Tuning Mixed‐Valent Eu2+/Eu3+ in Strontium Formate Frameworks for Multichannel Photoluminescence

Cooperative performance of mixed‐valent Eu²⁺/Eu³⁺ in single‐compound phosphors offers significant advantages in color rendering and luminescence efficiency, but their synthesis is challenging because of Eu²⁺ oxidation. Using the tunable nature of the metal‐ion nodes in metal–organic frameworks (MOFs), we present an in situ reduction and crystallization route for preparing MOFs and doping Eu²⁺/Eu³⁺ with a controlled ratio. These materials exhibit rich photoluminescence, including intrinsic‐ and sensitized‐emissions of Eu²⁺ and Eu³⁺, and long‐lived luminescence from charge transfer. Color rendering can be easily achieved by fine‐tuning the valence states of Eu. A linear relation between temperature and the intensity ratio of Eu²⁺/Eu³⁺ emissions provides outstanding properties for applications as self‐calibrated luminescent thermometers with a wide working temperature range. Further incorporation of Tb³⁺ into the MOFs results in white light, utilizing all Eu²⁺,Tb³⁺, and Eu³⁺ emissions in a single crystalline lattice.     

Luminescence‐Functionalized Metal–Organic Frameworks Based on a Ruthenium(II) Complex: A Signal Amplification Strategy for Electrogenerated Chemiluminescence Immunosensors

Novel luminescence‐functionalized metal–organic frameworks (MOFs) with superior electrogenerated chemiluminescence (ECL) properties were synthesized based on zinc ions as the central ions and tris(4,4′‐dicarboxylicacid‐2,2′‐bipyridyl)ruthenium(II) dichloride ([Ru(dcbpy)₃]²⁺) as the ligands. For potential applications, the synthesized MOFs were used to fabricate a “signal‐on” ECL immunosensor for the detection of N‐terminal pro‐B‐type natriuretic peptide (NT‐proBNP). As expected, enhanced ECL signals were obtained through a simple fabrication strategy because luminescence‐functionalized MOFs not only effectively increased the loading of [Ru(dcbpy)₃]²⁺, but also served as a loading platform in the ECL immunosensor. Furthermore, the proposed ECL immunosensor had a wide linear range from 5 pg mL^?1 to 25 ng mL^?1 and a relatively low detection limit of 1.67 pg mL^?1 (signal/noise=3). The results indicated that luminescence‐functionalized MOFs provided a novel amplification strategy in the construction of ECL immunosensors and might have great prospects for application in bioanalysis.     

Upconversion Luminescence through Cooperative and Energy-Transfer Mechanisms in Yb3+-Metal-Organic Frameworks

Lanthanide-doped metal–organic frameworks (Ln-MOFs) have versatile luminescence properties, however it is challenging to achieve lanthanide-based upconversion luminescence in these materials. Here, 1,3,5-benzenetricarboxylic acid (BTC) and trivalent Yb³⁺ ions were used to generate crystalline Yb-BTC MOF 1D-microrods with upconversion luminescence under near infrared excitation via cooperative luminescence. Subsequently, the Yb-BTC MOFs were doped with a variety of different lanthanides to evaluate the potential for Yb³⁺-based upconversion and energy transfer. Yb-BTC MOFs doped with Er³⁺, Ho³⁺, Tb³⁺, and Eu³⁺ ions exhibit both the cooperative luminescence from Yb³⁺ and the characteristic emission bands of these ions under 980 nm irradiation. In contrast, only the 497 nm upconversion emission band from Yb³⁺ is observed in the MOFs doped with Tm³⁺, Pr³⁺, Sm³⁺, and Dy³⁺. The effects of different dopants on the efficiency of cooperative luminescence were established and will provide guidance for the exploitation of Ln-MOFs exhibiting upconversion.     

Nanothermometry: From Microscopy to Thermal Treatments

Measuring temperature in cells and tissues remotely, with sufficient sensitivity, and in real time presents a new paradigm in engineering, chemistry and biology. Traditional sensors, such as contact thermometers, thermocouples, and electrodes, are too large to measure the temperature with subcellular resolution and are too invasive to measure the temperature in deep tissue. The new challenge requires novel approaches in designing biocompatible temperature sensors—nanothermometers—and innovative techniques for their measurements. In the last two decades, a variety of nanothermometers whose response reflected the thermal environment within a physiological temperature range have been identified as potential sensors. This review covers the principles and aspects of nanothermometer design driven by two emerging areas: single‐cell thermogenesis and image guided thermal treatments. The review highlights the current trends in nanothermometry illustrated with recent representative examples.     

The Series of Rare Earth Complexes [Ln2Cl6(μ‐4,4′‐bipy)(py)6], Ln=Y,Pr, Nd,Sm‐Yb: A Molecular Model System for Luminescence Properties in MOFs Based on LnCl3 and 4,4′‐Bipyridine

A series of 12 dinuclear complexes [Ln₂Cl₆(μ‐4,4′‐bipy)(py)₆], Ln=Y, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, ( 1 – 12 , respectively) was synthesized by an anhydrous solvothermal reaction in pyridine. The complexes contain a 4,4′‐bipyridine bridge and exhibit a coordination sphere closely related to luminescent lanthanide MOFs based on LnCl₃ and 4,4‐bipyridine. The dinuclear complexes therefore function as a molecular model system to provide a better understanding of the luminescence mechanisms in the Ln‐N‐MOFs ${\hbox{}{{\hfill 2\atop \hfill \infty }}}$ [Ln₂Cl₆(4,4′‐bipy)₃] ? 2(4,4′‐bipy). Accordingly, the luminescence properties of the complexes with Ln=Y, Sm, Eu, Gd, Tb, Dy, ( 1 , 4 – 8 ) were determined, showing an antenna effect through a ligand–metal energy transfer. The highest efficiency of luminescence is observed for the terbium‐based compound 7 displaying a high quantum yield (QY of 86 %). Excitation with UV light reveals typical emission colors of lanthanide‐dependent intra 4f–4f‐transition emissions in the visible range (Tb^III: green, Eu^III: red, Sm^III: salmon red, Dy^III: yellow). For the Gd^III‐ and Y^III‐containing compounds 6 and 1 , blue emission based on triplet phosphorescence is observed. Furthermore, ligand‐to‐metal charge‐transfer (LMCT) states, based on the interaction of Cl^? with Eu^III, were observed for the Eu^III compound 5 including energy‐transfer processes to the Eu^III ion. Altogether, the model complexes give further insights into the luminescence of the related MOFs, for example, rationalization of Ln‐independent quantum yields in the related MOFs.     

Luminescence Tuning and White‐Light Emission of Co‐doped Ln–Cd–Organic Frameworks

Four new three‐dimensional isostructural lanthanide–cadmium metal–organic frameworks (Ln–Cd MOFs), [LnCd₂(imdc)₂(Ac)(H₂O)₂]?H₂O (Ln=Pr ( 1 ), Eu ( 2 ), Gd ( 3 ), and Tb ( 4 ); H₃imdc=4,5‐imidazoledicarboxylic acid; Ac=acetate), have been synthesized under hydrothermal conditions and characterized by IR, elemental analyses, inductively coupled plasma (ICP) analysis, and X‐ray diffraction. Single‐crystal X‐ray diffraction shows that two Ln^III ions are surrounded by four Cd^II ions to form a heteronuclear building block. The blocks are further linked to form 3D Ln–Cd MOFs by the bridging imdc^3? ligand. Furthermore, the left‐ and right‐handed helices array alternatively in the lattice. Eu–Cd and Tb–Cd MOFs can emit characteristic red light with the Eu^III ion and green light with the Tb^III ion, respectively, while both Gd–Cd and Pr–Cd MOFs generate blue emission when they are excited. Different concentrations of Eu³⁺ and Tb³⁺ ions were co‐doped into Gd–Cd/Pr–Cd MOFs, and tunable luminescence from yellow to white was achieved. White‐light emission was obtained successfully by adjusting the excitation wavelength or the co‐doping ratio of the co‐doped Gd–Cd and Pr–Cd MOFs. These results show that the relative emission intensity of white light for Gd–Cd:Eu³⁺,Tb³⁺ MOFs is stronger than that of Pr–Cd:Eu³⁺,Tb³⁺ MOFs, which implies that the Gd complex is a better matrix than the Pr complex to obtain white‐light emission materials.     

Bismuth(III) based Metal Organic Frameworks: Luminescence,Gas Adsorption,and Antibacterial Studies

Bi^III‐MOFs 1 – 4 were prepared via solvothermal method using four organic linkers; 2‐mercapto‐3‐methyl‐4‐thiazoleacetic acid (H₂MMTA), 2,6‐naphthalenedicarboxylic acid (2,6‐NDA), 4,6‐dihydroxy‐2‐mercaptopyrimidine (H₂DMP), and 4‐mercaptobenzoic acid (H₂MBA), respectively. The resulting MOFs were structurally/morphologically characterized by UV/Vis, AAS/ICP‐MS, Fourier transform infrared spectroscopy (FT‐IR), ¹H NMR, thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and powder X‐ray diffraction technique. All these MOFs showed good luminescence properties exhibiting blue luminescence. N₂ gas adsorption isotherms of 1 – 4 confirmed the porosity of these frameworks. In order to evaluate the effect of metal ion upon chelation, the free organic linkers and respective MOFs were screened for their antibacterial potential against some pathogenic bacteria and appreciable activity was observed.     

Developing Luminescent Ratiometric Thermometers Based on a Covalent Organic Framework (COF)

Covalent Organic Frameworks (COFs), an emerging class of crystalline porous materials, are proposed as a new type of support for grafting lanthanide ions (Ln³⁺) and employing these hybrid materials as ratiometric luminescent thermometers. A TpBpy‐COF—prepared from 1,3,5‐triformylphloroglucinol (Tp) and 2,2′‐bipyridine‐5,5′‐diamine (Bpy) grafted with Eu/Tb and Dy acetylacetone (acac) complexes can be successfully used as a luminescent thermometer in the 10–360 K (Eu) and 280–440 K (Tb) ranges with good sensing properties (thermal sensitivity up to 1.403 % K^?1, temperature uncertainty δT<1 K above 110 K). For the Eu/Tb systems, we observe an unusual and rarely reported behavior, that is, no thermal quenching of the Tb³⁺ emission, a result of the absence of ion‐to‐ligand/host energy back‐transfer. The LnCOF materials proposed here could be a new class of materials employed for temperature‐sensing applications following up on the well‐known luminescent metal–organic framework thermometers.     

Lithium‐Doped Silica‐Rich MIL‐101(Cr) for Enhanced Hydrogen Uptake

Metal‐organic frameworks (MOFs) show promising characteristics for hydrogen storage application. In this direction, modification of under‐utilized large pore cavities of MOFs has been extensively explored as a promising strategy to further enhance the hydrogen storage properties of MOFs. Here, we described a simple methodology to enhance the hydrogen uptake properties of RHA incorporated MIL‐101 (RHA‐MIL‐101, where RHA is rice husk ash—a waste material) by controlled doping of Li⁺ ions. The hydrogen gas uptake of Li‐doped RHA‐MIL‐101 is significantly higher (up to 72 %) compared to the undoped RHA‐MIL‐101, where the content of Li⁺ ions doping greatly influenced the hydrogen uptake properties. We attributed the observed enhancement in the hydrogen gas uptake of Li‐doped RHA‐MIL‐101 to the favorable Li⁺ ion‐to‐H₂ interactions and the cooperative effect of silanol bonds of silica‐rich rice‐husk ash incorporated in MIL‐101.     

A Highly Sensitive and Recyclable Ln‐MOF Luminescent Sensor for the Efficient Detection of Fe3+ and CrVI Anions

Two new three‐dimensional (3D) Ln^III metal‐organic frameworks (MOFs) were designed and successfully obtained via a solvothermal reaction between lanthanide(III) nitrates and a semi‐flexible carbazole tetracarboxylate acid linker as a high‐performance chromophore. 1 and 2 possess porous 3D networks with channels along the a axis, and more importantly, they show a highly sensitive and selective fluorescence quenching response to Fe³⁺ and Cr^VI anions. The sensing mechanism investigation revealed that the weak interactions of Fe³⁺ with nitrogen atoms of carbazole and deprotonated carboxylic acids protruding into the pores of MOFs quenched the luminescence of 1 and 2 effectively. In addition, the competition absorption also played an important role in the luminescence quenching detection of Fe³⁺ based on 1 , and Cr^VI anions based on 1 and 2 . Therefore, 1 and 2 represent an alternative example of regenerable luminescence based sensors for the quantitative detection of Fe³⁺ and Cr^VI anions.     

Template‐Directed Approach Towards the Realization of Ordered Heterogeneity in Bimetallic Metal–Organic Frameworks

Controlling the arrangement of different metal ions to achieve ordered heterogeneity in metal–organic frameworks (MOFs) has been a great challenge. Herein, we introduce a template‐directed approach, in which a 1D metal–organic polymer incorporating well‐defined binding pockets for the secondary metal ions used as a structural template and starting material for the preparation of well‐ordered bimetallic MOF‐74s under heterogeneous‐phase hydrothermal reaction conditions in the presence of secondary metal ions such as Ni²⁺ and Mg²⁺ in 3 h. The resulting bimetallic MOF‐74s were found to possess a nearly 1:1 metal ratio regardless of their initial stoichiometry in the reaction mixture, thus demonstrating the possibility of controlling the arrangement of metal ions within the secondary building blocks in MOFs to tune their intrinsic properties such as gas affinity.     

Optimization of Reaction Conditions towards Multiple Types of Framework Isomers and Periodic‐Increased Porosity: Luminescence Properties and Selective CO2 Adsorption over N2

Three new metal‐organic frameworks (MOFs) were prepared by solvo(hydro)thermolysis and further characterized as framework isomers. The structural transformation from non‐porous to porous MOFs and the purity of these products can be modulated by controlling the reaction temperature. The periodic‐increased porosity observed was further confirmed by CO₂ adsorption isotherms. Owing to the presence of acylamide groups in the pore walls and the flexible nature of the skeleton of these MOFs, highly selective CO₂ adsorption over N₂ was observed, as well as structure‐dependent periodic varieties in luminescence properties.     

Photophysical Properties of Lanthanide (Eu3+, Tb3+) Hybrid Soft Gels of Double Functional Linker of Ionic Liquid–Modified Silane

Four kinds of luminescent hybrid soft gels have been assembled by introducing the lanthanide (Eu³⁺, Tb³⁺) tetrakis β‐diketonate into the covalently bonded imidazolium‐based silica through electrostatic interactions. Here, the imidazolium‐based silica matrices are prepared from imidazolium‐derived organotriethoxysilanes by the sol–gel process, in which the imidazolium cations are strongly anchored within the silica matrices while anions can still be exchanged following application for functionalization of lanthanide complexes. The photoluminescence measurements indicated that these hybrid soft gels exhibit characteristic red and green luminescence originating from the corresponding ternary lanthanide ions (Eu³⁺, Tb³⁺). Further investigation of photophysical properties reveals that these soft gels have inherited the outstanding luminescent properties from the lanthanide tetrakis β‐diketonate complexes such as strong luminescence intensities, long lifetimes and high luminescence quantum efficiencies.     

Divalent Europium Nanocrystals: Controllable Synthesis,Properties, and Applications

Magnetic and luminescent bifunctional divalent europium nanocrystals (Eu²⁺ NCs) are a promising class of novel advanced materials that have various applications in magneto‐optic devices, catalysis, bioimaging, and solar cells. In the past few decades, much work has been carried out to study the synthesis, properties, and applications of Eu²⁺ NCs. The aim of this Minireview is to present the progress in preparing Eu²⁺ NCs based on the reported research, by describing the advantages and disadvantages of the synthesis methods. The morphologies and size are controlled through adjusting the experimental conditions. Eu²⁺ NCs show superior magnetic and luminescence properties simultaneously. Self‐assembly and doping with other ions are important routes to improve their magnetic and luminescence properties. Their applications in magneto‐optic devices are discussed. Some difficulties and challenges in the fabrication of Eu²⁺ NCs are discussed, such as water‐soluble Eu²⁺ NCs and tunable luminescence in the whole visible region.     

Synthesis of Multifunctional Mn‐Doped CdTe/ZnS Core/Shell Quantum Dots

The synthesis of a novel water‐soluble Mn‐doped CdTe/ZnS core‐shell quantum dots using a proposed ultrasonic assistant method and 3‐mercaptopropionic acid (MPA) as stabilizer is descried. To obtain a high luminescent intensity, post‐preparative treatments, including the pH value, reaction temperature, reflux time and atmosphere, have been investigated. For an excellent fluorescence of Mn‐doped CdTe/ZnS, the optimal conditions were pH 11, reflux temperature 100°C and reflux time 3 h under N₂ atmosphere. While for phosphorescent Mn‐doped CdTe/ZnS QDs, the synthesis at pH 11, reflux temperature 100°C and reflux time 3 h under air atmosphere gave the best strong phosphorescence. The characterizations of Mn‐doped CdTe/ZnS QDs were also identified using AFM, IR, powder XRD and thermogravimetric analysis. The data indicated that the photochemical stability and the photoluminescence of CdTe QDs are greatly enhanced by the outer inorganic ZnS shell, and the doping Mn²⁺ ions in the as‐prepared quantum dots contribute to strong luminescence. The strong luminescence of Mn‐doped CdTe/ZnS QDs reflected that Mn ions act as recombination centers for the excited electron‐hole pairs, attributing to the transition from the triplet state (⁴T₁) to the ground state (⁶A₁) of the Mn²⁺ ions. All the experiments demonstrated that the surface states played important roles in the optical properties of Mn‐doped CdTe/ZnS core‐shell quantum dots.     

A self‐penetrated three‐dimensional zinc(II) coordination framework based on 4,4′,4′′‐(1,3,5‐triazine‐2,4,6‐triyl)tribenzoic acid and 1,3‐bis[(imidazol‐1‐yl)methyl]benzene ligands: synthesis,structure and properties

With the rapid development of metal–organic frameworks (MOFs), a variety of MOFs and their derivatives have been synthesized and reported in recent years. Commonly, multifunctional aromatic polycarboxylic acids and nitrogen‐containing ligands are employed to construct MOFs with fascinating structures. 4,4′,4′′‐(1,3,5‐Triazine‐2,4,6‐triyl)tribenzoic acid (H₃TATB) and the bidentate nitrogen‐containing ligand 1,3‐bis[(imidazol‐1‐yl)methyl]benzene (bib) were selected to prepare a novel Zn^II‐MOF under solvothermal conditions, namely poly[[tris{μ‐1,3‐bis[(imidazol‐1‐yl)methyl]benzene}bis[μ₃‐4,4′,4′′‐(1,3,5‐triazine‐2,4,6‐triyl)tribenzoato]trizinc(II)] dimethylformamide disolvate trihydrate], {[Zn₃(C₂₄H₁₂N₃O₆)₂(C₁₄H₁₄N₄)₃]·2C₃H₇NO·3H₂O}_n ( 1 ). The structure of 1 was characterized by single‐crystal X‐ray diffraction, IR spectroscopy and powder X‐ray diffraction. The properties of 1 were investigated by thermogravimetric and fluorescence analysis. Single‐crystal X‐ray diffraction shows that 1 belongs to the monoclinic space group Pc. The asymmetric unit contains three crystallographically independent Zn^II centres, two 4,4′,4′′‐(1,3,5‐triazine‐2,4,6‐triyl)tribenzoate (TATB^3?) anions, three complete bib ligands, one and a half free dimethylformamide molecules and three guest water molecules. Each Zn^II centre is four‐coordinated and displays a distorted tetrahedral coordination geometry. The Zn^II centres are connected by TATB^3? anions to form an angled ladder chain with large windows. Simultaneously, the bib ligands link Zn^II centres to give a helical Zn–bib–Zn chain. Furthermore, adjacent ladders are bridged by Zn–bib–Zn chains to form a fascinating three‐dimensional self‐penetrated framework with the short Schläfli symbol 6⁵·7·8¹³·9·10. In addition, the luminescence properties of 1 in the solid state and the fluorescence sensing of metal ions in suspension were studied. Significantly, compound 1 shows potential application as a fluorescent sensor with sensing properties for Zr⁴⁺ and Cu²⁺ ions.     

Design and Synthesis of a Water‐Stable Anionic Uranium‐Based Metal–Organic Framework (MOF) with Ultra Large Pores

Ionic metal–organic frameworks (MOFs) are a subclass of porous materials that have the ability to incorporate different charged species in confined nanospace by ion‐exchange. To date, however, very few examples combining mesoporosity and water stability have been realized in ionic MOF chemistry. Herein, we report the rational design and synthesis of a water‐stable anionic mesoporous MOF based on uranium and featuring tbo‐type topology. The resulting tbo MOF exhibits exceptionally large open cavities (3.9 nm) exceeding those of all known anionic MOFs. By supercritical CO₂ activation, a record‐high Brunauer‐Emmett‐Teller (BET) surface area (2100 m² g^?1) for actinide‐based MOFs has been obtained. Most importantly, however, this new uranium‐based MOF is water‐stable and able to absorb positively charged ions selectively over negatively charged ones, enabling the efficient separation of organic dyes and biomolecules.     

Clicked Isoreticular Metal–Organic Frameworks and Their High Performance in the Selective Capture and Separation of Large Organic Molecules

Three highly porous metal–organic frameworks (MOFs) with a uniform rht‐type topological network but hierarchical pores were successfully constructed by the assembly of triazole‐containing dendritic hexacarboxylate ligands with Zn^II ions. These transparent MOF crystals present gradually increasing pore sizes upon extension of the length of the organic backbone, as clearly identified by structural analysis and gas‐adsorption experiments. The inherent accessibility of the pores to large molecules endows these materials with unique properties for the uptake of large guest molecules. The visible selective adsorption of dye molecules makes these MOFs highly promising porous materials for pore‐size‐dependent large‐molecule capture and separation.     

Design of Fluorescent Nanocapsules as Ratiometric Nanothermometers

We have developed a novel design of optical nanothermometers that can measure the surrounding temperature in the range of 20–85 °C. The nanothermometers comprise two organic fluorophores encapsulated in a crosslinked polymethacrylate nanoshell. The role of the nanocapsule shell around the fluorophores is to form a well‐defined and stable microenvironment to prevent other factors besides temperature from affecting the dyes’ fluorescence. The two fluorophores feature different temperature‐dependent emission profiles; a fluorophore with relatively insensitive fluorescence (rhodamine 640) serves as a reference whereas a sensitive fluorophore (indocyanine green) serves as a sensor. The sensitivity of the nanothermometers depends on the type of nanocapsule‐forming lipid and is affected by the phase transition temperature. Both the fluorescence intensity and the fluorescence lifetime can be utilized to measure the temperature.     

Multiple Active Sites: Lithium Storage Mechanism of Cu‐TCNQ as an Anode Material for Lithium‐Ion Batteries

Recently, carboxylate metal‐organic framework (MOF) materials were reported to perform well as anode materials for lithium‐ion batteries (LIBs); however, the presumed lithium storage mechanism of MOFs is controversial. To gain insight into the mechanism of MOFs as anode materials for LIBs, a self‐supported Cu‐TCNQ (TCNQ: 7,7,8,8‐tetracyanoquinodimethane) film was fabricated via an in situ redox routine, and directly used as electrode for LIBs. The first discharge and charge specific capacities of the self‐supported Cu‐TCNQ electrode are 373.4 and 219.4 mAh g^?1, respectively. After 500 cycles, the reversible specific capacity of Cu‐TCNQ reaches 280.9 mAh g^?1 at a current density of 100 mA g^?1. Mutually validated data reveal that the high capacity is ascribed to the multiple‐electron redox conversion of both metal ions and ligands, as well as the reversible insertion and desertion of Li⁺ ions into the benzene rings of ligands. This work raises the expectation for MOFs as electrode materials of LIBs by utilizing multiple active sites and provides new clues for designing improved electrode materials for LIBs.