The next chapter in MOF pillaring strategies: trigonal heterofunctional ligands to access targeted high-connected three dimensional nets, isoreticular platforms

A new pillaring strategy, based on a ligand-to-axial approach that combines the two previous common techniques, axial-to-axial and ligand-to-ligand, and permits design, access, and construction of higher dimensional MOFs, is introduced and validated. Trigonal heterofunctional ligands, in this case isophthalic acid cores functionalized at the 5-position with N-donor (e.g., pyridyl- or triazolyl-type) moieties, are designed and utilized to pillar pretargeted two-dimensional layers (supermolecular building layers, SBLs). These SBLs, based on edge transitive Kagomé and square lattices, are cross-linked into predicted three-dimensional MOFs with tunable large cavities, resulting in isoreticular platforms.     

Two-Dimensional MOF and COF Nanosheets: Synthesis and Applications in Electrochemistry

Metal–organic framework (MOF) and covalent organic framework (COF) nanosheets are a new type of two-dimensional (2D) materials with unique design principles and various synthesis methods. They are considered ideal electrochemical devices due to the ultrathin thickness, easily tunable molecular structure, large porosity and other unique properties. There are two common methods to synthesize 2D MOF/COF nanosheets: bottom-up and top-down. The top-down strategy mainly includes ultrasonic assisted exfoliation, electrochemical exfoliation and mechanical exfoliation. Another strategy mainly includes interface synthesis, modulation synthesis, surfactant-assisted synthesis. In this Review, the development of ultrathin 2D nanosheets in the field of electrochemistry (supercapacitors, batteries, oxygen reduction, and hydrogen evolution) is introduced, and their unique dimensional advantages are highlighted.     

Tuning CO2 Uptake and Reversible Iodine Adsorption in Two Isoreticular MOFs through Ligand Functionalization

The synthesis and characterization of two isoreticular metal–organic frameworks (MOFs), {[Cd(bdc)(4‐bpmh)]}_n?2 n(H₂O) ( 1 ) and {[Cd(2‐NH₂bdc)(4‐bpmh)]}_n?2 n(H₂O) ( 2 ) [bdc=benzene dicarboxylic acid; 2‐NH₂bdc=2‐amino benzene dicarboxylic acid; 4‐bpmh=N,N‐bis‐pyridin‐4‐ylmethylene‐hydrazine], are reported. Both compounds possess similar two‐fold interpenetrated 3D frameworks bridged by dicarboxylates and a 4‐bpmh linker. The 2D Cd‐dicarboxylate layers are extended along the a‐axis to form distorted square grids which are further pillared by 4‐bpmh linkers to result in a 3D pillared‐bilayer interpenetrated framework. Gas adsorption studies demonstrate that the amino‐functionalized MOF 2 shows high selectivity for CO₂ (8.4 wt % 273 K and 7.0 wt % 298 K) over CH₄, and the uptake amounts are almost double that of non‐functional MOF 1 . Iodine (I₂) adsorption studies reveal that amino‐functionalized MOF 2 exhibits a faster I₂ adsorption rate and controlled delivery of I₂ over the non‐functionalized homolog 1 .     

Ligand Symmetry Modulation for Designing a Mesoporous Metal–Organic Framework: Dual Reactivity to Transition and Lanthanide Metals for Enhanced Functionalization

A promising alternative strategy for designing mesoporous metal–organic frameworks (MOFs) has been proposed, by modifying the symmetry rather than expanding the length of organic linkers. By means of this approach, a unique MOF material based on the target [Zn₈(ad)₄] (ad=adeninate) clusters and C₃‐symmetric organic linkers can be obtained, with trigonal microporous (ca., 0.8 nm) and hexagonal mesoporous (ca., 3.0 nm) 1D channels. Moreover, the resulting 446‐MOF shows distinct reactivity to transition and lanthanide metal ions. Significantly, the transmetalation of Co^II or Ni^II on the Zn^II centers in 446‐MOF can enhance the sorption capacities of CO₂ and CH₄ (16–21 %), whereas the impregnation of Eu^III and Tb^III in the channels of 446‐MOF will result in adjustable light‐emitting behaviors.     

Hollow Metal–Organic‐Framework‐Mediated In Situ Architecture of Copper Dendrites for Enhanced CO2 Electroreduction

Electrocatalytic reduction of CO₂ to a single product at high current densities and efficiencies remains a challenge. However, the conventional electrode preparation methods, such as drop‐casting, usually suffer from low intrinsic activity. Herein, we report a synthesis strategy for preparing heterogeneous electrocatalyst composed of 3D hierarchical Cu dendrites that derived from an in situ electrosynthesized hollow copper metal–organic framework (MOF), for which the preparation of the Cu‐MOF film took only 5 min. The synthesis strategy preferentially exposes active sites, which favor's the reduction of CO₂ to formate. The current density could be as high as 102.1 mA cm^?2 with a selectivity of 98.2 % in ionic‐liquid‐based electrolyte and a commonly used H‐type cell.     

Enhanced Sieving of C2-Hydrocarbon from Methane by Fluoro-Functionalization of In-MOF with Robust Stability

Developing efficient adsorbent materials is crucial for adsorption and separation to realize the purification of energy source and raw chemicals. Here, we report a novel and robust 3D In-based MOF built up with fluorine-functionalized ligands, QMOF-2F , with improved separation properties of C2-light hydrocarbons over methane at room temperature respect isoreticular non-fluorinated MOF. QMOF-2F shows a remarkable chemical stability in different solvents, including water, and pH (2–12). DFT calculations support the key role of fluorine-functionalization on the improved performance of QMOF-2F .     

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.     

Dehydrative Annulation Strategy for the Construction of Octahydroindolizine Framework: A Diastereoselective Synthesis of (6R,8aS)-Octahydroindolizin-6-ol

A dehydrative annulation strategy involving an intramolecular ring closure under a Mitsunobu-type reaction condition has been used for the construction of octahydroindolizine framework successfully. This strategy that was reported to be unsuccessful when applied to a similar system allowed us to perform a diastereoselective synthesis of (6R,8aS)-octahydroindolizin-6-ol [a precursor of (–)-8a-epidesacetoxyslaframine] starting from commercially available chiral (S)-epichlorohydrin via a piperidine intermediate, i.e., (3R,6S)-6-(3-hydroxypropyl)piperidin-3-ol. The methodology has potential to afford a library of optically pure small molecules of pharmacological importance based on the related indolizine framework.     

Ultra‐Tuning of the Rare‐Earth fcu‐MOF Aperture Size for Selective Molecular Exclusion of Branched Paraffins

Using isoreticular chemistry allows the design and construction of a new rare‐earth metal (RE) fcu ‐MOF with a suitable aperture size for practical steric adsorptive separations. The judicious choice of a relatively short organic building block, namely fumarate, to bridge the 12‐connected RE hexanuclear clusters has afforded the contraction of the well‐defined RE‐ fcu ‐MOF triangular window aperture, the sole access to the two interconnected octahedral and tetrahedral cages. The newly constructed RE (Y³⁺ and Tb³⁺) fcu ‐MOF analogues display unprecedented total exclusion of branched paraffins from normal paraffins. The resultant window aperture size of about 4.7 Å, regarded as a sorbate‐size cut‐off, enabled a complete sieving of branched paraffins from normal paraffins. The results are supported by collective single gas and mixed gas/vapor adsorption and calorimetric studies.     

Nanoporous Materials Can Tune the Critical Point of a Pure Substance

Molecular simulations and NMR relaxometry experiments demonstrate that pure benzene or xylene confined in isoreticular metal–organic frameworks (IRMOFs) exhibit true vapor–liquid phase equilibria where the effective critical point may be reduced by tuning the structure of the MOF. Our results are consistent with vapor and liquid phases extending over many MOF unit cells. These results are counterintuitive since the MOF pore diameters are approximately the same length scale as the adsorbate molecules. As applications of these materials in catalysis, separations, and gas storage rely on the ability to tune the properties of adsorbed molecules, we anticipate that the ability to systematically control the critical point, thereby preparing spatially inhomogeneous local adsorbate densities, could add a new design tool for MOF applications.     

Multivariate Hydrogen-Bonded Organic Frameworks with Tunable Permanent Porosities for Capture of a Mustard Gas Simulant

Precise synthesis of topologically predictable and discrete molecular crystals with permanent porosities remains a long-term challenge. Here, we report the first successful synthesis of a series of 11 isoreticular multivariate hydrogen-bonded organic frameworks (MTV-HOFs) from pyrene-based derivatives bearing −H, −CH₃, −NH₂ and −F groups achieved by a shape-fitted, π–π stacking self-assembly strategy. These MTV-HOFs are single-crystalline materials composed of tecton, as verified by single-crystal diffraction, nuclear magnetic resonance (NMR) spectra, Raman spectra, water sorption isotherms and density functional theory (DFT) calculations. These MTV-HOFs exhibit tunable hydrophobicity with water uptake starting from 50 to 80 % relative humidity, by adjusting the combinations and ratios of functional groups. As a proof of application, the resulting MTV-HOFs were shown to be capable of capturing a mustard gas simulant, 2-chloroethyl ethyl sulfide (CEES) from moisture. The location of different functional groups within the pores of the MTV-HOFs leads to a synergistic effect, which resulted in a superior CEES/H₂O selectivity (up to 94 %) compared to that of the HOFs with only pure component and enhanced breakthrough performance (up to 4000 min/g) when compared to benchmark MOF materials. This work is an important advance in the synthesis of MTV-HOFs, and provides a platform for the development of porous molecular materials for numerous applications.     

Metal–Organic Frameworks Based Electrocatalysts for the Oxygen Reduction Reaction

In view of the clean and sustainable energy, metal–organic frameworks (MOFs) based materials, including pristine MOFs, MOF composites, and their derivatives are emerging as unique electrocatalysts for oxygen reduction reaction (ORR). Thanks to their tunable compositions and diverse structures, efficient MOF‐based materials provide new opportunities to accelerate the sluggish ORR at the cathode in fuel cells and metal–air batteries. This Minireview first provides some introduction of ORR and MOFs, followed by the classification of MOF‐based electrocatalysts towards ORR. Recent breakthroughs in engineering MOF‐based ORR electrocatalysts are highlighted with an emphasis on synthesis strategy, component, morphology, structure, electrocatalytic performance, and reaction mechanism. Finally, some current challenges and future perspectives for MOF‐based ORR electrocatalysts are also discussed.     

Comparison of the behavior of metal-organic frameworks and zeolites for hydrocarbon separations

The objective of this work was to study the adsorption and separation of the most important families of hydrocarbon compounds on metal-organic frameworks (MOFs), in comparison with zeolites. For this purpose, we have selected four probe molecules, each of them representing one of these families, i.e., o- and p-xylene as aromatics, 1-octene as an alkene, and n-octane as an alkane. The separation of these four molecules was studied by binary breakthrough experiments. To represent the large diversity of MOF structures, the experiments were carried out with (i) two MOFs with coordinatively unsaturated metal sites (CUS), i.e., Cu-btc (HKUST-1) and CPO-27-Ni, (ii) a MOF with an anionic framework and extraframework cations, i.e. RHO-ZMOF, and (iii) two rather apolar zeolitic imidazolate framework (ZIF) materials with different pore sizes, i.e. ZIF-8 and ZIF-76. Zeolite NaY and zeolite β were used as polar and apolar reference adsorbents, respectively. The results can be briefly summarized as follows: ZIFs (not carrying any polar functional groups) behave like apolar adsorbents and exhibit very interesting and unexpected molecular sieving properties. CUS-MOFs behave like polar adsorbents but show the specificity of preferring alkenes over aromatics. This feature is rationalized thanks to DFT+D calculations. MOFs with extraframework cations behave like polar (cationic) zeolites.     

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.     

High-throughput assisted rationalization of the formation of metal organic frameworks in the Iron(III) aminoterephthalate solvothermal system

Through the use of high-throughput methods, solvothermal reactions of FeCl 3 and 2-aminoterephthalic acid in protic as well as aprotic reaction media were systematically studied. Thus, the fields of formation of the isoreticular structures of MIL-53, MIL-88, and MIL-101 based on Fe(III) and aminoterephthalate could be identified for the first time. The resulting 3D framework materials with amino-functionalized pores have been characterized using X-ray diffraction; IR spectroscopy; and thermogravimetric, elemental, and energy dispersive X-ray analysis. Due to the applied high-throughput method, a high density of information was obtained in a short period of time, which allows the extraction of important reaction trends and contributes to a better understanding of the role of compositional as well as process parameters in the synthesis of inorganic-organic hybrid materials. We have found that the nature of the reaction medium has the most profound impact on structure formation. Furthermore, the concentration of the starting mixture (i.e., the solvent content) and the temperature have also been identified as key parameters for the formation of the different hybrid phases.     

Function-Oriented: The Construction of Lanthanide MOF Luminescent Sensors Containing Dual-Function Urea Hydrogen-Bond Sites for Efficient Detection of Picric Acid

Two novel lanthanide metal–organic framework (Ln-MOF) luminescent sensors for the detection of picric acid have been successfully assembled. Following a function-oriented strategy, urea hydrogen-bonding functional sites were introduced into two MOF frameworks. A structural analysis indicated that the two MOFs have the exact same structure, namely 2D layers with diamond-shaped holes that are accumulated into a 3D framework through the hydrogen-bonding interactions between urea and carboxylate groups. Interestingly, only half of the urea units are involved in supporting the MOF framework through N−H⋅⋅⋅O hydrogen-bonding interactions, whereas the other half are located in the pore channel and act as empty recognition sites. Abundant N−H urea bonds are present in the inner walls of three types of interpenetrating 1D channels. Luminescence studies revealed that the two Ln-MOFs exhibit high sensitivity, good selectivity, and a fast luminescence quenching response towards picric acid. In particular, the two Ln-MOFs can be simply and quickly regenerated, and exhibit excellent recyclability. In summary, we have successfully used a function-oriented strategy to achieve multiple functions in a ligand to construct lanthanide MOF luminescent sensors for the detection of picric acid, thereby providing a potential strategy for the future development of MOF luminescent sensors with a specific target.     

Tandem postsynthetic modification of metal-organic frameworks using an inverse-electron-demand Diels-Alder reaction

A postsynthetic modification (PSM) scheme for metal-organic frameworks (MOFs) has been developed using a tetrazine-based "Click" reaction. It was found that the efficacy of this modification procedure was dependent on the MOF topology and, in the case of an isoreticular MOF (IRMOF) system, required the formation of a mixed-ligand IRMOF with a suitable ratio of 1,4-benzenedicarboxylate (BDC) and an olefin-tagged BDC derivative. On the basis of the versatile use of tetrazine "Click" chemistry in bioconjugate chemistry, we expect that this scheme will prove to be a useful reaction for preparing functionalized materials, including MOFs.     

Crystal Dynamics in Multi‐stimuli‐Responsive Entangled Metal–Organic Frameworks

An understanding of solid‐state crystal dynamics or flexibility in metal–organic frameworks (MOFs) showing multiple structural changes is highly demanding for the design of materials with potential applications in sensing and recognition. However, entangled MOFs showing such flexible behavior pose a great challenge in terms of extracting information on their dynamics because of their poor single‐crystallinity. In this article, detailed experimental studies on a twofold entangled MOF ( f‐MOF‐1) are reported, which unveil its structural response toward external stimuli such as temperature, pressure, and guest molecules. The crystallographic study shows multiple structural changes in f‐MOF‐1 , by which the 3 D net deforms and slides upon guest removal. Two distinct desolvated phases, that is, f‐MOF‐1 a and f‐MOF‐1 b , could be isolated; the former is a metastable one and transformable to the latter phase upon heating. The two phases show different gated CO₂ adsorption profiles. DFT‐based calculations provide an insight into the selective and gated adsorption behavior with CO₂ of f‐MOF‐1 b . The gate‐opening threshold pressure of CO₂ adsorption can be tuned strategically by changing the chemical functionality of the linker from ethanylene (?CH₂?CH₂?) in f‐MOF‐1 to an azo (?N=N?) functionality in an analogous MOF, f‐MOF‐2 . The modulation of functionality has an indirect influence on the gate‐opening pressure owing to the difference in inter‐net interaction. The framework of f‐MOF‐1 is highly responsive toward CO₂ gas molecules, and these results are supported by DFT calculations.     

Nd3+‐Sensitized Upconversion Metal–Organic Frameworks for Mitochondria‐Targeted Amplified Photodynamic Therapy

Herein, we report the design and synthesis of a mitochondria‐specific, 808 nm NIR light‐activated photodynamic therapy (PDT) system based on the combination of metal–organic frameworks (MOFs) and upconversion photochemistry with an organelle‐targeting strategy. The system was synthesized through the growth of a porphyrinic MOF on Nd³⁺‐sensitized upconversion nanoparticles to achieve Janus nanostructures with further asymmetric functionalization of the surface of the MOF domain. The PDT nanoplatform allows for photosensitizing with 808 nm NIR light, which could effectively avoid the laser‐irradiation‐induced overheating effect. Furthermore, mitochondria‐targeting could amplify PDT efficacy through the depolarization of the mitochondrial membrane and the initiation of intrinsic apoptotic pathway. This work sheds light on the hybrid engineering of MOFs to combat their current limitations for PDT.     

Tuning the Adsorption Properties of Isoreticular Pyrazolate-Based Metal-Organic Frameworks through Ligand Modification

Two isoreticular series of pyrazolate-based 3D open metal-organic frameworks, MBDP_X, adopting the NiBDP and ZnBDP structure types [H(2)BDP = 1,4-bis(1H-pyrazol-4-yl)benzene], were synthesized with the new tagged organic linkers H(2)BDP_X (X = -NO(2), -NH(2), -OH). All of the MBDP_X materials have been characterized through a combination of techniques. IR spectroscopy proved the effective presence of tags, while X-ray powder diffraction (XRPD) witnessed their isoreticular nature. Simultaneous TG/DSC analyses (STA) demonstrated their remarkable thermal stability, while variable-temperature XRPD experiments highlighted their high degree of flexibility related to guest-induced fit processes of the solvent molecules included in the channels. A structural isomer of the parent NiBDP was obtained with a sulfonate tagged ligand, H(2)BDP_SO(3)H. Structure solution from powder diffraction data collected at three different temperatures (room temperature, 90, and 250 °C) allowed the determination of its structure and the comprehension of its solvent-related flexible behavior. Finally, the potential application of the tagged MOFs in selective adsorption processes for gas separation and purification purposes was investigated by conventional single component adsorption isotherms, as well as by advanced experiments of pulse gas chromatography and breakthrough curve measurements. Noteworthy, the results show that functionalization does not improve the adsorption selectivity (partition coefficients) for the resolution of gas mixtures characterized by similar high quadrupole moments (e.g., CO(2)/C(2)H(2)); however, the resolution of gas mixtures containing molecules with highly differentiated polarities (i.e., N(2)/CO(2) or CH(4)/CO(2)) is highly improved.