Sequential Linker Installation in Metal–Organic Frameworks

Accounts of Chemical Research, Год журнала: 2024, Номер 57(21), С. 3217 - 3226

Опубликована: Окт. 16, 2024

ConspectusMetal–organic frameworks (MOFs) represent a sophisticated blend of inorganic and organic components, promoting the development coordination chemistry greatly offering versatile platform for tailored functionalities. By combining various metal nodes, linkers, functional guests, MOFs provide numerous pathways their design, synthesis, customization. Among these, sequential linker installation (SLI) stands out as novel crucial strategy, enabling precise integration desired properties functions at atomic scale. SLI enhances structural diversity stability while facilitating meticulous construction robust by leveraging open sites linkers targeted locations. Compared to direct synthesis MOFs, postsynthetic modification methods allow regulation structures corresponding properties. While unlike conventional methods, requires careful selection framework design ensure positioning installation, which gives rise well-designed ordered positions installed confirmed directly X-ray diffraction technology.Recent advancements in MOF have led creation increasingly flexible matrix structures, particularly due diverse connection modes multicore clusters, especially Zr6 cluster. The spatial hindrance certain ligands has resulted formation unsaturated clusters missing pockets. Examples these advanced include PCN-606, PCN-608, PCN-609, PCN-700, PCN-808, feature specific flexibility conducive SLI. Strategically positioned within serve predetermined anchor points molecules, frameworks' can accommodate molecules varying sizes extent, enlarging scopes application greatly. This groups enables enhanced applications, such adsorption, catalysis, recognition.In this Account, we delve into intricate process designing synthesizing with appropriate missing-linker pockets aforementioned applications. We discuss used insert them MOFs. Additionally, explore functionalities resulting focusing on adsorptive, catalytic, recognition performance. Furthermore, insights future trajectory complemented our recent works. Account not only reviews evolution method but also underscores its practical applications across domains, paving rational pathway multifunctional through method.

Язык: Английский

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Manipulating weak interactions between host/guest and analytes in Cu(I)-cluster-based MOF for fluorescent gas sensing towards chlorinated volatile organic compounds

Chemical Engineering Journal, Год журнала: 2025, Номер unknown, С. 159923 - 159923

Опубликована: Янв. 1, 2025

Язык: Английский

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Indirect Construction of Chiral Metal–Organic Frameworks for Enantioselective Luminescence Sensing

Accounts of Chemical Research, Год журнала: 2025, Номер unknown

Опубликована: Фев. 2, 2025

ConspectusChiral metal-organic frameworks (MOFs) are promising candidates as luminescent sensing materials for chiral species, which essential components in modern industries, pharmaceuticals, and biological processes. The discrimination of enantiomers with highly similar physical chemical properties is crucial because they often present concurrently the same system but may feature distinct effects on living matters. While rapid precise capabilities MOFs outshine traditional detection methods species daily life, production, natural environment, it requires well-matched electronic structures between species. Yet, conventional strategies to construct immensely challenging due crystallization difficulties based low-symmetric building blocks.Recent advancements MOF chemistry have led novel pathways synthesizing enantioselective sensing. Compared direct synthesis using optically pure ligands, usually complex costly, indirect has garnered significant attention reduced costs, simplified synthesis, enhanced material stability, broad application scope. In past few years, our group developed guest ion exchange, coordination modification, defect engineering indirectly MOFs. exchange cost-effective introducing ions into pores can be applied only charged frameworks. addition, also faces limitations availability tendency toward chirality loss during process. Besides, compared modification maintain stability stronger bonds. Still, accessible open metal sites that bind disordered dangling molecules, complicating structural determination. Therefore, specific such linker installation dual-end been afford well-defined crystal structures. all aforementioned decrease MOFs' pore sizes a certain degree, we further approach enlarge size introduce center simultaneously. Such competitive strategy facile low-cost expanded many well-known stable MOFs.In this Account, delve intricate evolution constructing tailored applications. We provide detailed analysis progression innovation within field, tracing development MOF-based luminescence sensors. By systematically reviewing various synthetic approaches, work highlights their respective strengths limitations. Beyond state art, Account offers forward-looking insights aiming inspire design next-generation These advanced hold promise versatile impactful applications across beyond.

Язык: Английский

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Regulating the Energy Level of a Ratiometric Luminescent Europium(III) Metal–Organic Framework Sensor with Smartphone Assistance for Real-Time and Visual Detection of Carcinoid Biomarker

Inorganic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Фев. 18, 2025

Regulating the energy level of a lanthanide (III) metal–organic framework (Ln-MOF) via an "antenna effect" is effective strategy for achieving ratiometric luminescent dynamics carcinoid biomarker sensing application. Herein, we present europium-based MOF material {[Eu(BPDC)(μ3–OH)(H2O)2]·2.5H2O}n (Eu-MOF, H2BPDC = 2,2′-bipyridine-4,4′-dicarboxylic acid and DMF N,N-dimethylformamide), incorporating tetranuclear cubane-like [Eu4(μ3–OH)4(COO)4]4– cluster cores, 5-hydroxyindole-3-acetic (5-HIAA) detection through influence Eu3+ ions sensitized by ligands as well 5-HIAA. Luminescence titration experiments indicate Eu-MOF can demonstrate simultaneous luminescence emission signals cations 5-HIAA, resulting in on–off 5-HIAA response to concentrations demonstrating superior stability excellent performance such low limit (LOD 37.16 nM), high selectivity (Ksv 2.39 × 104 M–1), fast (≤1 min), attractive recyclability (≥five times). Derived from contribution competitive absorption coordination interactions between exhibits visually observable color change red purple naked eye illuminated ultraviolet light, confirmed fabrication portable hydrogels. More importantly, smartphone assistance based on RGB chromaticity analysis has been developed intelligent Eu-MOF@PVA Eu-MOF@PU films have proposed real-time visual thereby enhancing practical applicability quantitative trace

Язык: Английский

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A stereodynamic probe of Pt(II) molecular hinge for chiroptical sensing of cryptochiral compounds

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Фев. 25, 2025

Cryptochiral compounds are indispensable in biology systems and medical applications, yet the development of high-performance detection method remains challenging. Here, we report a hinge-like dinuclear Pt(II) complex as stereodynamic probe for cryptochirality sensing. This features constrained, closed conformation achieved through synergistic intramolecular π − stacking metal-metal interactions between cyclometalated wings. The shows robust chiroptical response to center-to-axial chiral induction during rapid condensation with cryptochiral that adopts more energetically favorable conformation. resulting intense Cotton effects at long wavelengths enable in-situ circular dichroism analysis determinate absolute configuration enantiometric composition molecules. Furthermore, near-infrared phosphorescence characteristics hinge have been explored develop it an optical sensor accurate quantification With its dual CD capabilities, this great potential high-throughput screening analysis. authors complexes probes

Язык: Английский

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Zinc(II) 2D Coordination Polymer With Terephthalate and 4,6‐Bis(Imidazol‐1‐yl)‐2,1,3‐Benzoxadiazole Linkers as a Selective Luminescent Probe for Gallium(III) Cations

Applied Organometallic Chemistry, Год журнала: 2025, Номер 39(3)

Опубликована: Фев. 26, 2025

ABSTRACT A two‐dimensional (2D) zinc(II) coordination polymer CP‐1 , [Zn(im 2 bod)(bdc)] n (im bod = 4,6‐bis(imidazol‐1‐yl)‐2,1,3‐benzoxadiazole, bdc 2− 1,4‐benzenedicarboxylate), was synthesized and fully characterized. crystallizes in the monoclinic crystal system, space group P 1 /n. Zn 2+ ions adopt a four‐coordinated distorted tetrahedral geometry. The structure of comprises layer consisting cations connected by im ligands. adjutant layers participate π‐π stacking interactions via benzene 2,1,3‐benzoxadiazole rings. demonstrated blue emission with maximum at 490 nm photoluminescence quantum yield 24%. Luminescent sensing properties aqueous suspension toward metal were evaluated, selective quenching response observed Ga 3+ limit detection 10 μM.

Язык: Английский

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Elevating the Optical Nonlinearity: Design, Synthesis, and Properties of a Mixed-Ligand Zinc(II) Metal–Organic Framework

ACS Applied Materials & Interfaces, Год журнала: 2025, Номер unknown

Опубликована: Март 4, 2025

The molecular design of new compounds with enhanced third-order nonlinear optical (NLO) applications is an important research topic in the area functional materials. present study describes a 3D metal-organic framework [Zn3(μ3-bta)2(μ4-ata)2]n (abbreviated as NH2-Zn-MUM-6), generated solvothermally from multicomponent system composed zinc(II) ions and 2-aminoterephthalic acid (H2ata) 1H-benzotriazole (Hbta) linkers. Apart intricate porous structure seh-4,6-Imma topology, this MOF features good thermal stability exceptional NLO characteristics. These were investigated detail by Z-scan method, revealing remarkably high values refractive index (n2 = 30.83 × 10-8 cm2/W) absorption coefficient (β 4.06 10-4 cm/W). An extended π-conjugation both aromatic ligands, μ3-bta- μ4-ata2-, their interaction Zn centers contribute to formation highly polarizable system, thus significantly enhancing its capacity for behavior. This broadens family materials provides insights into relationship between properties amino-functionalized mixed-linker MOFs viewpoint such all-optical switching data transmission.

Язык: Английский

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Metal-polymer-coordinated complexes: An expedient class of hybrid functional materials

Coordination Chemistry Reviews, Год журнала: 2024, Номер 524, С. 216286 - 216286

Опубликована: Ноя. 8, 2024

Язык: Английский

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Highly Water‐Stable 2D MOF as Dual Sensor for the Ultra‐Sensitive Aqueous Phase Detection of Nitrofuran Antibiotics and Organochlorine Pesticides

Small, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 20, 2024

Abstract Misuse of antibiotics and pesticides has led to hazardous effects on human health, livestock, agriculture, aquaculture, which urges researchers find simple, rapid, efficient, cost‐effective methods for quick on‐site analysis these organic pollutants with functional materials. Herein, a 2D chemically robust MOF: IITKGP‐71 , {[Cd(MBPz)(2,6‐NDC)]·2H 2 O} n is strategically developed ease in scalability exploited as dual sensors toward the toxic antibiotic pesticide detection via luminescence quenching aqueous medium . The framework displays exceptional chemical robustness water 3 months, an open atmosphere over wide range pH solution (pH = 3–12) day. can selectively quench nitrofuran (NFZ NFT) organochlorine DCN while remaining unaffected by other interfering pesticides, respectively. An excellent trade‐off between high effectivity (high K sv ) sensitivity (low LOD) was achieved targeted analytes. easy scalability, stability, fast responsivity, multi‐responsive nature, recyclability outstanding structural stability made this viable playing crucial role safeguarding aquatic ecosystems public health from pesticides.

Язык: Английский

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Debus–Radziszewski Reaction Inspired In Situ “One-Pot” Approach to Construct Luminescent Zirconium-Organic Frameworks

Inorganic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 11, 2025

Metal–organic frameworks have received extensive development in the past three decades, which are generally constructed via reaction between inorganic building units and commercially available or presynthesized organic linkers. However, presynthesis of linkers is usually time-consuming unsustainable due to multiple-step separation purification. Therefore, methodology a new strategy fundamentally important for construction further exploration applications MOFs. Herein, we report an situ "one-pot" inspired by Debus–Radziszewski reaction, generation from kinds simple precursors sequential MOFs integrated into one solvothermal condition. Based on this method, two zirconium-tetracarboxylate (HIAM-4028-op HIAM-4029-op) were successfully prepared, exhibit bright blue near-infrared emissions, respectively. Due coordinatively unsaturated metal sites low symmetry HIAM-4028-op, coordination modes single crystal can transfer pristine 8-connected Zr6 cluster 8- 9-connected 9- 12-connected coexisting structures secondary linker installation. To best our knowledge, present work first time construct using reaction-inspired strategy, opens way design with specific properties structures.

Язык: Английский

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