Mixed-ligand Metal-organic Framework Research Articles

Nanoscale Mixed-Ligand Metal-Organic Framework for X-ray Stimulated Cancer Therapy.

Concurrent localized radiotherapy and systemic chemotherapy are standards of care for many cancers, but these treatment regimens cause severe adverse effects in many patients. Herein, we report the design of a mixed-ligand nanoscale metal-organic framework (nMOF) with the ability to simultaneously enhance radiotherapeutic effects and trigger the release of a potent chemotherapeutic under X-ray irradiation. We synthesized a new functional quaterphenyl dicarboxylate ligand conjugated with SN38 (H2QP-SN) via a hydroxyl radical-responsive covalent linkage. Because of the similar length of QP-SN and bis(p-benzoato)porphyrin (DBP) ligands, QP-SN was incorporated into Hf-DBP nMOF to afford a novel multifunctional mixed-ligand Hf-DBP-QP-SN nMOF with good biocompatibility. Hf-DBP-QP-SN not only enhances radiation damage to tumors via a unique radiotherapy-radiodynamic therapy (RT-RDT) process but also increases ·OH generation from radiolysis with electron-dense Hf12 secondary building units (SBUs) to release SN38 from Hf-DBP-QP-SN for chemotherapy. Elevated levels of hydrogen peroxide in the tumor microenvironment further stimulate the release of SN38 by enhancing ·OH generation under X-ray irradiation. With low doses of X-ray irradiation, Hf-DBP-QP-SN suppressed the growth of CT26 colon and 4T1 breast tumors by 93.5% and 95.2%, respectively, without any sign of general toxicity. Our study highlights the potential of using ionizing radiation-mediated chemistry for on-demand activation of nanotherapeutics for synergistic radiotherapy and chemotherapy without causing severe adverse effects.

Construction of a novel chemiluminescence system based on mixed-ligand metal-organic frameworks

Exploring new materials to enhance chemiluminescence (CL) and constructing novel CL systems are essential for expanding the application range of CL analysis and improving its sensitivity. Metal-organic frameworks (MOFs) have gained popularity in catalysis and other fields due to their unique structural features and properties. However, the research on the application of MOFs in CL is still in its infancy. In this study, one kind of mixed-ligand metal-organic frameworks using Zn as the metal ion (Zn m-MOFs) was successfully synthesized and applied to enhance the CL of NaClO-H2O2 system. The synthesized Zn m-MOFs catalyzed the generation of reactive oxygen species (ROS) (·O2−, 1O2 and ·OH) which injected holes and electrons to Zn m-MOFs to generate hole-injected and electron-injected Zn m-MOFs (Zn m-MOFs⋅+ and Zn m-MOFs⋅−). The subsequent annihilation of these charge carriers led to enhanced CL. At the same time, chemiluminescence resonance energy transfer (CRET) occurred during the process. Compared with the NaClO-H2O2 system without Zn m-MOFs, the CL intensity of the Zn m-MOFs-NaClO-H2O2 system was enhanced by approximately 1000 times. This study aims to provide new insights for the development of innovative CL systems based on MOFs, thereby broadening the application fields of CL analysis.

Eu3+-Doped Mixed-Ligand UiO-66-Type Metal-Organic Framework for Ratiometric Fluorescence Sensing Fluoride Ions with Ultralow Detection Limit.

Metal-organic frameworks (MOFs) have emerged as a highly promising platform for various sensing applications due to their tunable structures and functionalities. In the present work, a Eu3+-doped mixed-ligand MOF, namely, the Eu3+@UiO-66-IPA, exhibited excellent luminescent properties and high fluorescence stability in aqueous media, displaying dual-emission peaks under 395 and 615 nm excitation that were readily visible to the naked eye. Importantly, the presence of fluoride ions (F-) promoted the "antenna effect" between the ligand and the Eu3+ centers, which significantly enhanced the emission intensity of the Eu3+ characteristic peak. In addition, the addition of F- also inhibited the quenching effect of high-energy O-H bonds existing in the aqueous environment. Notably, Eu3+@UiO-66-IPA demonstrated exceptional selectivity for F- over a range of competing anions, with a remarkable limit of detection as low as 0.22 μM. The developed Eu3+-doped mixed-ligand MOF system offers a highly promising strategy for the simple and accurate sensing of F- in practical applications.

Heterobimetallic Synergism in Triple-Redox 2D Framework for Largely Boosted Water Oxidation and Flanked Carboxylic-Acid-Triggered Unconventional Tandem Catalysis.

A fish-bone-shaped and thermochemically stable 2D metal-organic framework (MOF) with multimodal active center-decked pore-wall is devised. Redox-active [Co2(COO)4] node and thiazolo[5,4-d]thiazole functionalization benefit this mixed-ligand MOF exhibiting electrochemical water oxidation with 375mV overpotential at 10mA cm-2 current density and 78mV per dec Tafel slope in alkaline medium. Pair of oppositely oriented carboxylic acids aids postmetalation with transition metal ions to engineer heterobimetallic materials. Notably, overpotential of Ni2+ grafted triple-redox composite reduces to 270mV with twofold declined Tafel slope than the parent MOF, ranking among the best-reported values, and outperforming majority of related catalysts. Significantly, turnover frequency and charge transfer resistance display 35.5 and 1.4-fold upsurge, respectively, with much uplifted chronopotentiometric stability and increase active surface area owing to synergistic Co(II)-Ni(II) coupling. The simultaneous presence of ─COOH and nitrogen-rich moieties renders this hydrogen-bonded MOF as acid-base synergistic catalyst for recyclable deacetalization-Knoevenagel reaction with >99% product yield under solvent-free mild condition. Besides control experiments, unique role of ─COOH as hydrogen-bond donor site in substrate activation is validated from comparing the performances of molecular-shearing approach-derived structurally similar unfunctionalized MOF, and the heterobimetallic composite. To the best of tandem Knoevenagel condensation, larger-sized acetal exhibits poor yield of α,β-unsaturated dicyanides, and demonstrates pore-fitting-mediated size-selectivity.

Zirconium-based mixed ligand metal–organic framework for efficient adsorption of organic dyes

Zirconium-based mixed ligand metal–organic framework for efficient adsorption of organic dyes

Regulation and synthesis of metal–organic frameworks through mixed-ligand strategy: A pathway to enhance adsorption of perfluoroalkyl acids

Metal-organic frameworks (MOFs) have been regarded as extremely promising adsorbent materials, with the repetitive coordination assembly of inorganic metal ions and organic ligands constituting their reticular structure and abundant pores. Herein, a ligand mixing approach to synthesizing and regulating MOFs is provided. By mixing multiple solvents and adding modifiers, imidazole-based linkers can be prepared MOFs with mixed ligand components at room temperature. In this study, we prepared four mixed-ligand MOFs: Zn(aIM + bIM), Zn(mIM + bIM), Zn(aIM + mIM), and Zn(mIM + 2-mbIM). Series of characterizations by SEM, XRD, NMR, etc. confirmed the successful preparation of mixed-ligand MOFs, and they exhibited the different surface areas, pore sizes, and surface properties. And the adsorption capabilities for perfluoroalkyl acids (PFAAs) were compared among the prepared MOFs adsorbents. Among them, Zn(aIM + bIM) consisting of benzimidazole and imidazole-2-formaldehyde linker possessed the optimum adsorption performance, with an equilibrium adsorption capacity qe of 245 mg/g for perfluorobutyric acid, and the calculated maximum adsorption capacity qm of 439 mg/g. And for the other chain lengths of perfluoroalkyl acids, the adsorption results are also acceptable. The potential adsorption mechanism and the reasons for the performance enhancement are discussed based on relevant characterization and simulation. It was proved that the ligand mixing strategy can provide new insights into the development of high-performance MOFs adsorbents for addressing environmental concerns.

Proton-induced switching of excitation-wavelength-dependent emission based on mixed-ligand metal–organic frameworks

Switchable Ex-De emission of ML-MOFs has been realized via a proton-controlled ET process, enabling the design of high-level anti-counterfeiting applications.

Linker engineering in mixed-ligand metal–organic frameworks for simultaneously enhanced benzene adsorption and benzene/cyclohexane separation

A novel mixed-ligand metal–organic framework, featuring naphthalene rings in its secondary linker, exhibits exceptional benzene adsorption and separation capacities.

Unexpected reversal of reactivity in organic functionalities when immobilized together in a metal-organic framework (MOF).

A mixed-ligand metal-organic framework (MOF) material composed of both amine- and hydroxyl-bearing linkers, KSU-1, was reacted with a variety of isocyanates. The hydroxyl groups reacted to a greater extent than the amines, in conflict with the previously observed relative nucleophilicities of these functionalities in the same MOF. When immobilized individually in monofunctional MOFs, the amine-functionalized linker was more reactive than the hydroxyl linker, indicating that the reactivity reversal observed in KSU-1 is due to the groups' mutual confinement within the MOF.

A mixed-ligand Co metal-organic framework and its carbon composites as excellent electrocatalysts for the oxygen evolution reaction in green-energy devices.

Oxygen evolution reaction (OER) electrocatalysts are frequently made from noble metal-based oxides like ruthenium/iridium oxides. However, because of their scarcity and high price, researchers are now focusing on creating innovative OER catalysts based on affordable transition metals that have improved electrical conductivity and accessibility to active sites. Metal-organic frameworks (MOFs), a unique class of inorganic materials with excellent physical and chemical properties, have witnessed significant progress in promising green energy systems. In this work, a novel mixed-ligand metal-organic framework [Co(μ-1κN,2κN'-BDP)(μ3-1κoo',2κo''2κo'''-BTC)]n·nH2O (BDP = boron-dipyrromethene or BODIPY; BTC = benzene tricarboxylate) denoted as CoBDPMOF has been synthesized, and its composites with different carbon materials have been designed. Compared to the pristine MOF, the composites showed enhanced electrocatalytic activity toward the oxygen evolution reaction (OER) in alkaline media. In addition, the CoBDPMOF with activated carbon showed the highest OER performance with a low Tafel slope (82 mV dec-1) and the highest j600 (59.8 mA cm-2), outperforming noble metal IrO2, the OER benchmark electrocatalyst. This study presents new insights into the design and application of CoBDPMOF-based materials for energy conversion and suggests promising avenues for further research and development in electrocatalysis.

Electron Donor Coordinated Metal-Organic Framework to Enhance Photoelectrochemical Performance.

To enhance photoelectrochemical (PEC) performance, additional electron donor/acceptor is generally required to inhibit the electron-hole recombination. However, the enhancement is limited due to the long-distance diffusion. Herein a self-supplying electron strategy is designed for PEC enhancement by coordinating an electron donor 1.4-diazabicyclo[2.2.2]octane (Dabco) in metal-organic framework (MOF). The intrareticular photoelectron transfer mechanism in mixed-ligand MOF (m-MOF) is experimentally revealed and verified by density functional theory calculations. The presence of Dabco efficiently inhibits the electron-hole recombination due to the self-supplying electrons and longer electron lifetime in the framework, and thus leads to 23.2-fold enhancement of photocurrent. As proof of concept, a simple PEC method is constructed with the designed m-MOF to demonstrate its application in sensitive bioanalysis. This work provides a new avenue for improving the PEC performance of nanomaterials.

Application of a Mixed-Ligand Metal–Organic Framework in Photocatalytic CO2 Reduction, Antibacterial Activity and Dye Adsorption

In this paper, a known mixed-ligand MOF {[Co2(TZMB)2(1,4-bib)0.5(H2O)2]·(H2O)2}n (compound 1) was reproduced, and its potential application potential was explored. It was found that compound 1 had high photocatalytic activity for CO2 reduction. After 12 h of illumination, the formation rate of CO, which is the product of CO2 reduction by compound 1, reached 3012.5 μmol/g/h. At the same time, compound 1 has a good antibacterial effect on Staphylococcus aureus (S. aureus), Escherichia coli (E. coli) and Candida albicans (C. albicans), which has potential research value in the medical field. In addition, compound 1 can effectively remove Congo Red from aqueous solutions and achieve the separation of Congo red from mixed dye solutions.

Large Degree of Variation in Sorption Properties within a System of Isoreticular, Mixed-Ligand Ni- and Co-Based 2-Periodic Metal–Organic Frameworks

Two Ni-based and two Co-based mixed-ligand metal–organic frameworks (MOFs), which are all isoreticular with each other, are shown to have a large variation in nitrogen, carbon dioxide, hydrogen, and water vapor sorption properties, despite their similar structures. The MOFs have 1,2-bis(4-pyridyl)ethane (bpe) as the common ligand with the second ligand being either 2-nitroterephthalate (2-nta) or 2-bromoterephthalate (2-bta) for the Ni-based MOFs or 2-nta or 2-aminoterephthalate (2-ata) for the Co-based MOFs. The four MOFs have the formula [Ni(2-nta)(bpe)(H2O)2]n·2(DMA)n (1), [Ni(2-bta)(bpe)(H2O)2]n·2.8(DMF)n (2), [Co(2-nta)(bpe)(H2O)2]n·2(DMA)n (3), and [Co(2-ata)(bpe)(H2O)2]n·3(DMA)n·(H2O)n (4), respectively, where DMA = N,N′-dimethylacetamide and DMF = N,N′-dimethylformamide. Variable-temperature powder X-ray diffraction (VT-PXRD) studies indicate that the activated MOF structures are different from those of the as-synthesized MOFs, showing that the 2-periodic layers are dynamic upon desolvation. For the same metal ion, the MOF involving the 2-nta ligand has higher sorption, while sorption for the Ni-based MOFs is higher than for the Co-based MOFs. MOF 1 has the highest sorption within the isoreticular series and also has the highest sorption (the highest for water vapor) compared to other MOFs with the same or related ligands.

Solid-phase extraction of personal care products using mixed-ligand metal–organic framework combined with spectrophotometric determination

The adsorption of personal care products (diclofenac sodium and chlorhexidine digluconate) on a mixed-ligand metal–organic framework based on a complex of nickel terephthalate with 2,2'-bipyridine was investigated by solid-phase extraction in combination with spectrophotometric analysis.

Two-Dimensional Mixed-Ligand Metal–Organic Framework Constructed from Bridging Bidentate V-Shaped Ligands

A two-dimensional and bifunctional pillar-layered metal–organic framework (MOF)—with the molecular formula [Zn(cba)(bpdb)]·DMF (2DTMU-1), H2cba = 4,4′-methylenedibenzoic acid, bpdb = 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene—was obtained via the reaction of zinc(II) nitrate with H2cba as the carboxylate linker and bpdb as the N-donor pillar. 2DTMU-1 is based on a binuclear paddlewheel Zn(II) unit complexed by four bridging bidentate (dicarboxylate) V-shaped ligands, which combine to from H2cba; this tetragonal array, which is connected by bpdb with a bridging azine group, presents a pore size of 18 × 12 Å2.

Structure and Properties of a Mixed-Ligand Co-MOF That Was Synthesized in Situ from a Single Imidazole–Pyridyl–Tetrazole Trifunctional Ligand

A mixed-ligand Co-MOF (SCNU-Z7) based on a new imidazole–pyridyl–tetrazole trifunctional ligand, 3-(imidazol-1-yl)-5-(tetrazol-5-yl) pyridine (HITP), was constructed using a solvothermal reaction. Single-crystal X-ray diffraction analysis revealed that in addition to HITP, the 5,5′-bis-(2H-tetrazol-5-yl)-[3,3′]bipyridinyl (H2BTBP) ligand obtained by the in situ reaction of HITP is also incorporated into the framework, thus generating a mixed-ligand metal–organic framework (MOF). SCNU-Z7 has a 3D porous framework with 1D channels along the c axis based on tetranuclear secondary building blocks and has a new highly (3,4,10)-connected network topology with the symbol (416·620·89)(43)2(44·62). SCNU-Z7 exhibits high stability in organic solvents but instability in water. Gas adsorption studies indicated that SCNU-Z7 can absorb CO2 more than N2. Magnetic studies indicate the existence of dominant antiferromagnetic interactions between Co(II) atoms. Due to porosity, Co(II) ions, nitrogen-rich conjugated aromatic rings, and uncoordinated nitrogen atoms in its framework, SCNU-Z7 can capture iodine in vapor with a capacity of 2.7 g/g. The strong interactions between the framework and the iodine molecules cause the amorphization of the framework, and approximately 60% of the adsorbed iodine molecules can be stably stored in the framework. This study provides a new possible route for obtaining mixed-ligand MOFs and provides a new example for stably capturing iodine in MOFs via amorphization.

Guest Editorial: Solar Energy Utilization

Guest Editorial: Solar Energy Utilization

Mixed-ligand metal-organic frameworks as an effective photocatalyst for selective oxidation reaction.

By incorporating tetrakis(4-carboxyphenyl)porphyrin and bis(3,5-dicarboxyphenyl)pyridine into one single metal-organic framework (MOF), a multifunctional mixed-ligand Zn-MIX with large pores was obtained. Under visible-light irradiation, Zn-MIX exhibits high photocatalytic activity for the oxidation of amines and sulfides.

A mixed-ligand Co(II) MOF synthesized from a single organic ligand to capture iodine and methyl iodide vapour.

Mixed-ligand metal-organic frameworks (MOFs) are usually synthesized from two or more organic ligands as initial reactants, and MOFs synthesized from one organic ligand precursor through partial in situ reactions remain very limited. Herein, by introducing an imidazole-tetrazole bifunctional ligand, 5-(4-imidazol-1-yl-phenyl)-2H-tetrazole (HIPT), as a single ligand and performing in situ hydrolysis of the tetrazolium group, a mixed-ligand Co(II)-MOF based on HIPT and 4-imidazol-1-yl-benzoic acid (HIBA), [Co2(μ3-O)(IPT)(IBA)]·x solvent (Co-IPT-IBA), was constructed and applied to capture I2 and methyl iodide vapours. Single crystal structural analyses reveal that Co-IPT-IBA exhibits a 3D porous framework with 1D channels based on the relatively few reported ribbon-like rod SBUs. The nitrogen adsorption-desorption isotherms indicate that the BET surface area of Co-IPT-IBA is 168.5 m2 g-1 and it possesses both micropores and mesopores. Due to its porosity, nitrogen-rich conjugated aromatic rings, and Co(II) ions, Co-IPT-IBA was applied to capture iodine molecules in vapour and exhibited an adsorption capacity of 2.88 g g-1. By combining the IR, Raman, XPS and grand canonical Monte Carlo (GCMC) simulation results, it was deduced that the tetrazole ring, coordination water molecules, and the redox potential of Co3+/Co2+ facilitate iodine capture. The presence of mesopores was also responsible for the high iodine adsorption capacity. In addition, Co-IPT-IBA showed the ability to capture methyl iodide in vapours with a moderate capacity of 625 mg g-1. The transformation of crystalline Co-IPT-IBA to amorphous MOFs may be due to the methylation reaction. This work represents a relatively rare example of methyl iodide adsorption by MOFs.

Mixed-ligand metal–organic frameworks with coordinatively un-saturated Co(II) and Ni(II) sites for regenerable O2-selective ad-sorption over N2

For air separation, the separation method relying on adsorbents has attracted wide attention as a low energy consumption process, and the development of O2-selective adsorbents is of great significance. Metal-organic frameworks with coordinatively unsaturated transition metal sites have great potential in O2-selective adsorption, but most of them cannot be completely regenerated at ambient temperature or can only be effective at very low temperatures. Herein, we report two mixed-ligand metal–organic framework adsorbents [M(AIP)(BPY)0.5·H2O]n·2nH2O with coordinatively unsaturated cobalt(II) and nickel(II) sites, which can preferentially adsorb O2 versus N2, and their IAST O2/N2 selectivities are both significantly greater than 1 at 25 °C. These materials exhibited excellent stability and had no loss of adsorption capacities even after immersion in water for 7 days. More importantly, O2 adsorption–desorption cycle experiments showed that these adsorbents can be completely regenerated at ambient temperature after adsorbing O2, and the breakthrough experiments further confirmed their dynamic O2/N2 separation potential and regeneration ability. The results of theoretical calculations suggested that the interactions between adsorbents and O2 are stronger than those of N2, and they have relatively obvious differences in the N2 and O2 interaction energies. This work provides inspirations for searching for metal–organic frameworks that can selectively adsorb O2 at ambient temperature.