Search Results (7)

Optimizing lanthanide catalyst performance with organic ligands often encounters significant challenges, including susceptibility to water or oxygen and complex synthesis pathways. To address these issues, our research focuses on developing inorganic lanthanide clusters with enhanced stability and functionality. In this study, we introduce the [Sm₆O(OH)₈(H₂O)₂₄]I₈(H₂O)₈ cluster (Sm-OC) as a sustainable and efficient catalyst for the aerobic oxidation of thiols under heating conditions. The Sm-OC catalyst demonstrated remarkable stability, outstanding recyclability, and excellent chemoselectivity across a diverse range of functional groups in 38 different tests. Notably, it enables efficient unsymmetrical disulfide synthesis and prevents the formation of over-oxidized by-products, highlighting its superior performance. This Sm-OC catalyst provides a practical and robust tool for the precise construction of versatile disulfides, thus establishing a template for the broader use of lanthanide clusters in organic synthesis. Full article

Two enantiomeric pairs of new 3d–4f heterometallic clusters have been synthesized from two enantiomer Schiff base derivatives: (R/S)-2-[(2-hydroxy-1-phenylethylimino)methyl] phenol (R-/S-H₂L). The formulae of the series clusters are Co₃Ln(R-L)₆ (Ln = Dy (1R), Gd (2R)), Co₃Ln (S-L)₆ (Ln = Dy (1S), Gd (2S)), whose crystal structures and magnetic properties have been characterized. Structural analysis indicated that the above clusters crystallize in the chiral P2₁3 group space. The central lanthanide ion has a coordination geometry of D₃ surrounded by three [Co^III(L)₂]^– anions using six aliphatic oxygen atoms of L²⁻ featuring a star-shaped [Co^III₃Ln^III] configuration. Magnetic measurements showed the presence of slow magnetic relaxation with an effective energy barrier of 22.33 K in the Dy^III derivatives under a zero-dc field. Furthermore, the circular dichroism (CD) spectra of 1R and 1S confirmed their enantiomeric nature. Full article

Heptanuclear {Gd^III₇} (complex 1) and tetradecanuclear {Gd^III₁₄} (complex 2) were synthesized using the rhodamine 6G ligand HL (rhodamine 6G salicylaldehyde hydrazone) and characterized. Complex 1 has a rare disc-shaped structure, where the central Gd ion is connected to the six peripheral Gd^III ions via CH₃O⁻/μ₃-OH⁻ bridges. Complex 2 has an unexpected three-layer double sandwich structure with a rare μ₆-O²⁻ ion in the center of the cluster. Magnetic studies revealed that complex 1 exhibits a magnetic entropy change of 17.4 J kg⁻¹ K⁻¹ at 3 K and 5 T. On the other hand, complex 2 shows a higher magnetic entropy change of 22.3 J kg⁻¹ K⁻¹ at 2 K and 5 T. Full article

We successfully synthesized millimeter-sized single crystals of the molecular erbium(III) complex Er(acac)₃(cphen), where acac = acetylacetonate and cphen = 5-chloro-1,10-phenanthroline. The novelty of this work stems from the exhaustive examination of the polar and electronic properties of the obtained samples at the macro-, micro-, and nanoscale levels. The single crystal X-ray diffraction method demonstrates the monoclinic (noncentrosymmetric space group P2₁) crystallographic structure of the synthesized samples and scanning electron microscopy exhibits the terrace–ledge morphology of the surface in erbium(III) crystals. By using the piezoelectric force microscopy mode, the origin of the polar properties and the hyperpolarizability in the synthesized samples were assigned to the internal domain structure framed by the characteristic terrace–ledge topography. The direct piezoelectric coefficient (~d33) was found to be intensely dependent on the local area and was measured in the range of 4–8 pm/V. A nanoscale study using the kelvin probe force and capacitance force (dC/dz) microscopy modes exposed the effect of the Er ions clustering in the erbium(III) complex. The PFM method applied solely to the Er ion revealed the corresponding direct piezoelectric coefficient (~d33) of about 4 pm/V. Given the maximum piezoelectric coefficient in the erbium(III) complex at 8 pm/V, we highlight the significant importance of the spatial coordination between the lanthanide ion and the ligands. The polar coordination between the lanthanide ion and the nitrogen and oxygen atoms was also corroborated by Raman spectroscopy supported by the density functional theory calculations. The obtained results can be of paramount importance for the application of molecular erbium(III) complex crystals in low-magnitude magnetic or electric field devices, which would reduce the energy consumption and speed up the processing switching in nonvolatile memory devices. Full article

The low absorption of biological substances and living tissues in the red/near-infrared region (therapeutic window) makes luminophores emitting in the range of ~650–1350 nm favorable for in vitro and in vivo imaging. In contrast to commonly used organic dyes, inorganic red/NIR emitters, including ruthenium complexes, quantum dots, lanthanide compounds, and octahedral cluster complexes of molybdenum and tungsten, not only exhibit excellent emission in the desired region but also possess additional functional properties, such as photosensitization of the singlet oxygen generation process, upconversion luminescence, photoactivated effects, and so on. However, despite their outstanding functional applicability, they share the same drawback—instability in aqueous media under physiological conditions, especially without additional modifications. One of the most effective and thus widely used types of modification is incorporation into silica, which is (1) easy to obtain, (2) biocompatible, and (3) non-toxic. In addition, the variety of morphological characteristics, along with simple surface modification, provides room for creativity in the development of various multifunctional diagnostic/therapeutic platforms. In this review, we have highlighted biomedical applications of silica-based materials containing red/NIR-emitting compounds. Full article

The incorporation of rare-earth ions into polymer matrices can lead to useful materials in various fields such as biomarkers, lasers, luminescent devices, optical storage materials, and so on. Methods of incorporation are either extremely simple, such as mixing the polymer and the ion of interest in adequate solvents, or more sophisticated such as synthesizing predesigned monomers that contain the rare-earth ion or binding the ion on an already formed polymer chain. Cationic gemini surfactants represent a class of surfactants that can be used to incorporate metal-oxygen cluster compounds by means of strong electrostatic interactions. In this study, first, a novel cationic gemini surfactant having double bonds on both side chains was designed and prepared. After characterization, the surfactant was used to synthesize hydrogels with different degrees of crosslinking and also as a surfmer in emulsion polymerization of methyl methacrylate. The resulted polymer matrices were able to bind europium-polyoxometalate Na₉[EuW₁₀O₃₆]^.32H₂O. In case of luminescent lanthanide ions, changing the microenvironment around the metal ion also changes the intensity of some emission peaks as well as other luminescent parameters. Investigation of emission spectra of Eu³⁺ indicates a decrease in the symmetry of the microenvironment, when the polyanions pass from water to latex, to surfactant solution, and to hydrogel. Full article

The reaction of the Schiff base ligand o-OH-C₆H₄-CH=N-C(CH₂OH)₃, H₄L, with Ni(O₂CMe)₂·4H₂O and lanthanide nitrate salts in a 4:2:1 ratio lead to the formation of the trinuclear complexes [Ni₂Ln(H₃L)₄(O₂CMe)₂](NO₃) (Ln = Sm (1), Eu (2), Gd (3), Tb (4)). The complex cations contain the strictly linear Ni^II-Ln^III-Ni^II moiety. The central Ln^III ion is bridged to each of the terminal Ni^II ions through two deprotonated phenolato groups from two different ligands. Each terminal Ni^II ion is bound to two ligands in distorted octahedral N₂O₄ environment. The central lanthanide ion is coordinated to four phenolato oxygen atoms from the four ligands, and four carboxylato oxygen atoms from two acetates which are bound in the bidentate chelate mode. The lattice structure of complex 4 consists of two interpenetrating, supramolecular diamond like lattices formed through hydrogen bonds among neighboring trinuclear clusters. The magnetic properties of 1–4 were studied. For 3 the best fit of the magnetic susceptibility and isothermal M(H) data gave J_NiGd = +0.42 cm⁻¹, D = +2.95 cm⁻¹ with g_Ni = g_Gd = 1.98. The ferromagnetic nature of the intramolecular Ni···Gd interaction revealed ground state of total spin S = 11/2. The magnetocaloric effect (MCE) parameters for 3 show that the change of the magnetic entropy (−ΔS_m) reaches a maximum of 14.2 J kg⁻¹ K⁻¹ at 2 K. A brief literature survey of complexes containing the Ni^II-Ln^III-Ni^II moiety is discussed in terms of their structural properties. Full article