge to manufacture room-temperature blue long afterglow phosphorescent materials adapted to environmental conditions. Herein, an Na-based metal-organic framework (MOF) was constructed using Na+ and 1H-1,2,4-triazole-3,5-dicarboxylic acid, which exhibits long-lived of 378.9 ms, deep blue and room-temperature phosphorescence, meanwhile possesses the visible blue afterglow for 3~6 seconds after removing excitation light source. The three-dimensional coordination bonds network provided by Na-based MOF protects the organic ligands intrinsic hydrogen bond network, resulting in the phosphor lifetime and residual color remaining unchanged in different gas atmospheres. Furthermore, first-principles time-dependent density functional theory reveals that the rigid Na-based MOF structure can limit the rotation and vibration of the room-temperature phosphorescent organic ligands. This limitation results in the suppression of non-radiative decay for both singlet and triplet excitons, promotes intersystem crossing, and increases the rate of radiative decay, ultimately achieving long-lived room-temperature phosphorescence.

Co-Carbonization of Straw and ZIF-67 to the Co/Biomass Carbon for Electrocatalytic Nitrate Reduction

Electrocatalytic nitrate reduction enables the recovery of nitrate from water under mild conditions and generates ammonia for nitrogen fertilizer feedstock in an economical and green means. In this paper, Co/biomass carbon (Co/BC) composite catalysts were prepared by co-carbonization of straw and metal–organic framework material ZIF-67 for electrocatalytic nitrate reduction using hydrothermal and annealing methods. The metal–organic framework structure disperses the catalyst components well and provides a wider specific surface area, which is conducive to the adsorption of nitrate and the provision of more reactive active sites. The introduction of biomass carbon additionally enhances the electrical conductivity of the catalyst and facilitates electron transport. After electrochemical testing, Co/BC-100 exhibited the best performance in electrocatalytic nitrate reduction to ammonia, with an ammonia yield of 3588.92 mmol gcat.−1 h−1 and faradaic efficiency of 97.01% at −0.5 V vs. RHE potential. This study provides a promising approach for the construction of other efficient cobalt-based electrocatalysts.

Enhancement of Synaptic Behavior in Organic Electrochemical Transistors via the Introduction of Layer‐by‐Layer Grown Metal‐Organic Framework

AbstractOrganic electrochemical transistors (OECTs) are promising for neuromorphic architectures as they can generate multiple electrical states through the control of ion transport. However, conventional OECTs face limitations in mimicking a fully functional biological synapse due to their inability to achieve long‐term plasticity. In this study, a metal‐organic framework (MOF)‐enhanced OECT (MOECT) is fabricated by introducing MOF into the ion‐organic semiconductor (OSC) layer. MOFs are synthesized using the layer‐by‐layer (LBL) method, and additional cross‐linked OSC is introduced to prevent damage to the semiconductor layers during synthesis. The synthesized MOF layers hinder the rediffusion of ions in OECT, allowing ions to remain in the OSC for an extended period. In this study, the MOECT showed a change in current depending on the doping level, recording a current state 4.4 × 107 times higher than that of pristine OECT. Ultimately, the developed MOECTs are applied as synaptic transistors. MOECTs show 14% higher excitatory postsynaptic current (EPSC) after 130 s compared to pristine OECT, thereby strengthening the long‐term plasticity characteristics of neuromorphic devices. This method enhances the performance of synaptic transistors by introducing MOF, offering various possibilities through the selection of different MOF structures and ions, indicating it is a methodological approach with high potential.

Leveraging Ligand Desymmetrization to Enrich Structural Diversity of Zirconium Metal-Organic Frameworks for Toxic Chemical Adsorption.

The discovery of metal-organic frameworks (MOFs) with novel structures provides significant opportunities for developing porous solids with new properties and enriching the structural diversity of functional materials for various applications. The rational design of building units with specific geometric conformations is essential to direct the construction of MOFs with unique properties. Herein, we leverage a ligand desymmetrization approach to construct a series of new MOFs. A flexible tetratopic carboxylate ligand with a tetrahedral geometry was designed and assembled with a Zr6 cluster, generating four Zr-based MOF structures: NU-2600, NU-2700, NU-2800, and NU-1802, in which the ligand configurations and Zr6 cluster connectivities can be controlled by varying solvents and modulators during synthesis. Except for NU-1802, these represent entirely new topologies. Notably, NU-1802 exhibits structural flexibility, with up to a 74% reduction in the unit cell volume as confirmed by single-crystal X-ray diffraction studies. Given their microporous structures, we studied the adsorption behaviors of n-hexane and 2-chloroethyl ethyl sulfide to explore the structure-property relationships of these MOFs. Overall, this work highlights ligand desymmetrization as a powerful method to enrich MOF structural diversity and access complex MOFs with non-default topologies suitable for applications such as toxic gas capture.

Leveraging Ligand Desymmetrization to Enrich Structural Diversity of Zirconium Metal–Organic Frameworks for Toxic Chemical Adsorption

The discovery of metal–organic frameworks (MOFs) with novel structures provides significant opportunities for developing porous solids with new properties and enriching the structural diversity of functional materials for various applications. The rational design of building units with specific geometric conformations is essential to direct the construction of MOFs with unique properties. Herein, we leverage a ligand desymmetrization approach to construct a series of new MOFs. A flexible tetratopic carboxylate ligand with a tetrahedral geometry was designed and assembled with a Zr6 cluster, generating four Zr‐based MOF structures: NU‐2600, NU‐2700, NU‐2800, and NU‐1802, in which the ligand configurations and Zr6 cluster connectivities can be controlled by varying solvents and modulators during synthesis. Except for NU‐1802, these represent entirely new topologies. Notably, NU‐1802 exhibits structural flexibility, with up to a 74% reduction in the unit cell volume as confirmed by single‐crystal X‐ray diffraction studies. Given their microporous structures, we studied the adsorption behaviors of n‐hexane and 2‐chloroethyl ethyl sulfide to explore the structure‐property relationships of these MOFs. Overall, this work highlights ligand desymmetrization as a powerful method to enrich MOF structural diversity and access complex MOFs with non‐default topologies suitable for applications such as toxic gas capture.