Search Results (49)

Lanthanide-based metal–organic frameworks (Ln-MOFs) represent a key material in various optical applications. Thus, they offer the possibility of fine-tuning their functional properties by adjusting the composition, stoichiometry, and ligand nature. This work reports for the first time the environmentally friendly one-pot synthesis of Eu-Tb-doped yttrium-1,3,5-benzenetricarboxylate MOF, i.e., Y-BTC: Eu (10%), Tb (10%), under mild conditions of temperature and pressure. Structural and morphological investigations were conducted through ATR-IR, XRD, and FE-SEM characterization. The doping percentage was analyzed by EDX spectroscopy. The luminescence properties confirm the down-shifting behavior of the MOF, paving the way for using this Eu-Tb-doped Y-BTC system in photovoltaic technology. Full article

Coordination polymers [Gd₂(5-iip)₃(DMF)₄]·0.4DMF (1) and [Dy₂(5-iip)₃DMF₂]·0.33DMF (2) (5-iip²⁻—5-iodoisophthalate) feature two different structural types, as follows from X-ray diffractometry data. We prepared and characterized an extended series of corresponding heterometallic complexes of the composition [Gd_xDy_2−x(5-iip)₃DMF₂]·0.33DMF and [Eu_xDy_2−x(5-iip)₃DMF₂]·0.33DMF, where x = 0.2, 0.4…1.8, and examined the changes of their luminescent properties induced by variations of metal composition, finding the promising white emission sources with high light purity. Full article

Traditional barcode encoding methods are constrained by the inability to dynamically control crystal orientations, thereby limiting their applications. In this work, we investigate the dynamic magnetic control of lanthanide metal–organic framework crystals and their potential for advancing photonic barcode technology. A paramagnetic fluorescent Eu-MOF microcrystal with sizes ranging from 30 to 40 μm in length and 5 to 10 μm in width was synthesized, and its magnetic orientation and polarized emission were systematically investigated. Eu-MOF crystallizes in an orthorhombic space group, growing along the crystallographic b-axis and ultimately forming an anisotropic cuboid shape. Eu-MOF microcrystals exhibit significant magnetic anisotropy, causing the crystallographic c-axis of the crystal to align with the magnetic field when a uniaxial magnetic field of ~10 mT is applied. Furthermore, the Eu-MOF microcrystal exhibited characteristic Eu emissions with peaks at 594 nm, 616 nm, and 695 nm, and showed a high degree of polarization (DOP), reaching 0.904 at 616 nm. Therefore, the utilization of a rotating magnetic field not only enables precise and dynamic control over the crystal orientations but also results in a significant variation in the luminescence intensity. This capability enabled us to propose an innovative encryption barcode scheme in which the emission intensities of different luminescence peaks are converted into barcode widths, with the sequence of magnetic field directions serving as the encryption key. This approach presents a novel method for data storage and anti-counterfeiting, significantly enhancing the versatility and capacity of photonic barcodes. Full article

Hybrid compounds have a significant impact on agriculture as slow macro- and micronutrient administration systems. This study aimed to evaluate the synthesis and effect of the hybrid compound Nd(NO₃)₃@Zn-MOF in different concentrations on the in vitro growth of vanilla (Vanilla planifolia Jacks. ex Andrews). A total of 13 vanilla plantlets per treatment were cultivated in test tubes with semi-solid Murashige and Skoog (MS) medium and without growth regulators and treated with 0, 5, 10, 15, and 30 mg L⁻¹ of Nd(NO₃)₃@Zn-MOF. After 60 days of culture, we evaluated different morphological and biochemical parameters, such as shoot length, root length, the number of roots, the number of leaves, total chlorophyll and carotenoid content, antioxidant capacity, and phenolic compound content. Our results showed that the Nd(NO₃)₃@Zn-MOF at 10 mg L⁻¹ concentration increased plantlet length. Furthermore, we observed an increase in root length and number with the 5 and 10 mg L⁻¹ concentrations, and a decrease in these same parameters with the 15 and 30 mg L⁻¹ Nd(NO₃)₃@Zn-MOF concentrations. There were no significant differences regarding the number of leaves or total chlorophyll content. As for the antioxidant capacity, we observed an increase with 5, 10, and 15 mg L⁻¹ of Nd(NO₃)₃@Zn-MOF and a decrease with the highest concentration. Finally, the phenolic and carotenoid content decreased with the 15 and 30 mg L⁻¹ Nd(NO₃)₃@Zn-MOF concentrations compared to the control. In conclusion, the hybrid compound Nd(NO₃)₃@Zn-MOF showed beneficial effects on the growth, physiology, and biochemistry of V. planifolia in vitro when plants were treated at low concentrations. Additionally, the high concentrations used in this study did not induce toxicity. Our findings suggest that Nd(NO₃)₃@Zn-MOF could be used as a biostimulant in vanilla during its in vitro culture. However, due to the hormetic effect and the possible different reactions of different genotypes, this requires further detailed research. Full article

Eu/Tb metal–organic frameworks (Eu/Tb-MOFs), exhibiting Eu³⁺ and Tb³⁺ emissions, stand out as some of the most fascinating luminescent thermometers. As the relative thermal sensitivity model is limited to its lack of precision for fitting ratio of Eu³⁺ and Tb³⁺ emissions, accurately predicting the sensing performance of Eu/Tb-MOFs remains a significant challenge. Herein, we report a series of luminescent Eu/Tb-MOF thermometers, Eu_xTb_1−xL, with excellent thermal sensitivity around physiological levels, achieved through the tuning energy transfer from ligands to Eu³⁺ and Tb³⁺ and between the Ln ions. It was found that the singlet lowest-energy excited state (S₁) of the ligand and the higher triplet energy level (T_n) are crucial in the energy transfer processes of ligand→Tb³⁺ and ligand→Eu³⁺. This enables Eu_xTb_1−xL to serve as an effective platform for exploring the impact of these energy transfer processes on the temperature-sensing properties of luminescent Eu/Tb-MOF thermometers. The relative thermal sensitivity is comparable to that of dual-center MOF-based luminescent thermometers operating at physiological levels. This study provides valuable insights into the design of new Eu/Tb thermometers and the accurate prediction of their sensing performance. Full article

The solvothermal synthesis of LnCl₃^.nH₂O with terephthalic acid (benzene-1,4-dicarboxylic acid, H₂BDC) produced metal–organic frameworks (LnBDC), [Ln₂(BDC)₃(H₂O)₄]_∞, where Ln = Sm, Eu, Tb, and Dy. The materials obtained were characterized by a number of physico-chemical techniques. The influence of the ionic radius of the lanthanides on the microstructural characteristics of the Ln-MOFs was evaluated by performing Rietveld refinement. The MOFs obtained were tested as fluorescent sensors for numerous cations and anions in water. The highly luminescent EuBDC and TbBDC demonstrated multi-responsive luminescence sensing functions to detect Ag(I), Fe(III), Cr(III), and Cr(VI), which are essential for their environmental applications. By applying the non-linear Stern–Volmer equation, the fluorescent quenching mechanism was determined. The stability of the obtained materials in water in a wide pH range (acidity pH = 4 and alkalinity pH = 9 solutions) was confirmed. Full article

Lanthanide Metal–Organic Frameworks (LnMOFs), in recent years, have developed into an interesting subclass of MOFs. While the number of published papers, in particular, were dedicated to their synthesis and functional properties, along with the application mechanisms of MOFs, only a few of them have been focused on LnMOFs thin films independently. LnMOFs have become interesting thanks to their outstanding properties, for example, excellent structural flexibility, tunable pore size, surface area, functionality, and good chemical stability. Significant progress over the past two decades in the preparation of MOF films has been achieved, especially towards the development of green, or at least greener, synthesis approaches. We begin with insight into various types of MOFs and summarize recent achievements in the production of LnMOF films, along with various film preparation approaches. Afterward, we briefly discuss the applications of luminescence features of lanthanide ions in films and their potential as white-light source materials. We also covered films based on Eu, Tb, and Gd with particular accents on different design approaches. Moreover, specifically, luminescent features applied for sensing temperature, a variety of ions, gases, and biomolecules are highlighted. The review ends with a comprehensive conclusion about the state-of-art-potential of LnMOFs together with an outlook on the future of LnMOF films in future technologies. Full article

A series of novel 3D coordination polymers [Ln₂(Qdca)₃(H₂O)_x]·yH₂O (x = 3 or 4, y = 0–4) assembled from selected lanthanide ions (Ln(III) = Nd, Eu, Tb, and Er) and a non-explored quinoline-2,4-dicarboxylate building block (Qdca²⁻ = C₁₁H₅NO₄²⁻) were prepared under hydrothermal conditions at temperatures of 100, 120, and 150 °C. Generally, an increase in synthesis temperature resulted in structural transformations and the formation of more hydrated compounds. The metal complexes were characterized by elemental analysis, single-crystal and powder X-ray diffraction methods, thermal analysis (TG-DSC), ATR/FTIR, UV/Vis, and luminescence spectroscopy. The structural variety of three-dimensional coordination polymers can be ascribed to the temperature effect, which enforces the diversity of quinoline-2,4-dicarboxylate ligand denticity and conformation. The Qdca²⁻ ligand only behaves as a bridging or bridging–chelating building block binding two to five metal centers with seven different coordination modes arising mainly from different carboxylate group coordination types. The presence of water molecules in the structures of complexes is crucial for their stability. The removal of both coordinated and non-coordinated water molecules leads to the disintegration and combustion of metal–organic frameworks to the appropriate lanthanide oxides. The luminescence features of complexes, quantum yield, and luminescent lifetimes were measured and analyzed. Only the Eu complexes show emission in the VIS region, whereas Nd and Er complexes emit in the NIR range. The luminescence properties of complexes were correlated with the crystal structures of the investigated complexes. Full article

Lanthanide metal–organic frameworks (Ln-MOFs) showing single-molecule magnet (SMM) properties are an ever-growing family of materials where the magnetic properties can be tuned by various interrelated parameters, such as the coordinated solvent, temperature, organic linkers, lanthanide ions and their coordination environment. An overview of the general synthetic methodologies to access MOFs/Ln-MOFs and the peculiarities and parameters to control and/or fine-tune their SMM behavior is herein presented. Additionally, diverse challenging strategies for inducing SMM/SIM behavior in an Ln-MOF are discussed, involving redox activity and chirality. Furthermore, intriguing physical phenomena such as the CISS effect and CPL are also highlighted. Full article

Metal–organic frameworks (MOFs) have excellent applicability in several fields and have significant structural advantages, due to their open pore structure, high porosity, large specific surface area, and easily modifiable and functionalized porous surface. In addition, a variety of luminescent guest (LG) species can be encapsulated in the pores of MOFs, giving MOFs a broader luminescent capability. The applications of a variety of LG@MOF sensors, constructed by doping MOFs with LGs such as lanthanide ions, carbon quantum dots, luminescent complexes, organic dyes, and metal nanoclusters, for fluorescence detection of various target analyses such as ions, biomarkers, pesticides, and preservatives are systematically introduced in this review. The development of these sensors for portable visual fluorescence sensing applications is then covered. Finally, the challenges that these sectors currently face, as well as the potential for future growth, are briefly discussed. Full article

Luminescent, heterometallic terbium(III)–lutetium(III) terephthalate metal-organic frameworks (MOFs) were synthesized via direct reaction between aqueous solutions of disodium terephthalate and nitrates of corresponding lanthanides by using two methods: synthesis from diluted and concentrated solutions. For (Tb_xLu_1−x)₂bdc₃·nH₂O MOFs (bdc = 1,4-benzenedicarboxylate) containing more than 30 at. % of Tb³⁺, only one crystalline phase was formed: Ln₂bdc₃·4H₂O. At lower Tb³⁺ concentrations, MOFs crystallized as the mixture of Ln₂bdc₃·4H₂O and Ln₂bdc₃·10H₂O (diluted solutions) or Ln₂bdc₃ (concentrated solutions). All synthesized samples that contained Tb³⁺ ions demonstrated bright green luminescence upon excitation into the ¹ππ* excited state of terephthalate ions. The photoluminescence quantum yields (PLQY) of the compounds corresponding to the Ln₂bdc₃ crystalline phase were significantly larger than for Ln₂bdc₃·4H₂O and Ln₂bdc₃·10H₂O phases due to absence of quenching from water molecules possessing high-energy O-H vibrational modes. One of the synthesized materials, namely, (Tb_0.1Lu_0.9)₂bdc₃·1.4H₂O, had one of the highest PLQY among Tb-based MOFs, 95%. Full article

Fluoride ion (F⁻) is one of the most hazardous elements in potable water. Over intake of F⁻ can give rise to dental fluorosis, kidney failure, or DNA damage. As a result, developing affordable, equipment-free and credible approaches for F⁻ detection is an important task. In this work, a new three dimensional rare earth cluster-based metal-organic framework assembled from lanthanide Y(III) ion, and a linear multifunctional ligand 3-nitro-4,4′-biphenyldicarboxylic acid, formulated as {[Y(μ₃-OH)]₄[Y(μ₃-OH)(μ₂-H₂O)_0.25(H₂O)_0.5]₄[μ₄-nba]₈}_n (1), where H₂nba = 3-nitro-4,4′-biphenyldicarboxylic acid, has been hydrothermally synthesized and characterized through infrared spectroscopy (IR), elemental and thermal analysis (EA), power X-ray diffraction (PXRD), and single-crystal X-ray diffraction (SCXRD) analyses. X-ray diffraction structural analysis revealed that 1 crystallizes in tetragonal system with P$\overline{4}$2₁m space group, and features a 3D framework with 1D square 18.07(3)² Ų channels running along the [0,0,1] or c-axis direction. The structure of 1 is built up of unusual eight-membered rings formed by two types of {Y₄O₄} clusters connected to each other via 12 μ₄-nba²⁻ and 4 μ₃-OH⁻ ligands. Three crystallographic independent Y³⁺ ions display two coordinated configurations with a seven-coordinated distorted monocapped trigonal-prism (YO₇) and an eight-coordinated approximately bicapped trigonal-prism (YO₈). 1 is further stabilized through O-H⋯O, O-H⋯N, C-H⋯O, and π⋯π interactions. Topologically, MOF 1 can be simplified as a 12-connected 2-nodal Au₄Ho topology with a Schläfli symbol {4²⁰·6²⁸·8¹⁸}{4³}₄ or a 6-connected uninodal pcu topology with a Schläfli symbol {4¹²·6³}. The fluorescent sensing application of 1 was investigated to cations and anions in H₂O. 1 exhibits good luminescence probing turn-on recognition ability toward F⁻ and with a limit detection concentration of F⁻ down to 14.2 μM in aqueous solution (K_ec = 11403 M⁻¹, R² = 0.99289, σ = 0.0539). The findings here provide a feasible detection platform of LnMOFs for highly sensitive discrimination of F⁻ in aqueous media. Full article

Just-in-time evaluation of drug resistance in situ will greatly facilitate the achievement of precision cancer therapy. The rapid elevation of reactive oxygen species (ROS) is the key to chemotherapy. Hence, suppressed ROS production is an important marker for chemotherapy drug resistance. Herein, a NIR-II emission smart nanoprobe (LnNP@ZIF8, consisting of a lanthanide-doped nanoparticle (LnNP) core and metal-organic framework shell (ZIF8)) is constructed for drug delivery and in vivo NIR-II ratiometric imaging of ROS for tumor drug resistance evaluation. The drug-loaded nanoprobes release therapeutic substances for chemotherapy in the acidic tumor tissue. As the level of ROS increases, the LnNPs shows responsively descending fluorescence intensity at 1550 nm excited by 980 nm (F1550, 980Ex), while the fluorescence of the LnNPs at 1060 nm excited by 808 nm (F1060, 808Ex) is stable. Due to the ratiometric F1550, 980Ex/F1060, 808Ex value exhibiting a linear relationship with ROS concentration, NIR-II imaging results of ROS change based on this ratio can be an important basis for determining tumor drug resistance. As the chemotherapy and resistance evaluation are explored continuously in situ, the ratiometric imaging identifies drug resistance successfully within 24 h, which can greatly improve the timeliness of accurate treatment. Full article

Formic acid is a common chemical raw material, the effective detection of which is of importance to food safety and environmental quality. In this work, the lanthanide functionalized dual-emission metal-organic framework (TH25) was prepared as a ratiometric fluorescent sensor for formic acid. This ratiometric sensor has a good detection performance with high selectivity, sensitivity, and reproducibility. Together with a low limit of detection of 2.1 ppm, these characters promise the ability to sense at low levels as well as a practical detection ability. This work provides ideas for the design and synthesis of effective chemical sensors for organic acids. Full article

A coordination polymer has been synthesized using ferrocene-based ligand-bearing phosphinic groups of 1,1′-ferrocene-diyl-bis(H-phosphinic acid)), and samarium (III). The coordination polymer’s structure was studied by both single-crystal and powder XRD, TG, IR, and Raman analyses. For the first time, the Mössbauer effect studies were performed on ferrocenyl phosphinate and the polymer based on it. Additionally, the obtained polymer was studied by the method of cyclic and differential pulse voltammetry. It is shown that it has the most positive potential known among ferrocenyl phosphinate-based coordination polymers and metal–organic frameworks. Using the values of the oxidation potential, the polymer was oxidized and the ESR method verified the oxidized Fe(III) form in the solid state. Additionally, the effect of the size of the phosphorus atom substituent of the phosphinate group on the dimension of the resulting coordination compounds is shown. Full article