Polyoxometalate (POM)-based lanthanide-oxo clusters (LnOCs) are a class of polynuclear lanthanide–oxygen complexes formed by polyoxometalate stabilization through oxygen bridges in which POMs can be viewed as multidentate inorganic ligands. POM-based LnOCs have received interest owing to their interesting structures and potential applications. In this paper, we summarize the classification, synthesis strategies, and properties of POM-based LnOCs. POM-based LnOCs are classified into three main categories according to their metal core element type and quantity: pure 4f clusters, 5d–4f clusters, and 3d–4f clusters. Their synthetic strategies are divided into four categories based on the source of the POM involved in the structural assembly: the lacunary POMs ligand-directed method, the in-situ transformation of lacunary POMs ligand-directed method, the in-situ generation of lacunary POMs ligand-directed method, and mixed synthesis strategies. In addition, the single-molecule magnets of POM-based LnOCs and their proton conduction properties are summarized. 

https://www.sciopen.com/article_pdf/1605824813563789313.pdf

Recent advances of polyoxometalates-based lanthanide-oxo clusters 

The application of one kind of metal-organic framework (MOF) material used in multiple fields is one of the most interesting research topics. In this work, four new tetra-nuclear cluster-based lanthanide metal-organic frameworks (LnMOFs) [Ln2(BTDB)3(DMA)(phen)]n (Ln = Tb TbMOF, Eu EuMOF, Gd GdMOF, Tb1.830Eu0.170 Tb,EuMOF, 3,5-bis(trifluoromethyl)-4',4″-dicarboxytriphenylamine = H2BTDB, 1,10-phenanthroline = phen) are obtained based on the ligand of H2BTDB that is synthesized in our laboratory, and the precise single-crystal structure of H2BTDB is obtained for the first time. The white phosphor was obtained by facilely hybridizing two components of the orange-yellow emission phosphor of Tb,EuMOF and the blue luminescence material of triphenylamine according to the trichromatic theory. At the same time, TbMOF, EuMOF, Tb,EuMOF, and the white phosphor can be used for information encryption, demonstrating their potential application in the field of anti-counterfeiting. Tb,EuMOF is also a multi-mode and self-calibrating thermometer within a broad temperature range of 110-300 K. Further studies show that EuMOF is a rapid response sensor for Fe2+, with a very low limit of detection of 2.0 nM, which is much lower than the national standards for Fe2+ (GB 5749-2005, 5.357 μM). It can achieve strong anti-interference detection of Fe2+ in actual samples of tap water and lake water. In addition, EuMOF can also be made into an easy-to-use sensing device of test paper for real-time and visual sensing of Fe2+.

Tetra-Nuclear Cluster-Based Lanthanide Metal-Organic Frameworks as White Phosphor, Information Encryption, Self-Calibrating Thermometers, and Fe2+ Sensors.

A series of acetylacetone-protected lanthanide-titanium-oxo clusters (LTOCs), formulated as [La6Ti(μ3-OH)8(acac)12(CH3O)2(CH3OH)6] (La6Ti; Hacac = acetylacetone) and [Ln9Ti2(μ4-O)(μ3-OH)14(acac)17(CH3O)2(CH3OH)3] [Ln = Eu (Eu9Ti2) and Tb (Tb9Ti2)], were synthesized through the reactions of LnCl3·6H2O (Ln = La, Eu, and Tb), Hacac, Ti(OiPr)4, and triethylamine in methanol. Crystal structural analysis shows that La6Ti exhibits an hourglass-like structure consisting of two La3Ti cubane subunits by sharing one Ti4+ ion, while Eu9Ti2 can be viewed as a combination of four Eu3Ti cubane subunits by sharing three corners and one side. The photoluminescence (PL) measurements show that Tb9Ti2 exhibits excellent PL properties with a high quantum yield (QY) of 34.8%, while Eu9Ti2 only has a QY of 1.4% because of the different photosensitizations of ligands to Eu3+ and Tb3+ ions in the photophysical process.

Photoluminescence of Lanthanide-Titanium-Oxo Clusters Eu9Ti2 and Tb9Ti2 Based on a β-Diketone Ligand.

The design of metal cluster-based materials possessing exceptional circular dichroism (CD) and circularly polarized luminescence (CPL) performance has garnered significant attention due to their promising applications in 3D display, photoelectric...

Progress in Optical Properties of Chiral Metal Clusters: Circular Dichroism and Circularly Polarized Luminescence

The self-assembly of the high-nuclearity Ln-exclusive nanoclusters is challenging but of significance due to its aesthetically pleasing architectures and far-reaching latent applications in magnetic cooling technologies. Herein, two novel high-nuclearity lanthanide nanoclusters were successfully synthesized under solvothermal conditions, formulated as {[Gd18(IN)20(HCOO)8(μ6-O)(μ3-OH)24(H2O)4]·4H2O}n and {[Eu18(IN)16(HCOO)8(CH3COO)4(μ6-O)(μ3-OH)24(H2O)4]·5H2O}n (abbreviated as Gd18 and Eu18, HIN = isonicotinic acid). Both of them possess novel and exquisite windmill-shaped cationic cores in the family of high-nuclearity Ln-exclusive nanoclusters. Remarkably, the adjacent second building units are interconnected into a three-dimensional (3D) metal-organic framework by IN- ligands. As expected, the abundant existence of GdIII ions endows Gd18 with a favorable magnetic entropy change at 2.0 K for ΔH = 7.0 T (-ΔSmmax = 40.0 J kg-1 K-1), and Eu18 displays the typical luminescence of EuIII ions.

Two Windmill-Shaped Ln18 Nanoclusters Exhibiting High Magnetocaloric Effect and Luminescence.

Recent Advances in Lanthanide-titanium-oxo Clusters

Synthesis, Structure and Luminescence Characterizations of Pyramid-like Lanthanide-Titanium-Oxo Clusters EuTi9 and TbTi9

Circularly polarized luminescence and performance modulation of chiral europium-titanium (Eu2Ti4)-oxo clusters.

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Papers

Photoluminescence of Lanthanide-Titanium-Oxo Clusters Eu9Ti2 and Tb9Ti2 Based on a β-Diketone Ligand.

Recent Advances in Lanthanide-titanium-oxo Clusters

Synthesis, Structure and Luminescence Characterizations of Pyramid-like Lanthanide-Titanium-Oxo Clusters EuTi9 and TbTi9

Circularly polarized luminescence and performance modulation of chiral europium-titanium (Eu2Ti4)-oxo clusters.