A Fluorescent Sensor for Highly Selective Detection of Nitroaromatic Explosives Based on a 2D,Extremely Stable,Metal–Organic Framework

A 2D, extremely stable, metal–organic framework (MOF), NENU‐503 , was successfully constructed. It displays highly selective and recyclable properties in detection of nitroaromatic explosives as a fluorescent sensor. This is the first MOF that can distinguish between nitroaromatic molecules with different numbers of ?NO₂ groups.     

A Luminescent Microporous Metal–Organic Framework for the Fast and Reversible Detection of High Explosives

Sensors and sensitivity : A highly luminescent microporous metal–organic framework, [Zn₂(bpdc)₂(bpee)] (bpdc=4,4′‐biphenyldicarboxylate; bpee=1,2‐bipyridylethene), is capable of very fast and reversible detection of the vapors of the nitroaromatic explosive 2,4‐dinitrotoluene and the plastic explosive taggant 2,3‐dimethyl‐2,3‐dinitrobutane, through redox fluorescence quenching with unprecedented sensitivity (see spectra).

     

Highly Selective Sorption and Luminescent Sensing of Small Molecules Demonstrated in a Multifunctional Lanthanide Microporous Metal–Organic Framework Containing 1D Honeycomb‐Type Channels

A rare, robust microporous lanthanide metal–organic framework with 1D honeycomb‐type channels is presented. Excellent adsorption capabilities for N₂, H₂, and CO₂ and significant selective sorption of CO₂ over N₂ and CH₄ were observed. Moreover, the guest‐dependent luminescent behavior of these lanthanide materials shows a potential use for the sensing of small‐molecule pollutants such as benzene and acetone.     

A Microporous Covalent–Organic Framework with Abundant Accessible Carbonyl Groups for Lithium‐Ion Batteries

A key challenge faced by organic electrodes is how to promote the redox reactions of functional groups to achieve high specific capacity and rate performance. Here, we report a two‐dimensional (2D) microporous covalent–organic framework (COF), poly(imide‐benzoquinone), via in situ polymerization on graphene (PIBN‐G) to function as a cathode material for lithium‐ion batteries (LIBs). Such a structure favors charge transfer from graphene to PIBN and full access of both electrons and Li⁺ ions to the abundant redox‐active carbonyl groups, which are essential for battery reactions. This enables large reversible specific capacities of 271.0 and 193.1 mAh g^?1 at 0.1 and 10 C, respectively, and retention of more than 86 % after 300 cycles. The discharging/charging process successively involves 8 Li⁺ and 2 Li⁺ in the carbonyl groups of the respective imide and quinone groups. The structural merits of PIBN‐G will trigger more investigations into the designable and versatile COFs for electrochemistry.     

A Water‐Stable Terbium(III)–Organic Framework as a Chemosensor for Inorganic Ions,Nitro‐Containing Compounds and Antibiotics in Aqueous Solutions

Effective detection of organic/inorganic pollutants, such as antibiotics, nitro‐compounds, excessive Fe³⁺ and MnO₄^?, is crucial for human health and environmental protection. Here, a new terbium(III)–organic framework, namely [Tb(TATAB)(H₂O)]?2H₂O ( Tb‐MOF , H₃TATAB=4,4′,4′′‐s‐triazine‐1,3,5‐triyltri‐m‐aminobenzoic acid), was assembled and characterized. The Tb‐MOF exhibits a water‐stable 3D bnn framework. Due to the existence of competitive absorption, Tb‐MOF has a high selectivity for detecting Fe³⁺, MnO₄^?, 4‐nirophenol and nitroimidazole (ronidazole, metronidazole, dimetridazole, ornidazole) in aqueous through luminescent quenching. The results suggest that Tb‐MOF is a simple and reliable reagent with multiple sensor responses in practical applications. To the best of our knowledge, this work represents the first Tb^III‐based MOF as an efficient fluorescent sensor for detecting metal ions, inorganic anions, nitro‐compounds, and antibiotics simultaneously.     

Lanthanide Organic Framework Luminescent Thermometers

Metal–organic frameworks (MOFs) are excellent platforms for engineering luminescence properties as their building blocks, metal ions, linkers, and guest ions or molecules, are all potential sources of light emission. Temperature is one of the most important physical properties affecting the dynamics and viability of natural and engineered systems. Because the luminescence of certain lanthanide‐bearing MOFs changes considerably with temperature, in the last few years, these materials have been explored as optical thermometers, especially in temperature sensing based on the intensity ratios of two separate electronic transitions. This review discusses the main concepts and ideas assisting the design of such ratiometric thermometers, and identifies the main challenges presented to this nascent field: develop nanothermometers for bio‐applications and nanomedicine; understand the energy transfer mechanisms determining the thermal sensitivity; achieve effective primary thermometers; realize multifunctional nanothermometers; integrate Ln³⁺‐based thermometers in commercial products.     

Controllable Syntheses of Porous Metal–Organic Frameworks: Encapsulation of LnIII Cations for Tunable Luminescence and Small Drug Molecules for Efficient Delivery

Two porous metal–organic frameworks (MOFs), [Zn₃(L)(H₂O)₂] ? 3 DMF ? 7 H₂O ( MOF‐1 ) and [(CH₃)₂NH₂]₆[Ni₃(L)₂(H₂O)₆] ? 3 DMF ? 15 H₂O ( MOF‐2 ), were synthesized solvothermally (H₆L=1,2,3,4,5,6‐hexakis(3‐carboxyphenyloxymethylene)benzene). In MOF ‐ 1 , neighboring Zn^II trimers are linked by the backbones of L ligands to form a fascinating 3D six‐connected framework with the point symbol (4¹².6³) (4¹².6³). In MOF‐2 , eight L ligands bridge six Ni^II atoms to generate a rhombic‐dodecahedral [Ni₆L₈] cage. Each cage is surrounded by eight adjacent ones through sharing of carboxylate groups to yield an unusual 3D porous framework. Encapsulation of Ln^III cations for tunable luminescence and small drug molecules for efficient delivery were investigated in detail for MOF‐1 .     

A Highly Chemically Stable Metal–Organic Framework as a Luminescent Probe for the Regenerable Ratiometric Sensing of pH

A heteroatom‐rich 3D noninterpenetrating metal–organic framework (MOF) Cd‐EDDA constructed from an ethylene glycol ether bridging tetracarboxylate ligand H₄EDDA (5,5′‐(ethane‐1,2‐diylbis(oxy))diisophthalic acid) shows good chemical resistance to both acidic and alkaline solutions with a pH ranging from 2.0 to 12.2. There is a corresponding ratiometric luminescence response to pH from 2.0 to 11.5, and the sensing mechanism is also discussed through ion chromatography and molecular force field‐based calculations. Importantly, the probe can easily be regenerated simply by modulating the pH of the solution, thus being the first example of a regenerable MOF‐based ratiometric luminescent probe for pH.     

A Multi‐responsive Regenerable Europium–Organic Framework Luminescent Sensor for Fe3+, CrVI Anions,and Picric Acid

A novel luminescent microporous lanthanide metal–organic framework (Ln‐MOF) based on a urea‐containing ligand has been successfully assembled. Structural analysis revealed that the framework features two types of 1D channels, with urea N?H bonds projecting into the pores. Luminescence studies have revealed that the Ln‐MOF exhibits high sensitivity, good selectivity, and a fast luminescence quenching response towards Fe³⁺, Cr^VI anions, and picric acid. In particular, in the detection of Cr₂O₇^2? and picric acid, the Ln‐MOF can be simply and quickly regenerated, thus exhibiting excellent recyclability. To the best of our knowledge, this is the first example of a multi‐responsive luminescent Ln‐MOF sensor for Fe³⁺, Cr^VI anions, and picric acid based on a urea derivative. This Ln‐MOF may potentially be used as a multi‐responsive regenerable luminescent sensor for the quantitative detection of toxic and harmful substances.     

A Nanoscale Multiresponsive Luminescent Sensor Based on a Terbium(III) Metal–Organic Framework

A nanoscale terbium‐containing metal–organic framework ( nTbL ), with a layer‐like structure and [H₂NMe₂]⁺ cations located in the framework channels, was synthesized under hydrothermal conditions. The structure of the as‐prepared sample was systematically confirmed by powder XRD and elemental analysis; the morphology was characterized by field‐emission SEM and TEM. The photoluminescence studies revealed that rod‐like nTbL exhibited bright‐green emission, corresponding to ⁵D₄→⁷F_J (J=6–3) transitions of the Tb³⁺ ion under excitation. Further sensing measurements revealed that as‐prepared nTbL could be utilized as a multiresponsive luminescent sensor, which showed significant and exclusive detection ability for Fe³⁺ ions and phenylmethanol. These results highlight the practical applications of lanthanide‐containing metal–organic frameworks as fluorescent probes.     

Coordination Polymers: From Metal–Organic Frameworks to Spheres

Sphere of destiny : Metal–organic spheres with remarkable encapsulation properties are readily prepared and their ability to host a wide range of guest species, including nanoparticles, fluorescent dyes, and quantum dots, is demonstrated. Both the metal–organic spheres and the encapsulated species maintain their fluorescent or magnetic properties, highlighting the importance of these systems as new multifunctional materials.

     

Instant Visual Detection of Picogram Levels of Trinitrotoluene by Using Luminescent Metal–Organic Framework Gel‐Coated Filter Paper

There is an ongoing need for explosive detection strategies to uncover threats to human security including illegal transport and terrorist activities. The widespread military use of the explosive trinitrotoluene (TNT) for landmines poses another particular threat to human health in the form of contamination of the surrounding environment and groundwater. The detection of explosives, particularly at low picogram levels, by using a molecular sensor is seen as an important challenge. Herein, we report on the use of a fluorescent metal–organic framework hydrogel that exhibits a higher detection capability for TNT in the gel state compared with that in the solution state. A portable sensor prepared from filter paper coated by the hydrogel was able to detect TNT at the picogram level with a detection limit of 1.82 ppt (parts per trillon). Our results present a simple and new means to provide selective detection of TNT on a surface or in aqueous solution, as afforded by the unique molecular packing through the metal–organic framework structure in the gel formation and the associated photophysical properties. Furthermore, the rheological properties of the MOF‐based gel were similar to those of a typical hydrogel.     

A Bifunctional Luminescent Metal–Organic Framework for the Sensing of Paraquat and Fe3+ Ions in Water

The hydrothermal reaction of Zn²⁺ ions with a mixture of two ligands, Hcptpy and H₃btc (Hcptpy=4‐(4‐carboxyphenyl)‐2,2′:4′,4′′‐terpyridine; H₃btc=1,3,5‐benzenetricarboxylic acid), led to the formation of a 3D metal–organic framework (MOF) with 1D channels, [Zn₂(cptpy)(btc)(H₂O)]_n ( 1 ), which was structurally characterized by using single‐crystal X‐ray diffraction (SXRD). In MOF 1 , two independent Zn²⁺ ions were interconnected by btc^3? ligands to form a 1D chain, whilst adjacent Zn²⁺ ions were alternately bridged by cptpy^? ligands to generate a 2D sheet, which was further linked by 1D chains to form a 3D framework with a new (3,3,4,4)‐connected topology. Furthermore, compound 1 also exhibited excellent stability towards air and water and, more importantly, luminescence experiments indicated that it could serve as a probe for the sensitive detection of paraquat (PAQ) and Fe³⁺ ions in aqueous solution.     

A Robust Porous Metal–Organic Framework with a New Topology That Demonstrates Pronounced Porosity and High‐Efficiency Sorption/Selectivity Properties of Small Molecules

A robust porous metal–organic framework (MOF), [Co₃(ndc)(HCOO)₃(μ₃‐OH)(H₂O)]_n ( 1 ) (H₂ndc=5‐(4‐pyridyl)‐isophthalic acid), was synthesized with pronounced porosity. MOF 1 contained two different types of nanotubular channels, which exhibited a new topology with the Schlafli symbol of {4².6⁵.8³}{4².6}. MOF 1 showed high‐efficiency for the selective sorption of small molecules, including the energy‐correlated gases of H₂, CH₄, and CO₂, and environment‐correlated steams of alcohols, acetone, and pyridine. Gas‐sorption experiments indicated that MOF 1 exhibited not only a high CO₂‐uptake (25.1 wt % at 273 K/1 bar) but also the impressive selective sorption of CO₂ over N₂ and CH₄. High H₂‐uptake (2.04 wt % at 77 K/1 bar) was also observed. Moreover, systematic studies on the sorption of steams of organic molecules displayed excellent capacity for the sorption of the homologous series of alcohols (C₁–C₅), acetone, pyridine, as well as water.     

Effective and Selective Catalysts for Cinnamaldehyde Hydrogenation: Hydrophobic Hybrids of Metal–Organic Frameworks,Metal Nanoparticles,and Micro‐ and Mesoporous Polymers

Metal–organic frameworks (MOFs) as selectivity regulators for catalytic reactions have attracted much attention, especially MOFs and metal nanoparticle (NP) shelled structures, e.g., MOFs@NPs@MOFs. Nevertheless, making hydrophilic MOF shells for gathering hydrophobic reactants is challenging. Described here is a new and viable approach employing conjugated micro‐ and mesoporous polymers with iron(III) porphyrin (FeP‐CMPs) as a new shell to fabricate MIL‐101@Pt@FeP‐CMP. It is not only hydrophobic and porous for enriching reactants, but also possesses iron sites to activate C=O bonds, thereby regulating the selectivity for cinnamyl alcohol in the hydrogenation of cinnamaldehyde. Interestingly, MIL‐101@Pt@FeP‐CMP^sponge can achieve a high turnover frequency ( 1516.1 h^?1), with 97.3 % selectivity for cinnamyl alcohol at 97.6 % conversion.     

Solvatochromic Behavior of Chiral Mesoporous Metal–Organic Frameworks and Their Applications for Sensing Small Molecules and Separating Cationic Dyes

Two anionic metal–organic frameworks (MOFs) with 1D mesoporous tubes ( 1 ) and chiral mesoporous cages ( 2 ) have been rationally constructed by means of a predesigned size‐extended hexatopic ligand, namely, 5,5′,5′′‐(1,3,5‐triazine‐2,4,6‐triyl)tris‐ (azanediyl)triisophthalate (TATAT). Charge neutrality is achieved by protonated dimethylamine cations. Notably, the two MOFs can be used to separate large molecules based on ionic selectivity rather than the size‐exclusion effect so far reported in the literature. Owing to the imino triazine backbone and carboxyl groups of the hexatopic ligand, which provide important host–guest interactions, rare solvatochromic phenomena of 1 and 2 are observed on incorporating acetone and ethanol guests. Furthermore, guest‐dependent luminescence properties of compound 2 were investigated, and the results show that luminescence intensity is significantly enhanced in toluene and benzene, while quenching effects are observed in acetone and ethanol. Thus, compound 2 may be a potential material for luminescent probes.