Three-dimensional Metal-organic Framework Research Articles

Stable Europium(III) Metal-Organic Framework Fluorescence Probe for Intelligent Visualization Detection of Gossypol and Nitrofuran Antibiotics in Real Samples.

Gossypol (Gsp) and antibiotics present in water bodies become organic pollutants that are harmful to human health and the ecological environment. Accurate and effective detection of these pollutants has far-reaching significance in many fields. A new three-dimensional metal-organic framework (MOF), {[Eu3(L)2(HCOO-)(H2O)3]·2H2O·2DMF}n (Eu-MOF), was synthesized from 3,5-bis(2,4-dicarboxylphenyl)nitrobenzene (H4L) ligand and Eu3+ via the solvothermal method in this paper. The Eu-MOF demonstrates strong red fluorescence and can remain stable in different pH solutions. The MOF fluorescence probe could detect organic pollutants through the "shut-off" effect, with a fast response speed and a low detection limit [Gsp, nitrofurantoin (NFT), and nitrofurazone (NFZ) for 0.43, 0.38, and 0.41 μM, respectively]. During the testing process, Eu-MOF exhibited good selectivity and recoverability. Furthermore, the mechanism of fluorescence quenching was investigated, and the recoveries were also good in real samples. This paper introduced a deep learning model to recognize the fluorescence images, a portable intelligent logic detector designed for real-time detection of Gsp by logic gate strategy, and an anticounterfeiting mark prepared based on inkjet printing. Importantly, this work provides a new way of thinking for the detection of organic pollutants in water with high sensitivity and practicality by combining the fluorescence probe with machine learning and logical judgment.

Enhanced catalytic reduction of 4-nitrophenol using bimetallic MOFs: a one-pot synthesis approach

ABSTRACT Several organic pollutants can harm the environment and human health. A typical environmentally toxic contaminant, 4-Nitrophenol (4-NP), may cause serious health issues. Therefore, catalytic reduction (hydrogenation) of 4-nitrophenol into less toxic 4-aminophenol (4-AP) is mostly preferred. A three-dimensional (3D) metal-organic framework of Ni-MOF-74 is mostly used which contains maximum unsaturated metal sites and the catalytic activity is enhanced due to partial exchange at the node position in MOF. In order to study the catalytic hydrogenation/reduction of organic dye, 4-nitrophenol as a model reaction, a bimetallic MOF, FeNi-MOF-74 was prepared by partially substituting Ni with Fe metal. The catalyst was synthesised using a one-pot solvothermal technique, and 4-nitrophenol was then reduced catalytically in aqueous media. For the reduction of nitrophenol, the FeNi-MOF-74 catalyst surpassed Ni-MOF (9.3 × 10−3 s−1) and Fe-MOF (5.4 × 10−3 s−1) with a lower reduction time and a higher rate constant; (1.6 × 10−2 s−1). The high conversion rate and economical induction time are attributed to the bimetallic synergistic effect.

Breaking Boundaries: Innovations in Two- and Three-Dimensional Metal-Organic Framework (MOF)-Based Mixed-Matrix Membranes for Effective Post-Combustion CO 2 Capture

Breaking Boundaries: Innovations in Two- and Three-Dimensional Metal-Organic Framework (MOF)-Based Mixed-Matrix Membranes for Effective Post-Combustion CO ₂ Capture

Tailored Porous Ferrocene-Based Metal-Organic Frameworks as High-Performance Proton Conductors.

Although crystalline metal-organic frameworks (MOFs) have gained a great deal of interest in the field of proton conduction in recent years, the low stability and poor proton conductivity (σ) of some MOFs have hindered their future applications. As a result, resolving the issues listed above must be prioritized. Due to their exceptional structural stability, MOFs with ferrocene groups that exhibit particular physical and chemical properties have drawn a lot of attention. This study describes the effective preparation of a set of three-dimensional ferrocene-based MOFs, MIL-53-FcDC-Al/Ga and CAU-43, containing both main group metals and 1,1'-ferrocene dicarboxylic acid (H2FcDC). Multiple measurements, including powder X-ray diffraction (PXRD), infrared (IR), and scanning electron microscopy (SEM), confirmed that the addition of ferrocene groups enhanced the thermal, water, and acid-base stabilities of the three MOFs. Consequently, their proton-conductive behaviors were meticulously measured utilizing the AC impedance approach, and their best proton conductivities are 5.20 × 10-3, 2.31 × 10-3, and 1.72 × 10-4 S/cm at 100 °C/98% relative humidity (RH), respectively. Excitingly, MIL-53-FcDC-Al/Ga demonstrated an extraordinarily ultrahigh σ of above 10-4 S·cm-1 under 30 °C/98% RH. Using data from structural analysis, PXRD, SEM, thermogravimetry (TG), and activation energy, their proton transport mechanisms were thoroughly examined. The fact that these MOFs are notably easy to assemble, inexpensive, toxin-free, and stable will increase the range of practical uses for them.

A Porphyrin-Based 3D Metal-Organic Framework Featuring [Cu8Cl6]10+ Cluster Secondary Building Units: Synthesis, Structure Elucidation, Anion Exchange, and Peroxidase-Like Activity.

Herein, we report a rare example of cationic three-dimensional (3D) metal-organic framework (MOF) of [Cu5Cl3(TMPP)]Cl5 ⋅ xSol (denoted as Cu-TMPP; H2TMPP=meso-tetrakis (6-methylpyridin-3-yl) porphyrin; xSol=encapsulated solvates) supported by [Cu8Cl6]10+ cluster secondary building units (SBUs) wherein the eight faces of the Cl--based octahedron are capped by eight Cu2+. Surface-area analysis indicated that Cu-TMPP features a mesoporous structure and its solvate-like Cl- counterions can be exchanged by BF4 -, PF6 -, and NO3 -. The polyvinylpyrrolidone (PVP) coated Cu-TMPP (denoted as Cu-TMPP-PVP) demonstrated good ROS generating ability, producing ⋅OH in the absence of light (peroxidase-like activity) and 1O2 on light irradiation (650 nm; 25 mW cm-2). This work highlights the potential of Cu-TMPP as a functional carrier of anionic guests such as drugs, for the combination therapy of cancer and other diseases.

Modulated Self-Assembly of Catalytically Active Metal-Organic Nanosheets Containing Zr6 Clusters and Dicarboxylate Ligands.

Two-dimensional metal-organic nanosheets (MONs) have emerged as attractive alternatives to their three-dimensional metal-organic framework (MOF) counterparts for heterogeneous catalysis due to their greater external surface areas and higher accessibility of catalytically active sites. Zr MONs are particularly prized because of their chemical stability and high Lewis and Brønsted acidities of the Zr clusters. Herein, we show that careful control over modulated self-assembly and exfoliation conditions allows the isolation of the first example of a two-dimensional nanosheet wherein Zr6 clusters are linked by dicarboxylate ligands. The hxl topology MOF, termed GUF-14 (GUF = Glasgow University Framework), can be exfoliated into monolayer thickness hns topology MONs, and acid-induced removal of capping modulator units yields MONs with enhanced catalytic activity toward the formation of imines and the hydrolysis of an organophosphate nerve agent mimic. The discovery of GUF-14 serves as a valuable example of the undiscovered MOF/MON structural diversity extant in established metal-ligand systems that can be accessed by harnessing the power of modulated self-assembly protocols.

Layer-by-layer growth of Cu3(HHTP)2 films on Cu(OH)2 nanowire arrays for high performance ascorbic acid sensing

Growing three-dimensional (3D) metal organic frameworks (MOFs) via heterogeneous epitaxial growth on metal hydroxide arrays are effective for constructing electrochemical sensor. However, the growth of MOFs is difficult to control, resulting in thick and irregular morphologies and even damage the metal hydroxide template. In this work, Cu3(HHTP)2 (HHTP = 2, 3, 6, 7, 10, 11-hexahydroxytriphenylene) films with controllable thickness and morphology were successfully prepared on Cu(OH)2 nanowire arrays (NWAs) through layer-by-layer (LBL) growth method. We have discovered that the LBL cycle and the reaction solvent composition are crucial for growing homogenous MOF thin films. The Cu3(HHTP)2 based ascorbic acid (AA) sensor, fabricated in ethanol within 10 LBL cycles, generated an ultrahigh sensitivity of 821.64 μA mM−1 cm−2 in the range of 6–981.41 μM, a low detection limit of 60 nM as well as the great selectivity, stability and reproducibility. Moreover, the relative deviation for AA detection in two fruit juices were 3.22 % and 3.71 %, and the test result for human sweat fall within the normal AA concentration range, verifying the feasibility of as-prepared sensor for practical application.

A comprehensive transformer-based approach for high-accuracy gas adsorption predictions in metal-organic frameworks

Gas separation is crucial for industrial production and environmental protection, with metal-organic frameworks (MOFs) offering a promising solution due to their tunable structural properties and chemical compositions. Traditional simulation approaches, such as molecular dynamics, are complex and computationally demanding. Although feature engineering-based machine learning methods perform better, they are susceptible to overfitting because of limited labeled data. Furthermore, these methods are typically designed for single tasks, such as predicting gas adsorption capacity under specific conditions, which restricts the utilization of comprehensive datasets including all adsorption capacities. To address these challenges, we propose Uni-MOF, an innovative framework for large-scale, three-dimensional MOF representation learning, designed for multi-purpose gas prediction. Specifically, Uni-MOF serves as a versatile gas adsorption estimator for MOF materials, employing pure three-dimensional representations learned from over 631,000 collected MOF and COF structures. Our experimental results show that Uni-MOF can automatically extract structural representations and predict adsorption capacities under various operating conditions using a single model. For simulated data, Uni-MOF exhibits remarkably high predictive accuracy across all datasets. Additionally, the values predicted by Uni-MOF correspond with the outcomes of adsorption experiments. Furthermore, Uni-MOF demonstrates considerable potential for broad applicability in predicting a wide array of other properties.

Isostructural dual-ligand-based MOFs with different metal centers in response to diverse capacity lithium-ion battery anode

Metal-organic frameworks (MOFs) have become one of the most promising active materials in lithium-ion batteries (LIBs) due to their designable molecular architecture and tunable functionality. Herein, we report a series of isostructural three-dimensional MOFs of divalent Mn (1), Co (2), and Zn (3), [MII2(H2O)2(4,4′-bipy)(mal)2]n as anode materials for LIBs. The MOFs can be prepared within a few minutes using a facile microwave-heating technique. Investigations on electrochemical properties and performance as active materials for LIBs anodes showed that Co-MOF 2 has higher efficiency than the Mn and Zn congeners, with an excellent specific capacity of 732 mA h g−1 after 200 cycles, which is distinguished electrochemical performance in specific capacity and rate cycle performance over the previous MOF-based materials. First-principles computations revealed the importance of the metal center of MOFs on the Li-ion batteries performance since it is involved in the Li diffusion mechanism.

Three-dimensional metal–organic frameworks (MOFs) containing substituted diimide ligands: synthesis, structures and gas sorption studies

This study discusses the synthesis, characterization and gas sorption studies of two MOFs containing substituted diimide ligands.

Facile synthesis of a three-dimensional Ln-MOF@FCNT composite for the fabrication of a symmetric supercapacitor device with ultra-high energy density: overcoming the energy storage barrier.

In order to quench the thirst for efficient energy storage devices, a novel praseodymium-based state-of-the-art three-dimensional metal-organic framework (MOF), {[Pr(pdc)2]Me2NH2}n (YK-1), has been synthesized by using a simple solvothermal method employing a readily available ligand. YK-1 was characterised by single-crystal XRD and crystallographic analysis. The electrochemical measurements of YK-1 show that it exhibits a specific capacitance of 363.5 F g-1 at a current density of 1.5 A g-1 with 83.8% retention after 5000 cycles. In order to enhance its electrochemical performance for practical application, two composites of YK-1 with graphene oxide (GO) and functionalised multi-walled carbon nanotubes (FCNTs), namely YK-1@GO and YK-1@FCNT, were fabricated by employing a facile ultrasonication technique. The as-synthesized MOF and the composites were characterized by PXRD, FTIR, SEM, and TEM techniques. YK-1@GO and YK-1@FCNT offer enhanced specific capacitances of 488.2 F g-1 and 730.2 F g-1 at the same current density with 93.8% and 97.7% capacity retention after 5000 cycles, respectively (at 16 A g-1). Fascinated by the outstanding results shown by YK-1@FCNT, a symmetric supercapacitor device (SSC) based on it was fabricated. The assembled SSC achieved a remarkable energy density (87.6 W h kg-1) and power density (750.2 W kg-1) at a current density of 1 A g-1, along with very good cycling stability of 91.4% even after 5000 GCD cycles. The SSC device was able to power up several LED lights and even operated a DC brushless fan for a significant amount of time. To the best of our knowledge, the assembled SSC device exhibits the highest energy density among the MOF composite-based SSCs reported so far.

MIL-101(Cr)/aminoclay nanocomposites for conversion of CO2 into cyclic carbonates.

We present the use of an amine functionalized two-dimensional clay i.e., aminoclay (AC), in the chemistry of a three-dimensional metal-organic framework (MOF) i.e., MIL-101(Cr), to prepare MIL-101(Cr)/AC composites, which are exploited as catalysts for efficient conversion of CO2 gas into cyclic carbonates under ambient reaction conditions. Three different MOF nanocomposites, denoted as MIL-101(Cr)/AC-1, MIL-101(Cr)/AC-2, and MIL-101(Cr)/AC-3, were synthesized by an in situ process by adding different amounts of AC to the precursor solutions of the MIL-101(Cr). The composites were characterized by various techniques such as FT-IR, PXRD, FESEM, EDX, TGA, N2 adsorption, as well as CO2 and NH3-TPD measurements. The composites were exploited as heterogeneous catalysts for CO2 cycloaddition reactions with different epoxides and the catalytic activity was investigated at atmospheric pressure under solvent-free conditions. Among all the materials, MIL-101(Cr)/AC-2 shows the best catalytic efficiency under the optimized conditions and exhibits enhanced efficacy compared to various MIL-101(Cr)-based MOF catalysts, which typically need either high temperature and pressure or a longer reaction time or a combination of all the parameters. The present protocol using MIL-101(Cr)/AC-2 as the heterogeneous catalyst gives 99.9% conversion for all the substrates into the products at atmospheric pressure.

Two isomorphic rare earth coordination polymer based on 1-imidazol-1-yl-2,4,6-phenyltricarboxylic acid ligand: Synthesis, structure, fluorescence sensing and practical applications

Two three-dimensional metal organic framework {[Ln2 (ttc)3]∙1.5 DMF}n{Ln3+=Tb3+(1), Sm3+(2)} was synthesized by solvothermal reaction of rare earth metal Ln3+ ions and 1-imidazol-1-yl-2,4,6-benzene-tricarboxylic acid (H3ttc). The crystal characteristics and composition of the two compounds were confirmed by powder X-ray diffraction (PXRD) and thermogravimetric analysis (TG), and the single crystal X-ray diffraction confirmed that they are isomorphic. The luminescence and sensing properties of the two compounds were investigated in detail, the Tb-MOF exhibits characteristic emission of Tb3+ through effective sensitization by antenna effect and emits bright green fluorescence under excitation light of 254 nm. Fluorescence experiments show that Tb-MOF has high selectivity and sensitivity for the detection of TNP, Cr2O72−, and Al3+ with the limit of detection of 2.89×10−8 mol·L−1, 2.35×10−8 mol·L−1 and 2.69×10−8 mol·L−1, respectively. In addition, possible luminescence quenching mechanisms are discussed. As a result, such a Tb-MOF will be a promising candidate and applies to the field of fluorescent ink and fingerprint retrieval.

MOFs-derived Co/C nanoparticle embedded in N, S co-doped graphene for superior electromagnetic wave absorption capacity

Due to their physicochemical properties, the three-dimensional Metal-organic frameworks (MOFs) derived composites show great potential as electromagnetic wave (EMW) absorbers. However, poor impedance matching limits their actual EMW absorption performance. Composite materials that combine magnetic and dielectric losses offer a potential solution to enhance impedance match and significantly improve microwave absorption. In this work, a novel N,S-GS/Co/C composite was fabricated via a solvothermal method and a subsequent pyrolysis process to introducing nitrogen and sulfur co-doped graphene (N,S-GS) into Co-MOF. By co-doping nitrogen and sulfur, abundant defects and disordered sites were introduced on graphene, which stimulate interfacial polarization and dipole polarization. The minimum reflection loss (RL) of the sample obtained by pyrolysis at 600 °C is −68.8 dB at 9.7 GHz. Simultaneously, the thickness is 2.51 mm, and the effective absorption bandwidth (EAB) can reach 3.04 GHz. Its excellent EMW absorption performance is mainly attributed to interfacial polarization, multiple reflections, dipole polarization, magnetic resonance and eddy current loss. Accordingly, the N,S-GS/Co/C composite is convinced to be a competent candidate among EMW absorbers with high absorption intensity.

ZIF-67 derived CoSx mediated 1D hollow carbon nitride for high photocatalytic hydrogen performance

Metal-Organic Framework (MOFs) consist of organic ligands having metal ions at the center that have many properties especially large surface area, polymetallic sites, tunable organic ligands, and porous structure. In this work, a three-dimensional MOF ZIF-67 was decorated over the g-C3N4 1D hollow tubular structure by a simple precipitation technique. The proposed CoSx co-catalyst was introduced as a free condition in the solution derived from ZIF-67 rather than loaded on the 1D g-C3N4. It is suggested that CoSx offers an active site for the reduction of water molecules after accepting the photogenerated electrons from the 1D g-C3N4. The composite reveals high hydrogen performance (13911 μmol∙g−1 h−1) in comparison with ZIF-67 (4885 μmol∙g−1 h−1) and h-CN (1229 μmol∙g−1 h−1). Additionally, the composite sample has Quantum efficiency (Q.E) of about 19.5 % for hydrogen evolution reaction (HER) at 420 nm which is significantly greater than the h-CN (1.72 %) and ZIF-67 (6.87 %) sample. The work opened a new avenue in the field of photocatalysis by suggesting noble metal-free and high-efficiency MOF heterojunction.

Polydopamine-Induced Metal-Organic Framework Network-Enhanced High-Performance Composite Solid-State Electrolytes for Dendrite-Free Lithium Metal Batteries.

Due to the high safety, flexibility, and excellent compatibility with lithium metals, composite solid-state electrolytes (CSEs) are the best candidates for next-generation lithium metal batteries, and the construction of fast and uniform Li+ transport is a critical part of the development of CSEs. In this paper, a stable three-dimensional metal-organic framework (MOF) network was obtained using polydopamine as a medium, and a high-performance CSE reinforced by the three-dimensional MOF network was constructed, which not only provides a continuous channel for Li+ transport but also restricts large anions and releases more mobile Li+ through a Lewis acid-base interaction. This strategy endows our CSEs with an ionic conductivity (7.1 × 10-4 S cm-1 at 60 °C), a wide electrochemical window (5.0 V), and a higher Li+ transfer number (0.54). At the same time, the lithium symmetric batteries can be stably cycled for 2000 h at 0.1 mA cm-2, exhibiting excellent electrochemical stability. The LiFePO4/Li cells have a high initial discharge specific capacity of 153.9 mAh g-1 at 1C, with a capacity retention of 80% after 915 cycles. This paper proposes an approach for constructing three-dimensional MOF network-enhanced CSEs, which provides insights into the design and development of MOFs for the positive effects of high-performance CSEs.

Icing on the Cake: Imidazole-Anchored Strategy To Enhance the Proton Conductivity of Two Isostructural Ce(IV)/Hf(IV) Metal-Organic Frameworks.

In the field of proton conduction, the acquisition of crystalline metal-organic frameworks (MOFs) with high stability and ultrahigh proton conductivity has been of great research value and is worth continuous exploration. Here, we greenly synthesized a three-dimensional porous MOF (MOF-801-Ce) by using [(NH4)2Ce(NO3)6 and fumaric acid as starting materials and solvothermally synthesized Hf-UiO-66-NO2 by using HfCl4 and 2-nitroterephthalic acid as starting materials. A series of measurements have shown that both MOFs exhibit good water stability, acid-base stability, and thermal stability and demonstrate outstanding proton conductivity. At 100 °C and 98% relative humidity (RH), the proton conductivities (σ) could be 2.59 × 10-3 S·cm-1 for MOF-801-Ce and 0.89 × 10-3 S·cm-1 for Hf-UiO-66-NO2. To pursue higher proton conductivity, we further adopted the evaporation approach to encapsulate imidazole molecules in the pores of the two compounds, achieving the imidazole-encapsulated MOFs, Im@MOF-801-Ce and Im@Hf-UiO-66-NO2. As expected, their σ values were significantly boosted by almost an order of magnitude up to 10-2 S·cm-1. Finally, their proton-conductive mechanisms were explored in light of the structural information, gas adsorption/desorption, and other tests. The outstanding structural stability of these MOFs and their durability of the proton conduction capability manifested that they have great promise in electrochemical fields.

SOLVOTHERMAL SYNTHESIS, STRUCTURE, AND PROPERTIES OF CADMIUM(II)-ORGANIC COORDINATION POLYMER CONTAINING CARBOXYL GROUPS

Under the conditions of solvothermal synthesis, a new metal-organic coordination polymer of the composition Cd[H2L] (I, H4L = 4,4'-([2,2'-bipyridine]-6,6'-diylbis(oxy))diphthalic acid). According to X-ray diffraction analysis, each Cd(II) cation binds four organic ligands: one via the coordination of the chelate bipyridyl fragment, two via the bidentate coordination of deprotonated COO groups, and one more via the monodentate coordination of the protonated carboxylate group. The obtained three-dimensional metal-organic framework does not contain free space capable of including guest molecules. Compound I was characterized by powder X-ray diffraction, IR spectroscopy, elemental (C, H, N) and thermogravimetric analyses, and luminescence spectra were recorded for it.

An octa-nuclear nickel(II) pyrazolate cluster with a cubic Ni8 core and its methyl- and n-octyl-functionalized derivatives.

The mol-ecular and crystal structure of a discrete [Ni8(μ4-OH)6(μ-4-Rpz)12]2- (R = H; pz = pyrazolate anion, C3H3N2 -) cluster with an unprecedented, perfectly cubic arrangement of its eight Ni centers is reported, along with its lower-symmetry alkyl-functionalized (R = methyl and n-oct-yl) derivatives. Crystals of the latter two were obtained with two identical counter-ions (Bu4N+), whereas the crystal of the complex with the parent pyrazole ligand has one Me4N+ and one Bu4N+ counter-ion. The methyl derivative incorporates 1,2-di-chloro-ethane solvent mol-ecules in its crystal structure, whereas the other two are solvent-free. The compounds are tetra-butyl-aza-nium tetra-methyl-aza-nium hexa-μ4-hydroxido-dodeca-μ2-pyrazolato-hexa-hedro-octa-nickel, (C16H36N)(C4H12N)[Ni8(C3H3N2)12(OH)6] or (Bu4N)(Me4N)[Ni8(μ4-OH)6(μ-pz)12] (1), bis-(tetra-butyl-aza-nium) hexa-μ4-hydroxido-dodeca-μ2-(4-methyl-pyrazolato)-hexa-hedro-octa-nickel 1,2-di-chloro-ethane 7.196-solvate, (C16H36N)2[Ni8(C4H5N2)12(OH)6]·7.196C2H4Cl2 or (Bu4N)2[Ni8(μ4-OH)6(μ-4-Mepz)12]·7.196(ClCH2CH2Cl) (2), and bis-(tetra-butyl-aza-nium) hexa-μ4-hydroxido-dodeca-μ2-(4-octylpyrazolato)-hexa-hedro-octa-nickel, (C16H36N)2[Ni8(C11H19N2)12(OH)6] or (Bu4N)2[Ni8(μ4-OH)6(μ-4-nOctpz)12] (3). All counter-ions are disordered (with the exception of one Bu4N+ in 3). Some of the octyl chains of 3 (the crystal is twinned by non-merohedry) are also disordered. Various structural features are discussed and contrasted with those of other known [Ni8(μ4-OH)6(μ-4-Rpz)12]2- complexes, including extended three-dimensional metal-organic frameworks. In all three structures, the Ni8 units are lined up in columns.

Synergistic Induction of Solvent and Ligand-Substitution in Single-Crystal to Single-Crystal Transformations toward a MOF with Photocatalytic Dye Degradation.

External-stimuli responsiveness as found in natural organisms and smart materials is attractive for functional materials scientists who attempt to design and imitate fascinating behavior into their materials. Herein, we report a couple of new solvent-responsive isostructural two-dimensional cationic metal-organic frameworks (MOFs) of Mn(II) (1a) and Zn(II) (2a) that undergo unprecedented single-crystal to single-crystal (SCSC) transformation toward the corresponding isostructural three-dimensional MOFs of Mn(II) (1b) and Zn(II) (2b). The 2D MOFs 1a and 2a have been effortlessly and rapidly synthesized via the microwave-heating technique. The SCSC transformations are synergistically induced by solvent and ligand-substitution reactions and able to be triggered by water, methanol, ethanol, and n-propanol. Time-dependent SCSC transformations were studied by in situ X-ray diffraction. Investigations on photodegradation of methyl orange showed that Zn-MOF 2b has higher efficiency than Mn-MOF 1b under UV-C irradiation at 300 min, 94.27%, and 21.91%, respectively. The influence of charge on the dye molecules, heterogeneity of the catalysis, and •OH radical-scavenging test was studied. First-principles computations suggest that the high photocatalytic activity of 2b may be attributed to its suitable band-edge position for redox reactions.