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Cluster-based functional materials have made remarkable progress owing to their wonderful structures and distinctive physicochemical performances, one of on-going advancements of which is basically driven by synthetic chemistry of exploring and constructing novel nanosized gigantic polyoxometalate (POM) aggregates. In this article, an unprecedented nanoscale hexameric arsenotungstate aggregate Na 9 K 16 H 4 [Er 0.5 K 0.5 (H 2 O) 7 ][Er 5 W 10 O 26 (H 2 O) 14 ][B- α -AsW 9 O 33 ] 6 ·102H 2 O ( 1 ) has been synthesized by the combined synthetic strategy of simultaneously using the arsenotungstate precursor and simple tungstate material in a highly acidic aqueous solution. The {[Er 5 W 10 O 26 (H 2 O) 14 ][B-α-AsW 9 O 33 ] 6 } 31− polyanion in 1 consists of an intriguing dumbbell-shaped pentadeca-nuclear W-Er heterometal {Er 5 W 10 O 26 (H 2 O) 14 } 23+ cluster connecting six trilacunary [B-α-AsW 9 O 33 ] 9− moieties, which has never been seen previously. Furthermore, through electropolymerization of 1 and pyrrole on the conductive substrate, a thickness-controllable and robust 1 -PPY (PPY = polypyrrole) hybrid film was successfully prepared, which represents the first POM-PPY film assembled from high-nuclear lanthanide (Ln) encapsulated POM and PPY hitherto. The 1 -PPY film-based electrochemical biosensor exhibits a favorable recognition performance for ochratoxin A in multiple media. This work not only provides a feasible combined synthetic strategy of the POM precursor and simple tungstate material for constructing complicated multi-Ln-inserted POM aggregates, but also offers a promising electrochemical platform constructed from POM-based conductive films for identifying trace biomolecules in complex environments.

Fracture nonunion or delayed union presents a significant challenge in orthopedic practice. Bone healing is a complex physiological process that initiates with the modulation of inflammatory immunity and progresses through critical stages, including angiogenesis, osteogenic differentiation, and biomineralization. The intrinsic link among immune homeostasis, bacterial clearance, and osteogenic microenvironments underscores the need for an integrated therapeutic strategy. To address these challenges, we developed a multifunctional molybdenum-based polyoxometalate cluster (Mo-POM) modified with gallic acid (GA). Theoretical and experimental evidence confirms that electron transfer from GA to the Mo-POM cluster narrows the HOMO-LUMO energy gap, enhancing its multi-enzyme mimetic activity for effective reactive oxygen species (ROS) scavenging, thereby remodeling the immune microenvironment. The Mo-POM also exhibits broad-spectrum antibacterial function through synergistic disruption of bacterial membranes and biofilms. To ensure practical applicability and sustained release, the Mo-POM was encapsulated within a gellan gum/nano-hydroxyapatite (GG/nHA) hydrogel scaffold. The resulting Mo-POM@GG/nHA system effectively coordinates early immunomodulation and antibacterial activity with enhanced biomineralization in the bone regeneration process. Although polyoxometalates have demonstrated versatile biochemical properties, their application in bone regeneration remains largely unexplored. This work demonstrates that a single Mo-POM cluster acts as a core modulator, achieving the “three birds with one stone” effect by eliminating inflammation, modulating the immune microenvironment, and boosting osteogenesis, thereby providing a new avenue for designing a new class of integrated biomaterials for orthopedic applications. [Display omitted] •A multifunctional Mo-POM@GG/nHA hydrogel was developed to orchestrate immunomodulation and osteogenesis for bone repair.•Gallic acid modification enhances the multi-enzyme mimicking activity of POM nanoclusters for effective ROS scavenging.•Mo-POM nanoclusters exert broad-spectrum antibacterial activity by disrupting bacterial membranes and biofilms.•The hydrogel provides a bioactive matrix for sustained release of Mo-POM NCs and promotes osteogenic mineralization.•Mo-POM@GG/nHA hydrogel promotes regeneration through immunomodulation, antibacterial activity, and biomineralization.

Developing high−efficiency membrane materials for the rapid removal of organic dyes is crucial but remains a challenge. Polyoxometalates (POMs) clusters with anionic structures are promising candidates for the removal of cationic dyes via electrostatic interactions. However, their shortcomings, such as their solubility and inability to be mass−produced, hinder their application in water pollution treatment. Here, we propose a simple and green strategy utilizing the room temperature stirring method to mass produce nanoscale polyoxometalate−based metal−organic frameworks (POMOFs) with porous rhomboid−shaped dodecahedral and hexagonal prism structures. The products were labeled as POMOF1 (POMOF-PW12) and POMOF2 (POMOF-PMo12). Subsequently, a series of x wt% POMOF1/PAN (x = 0, 3, 5, and 10) nanofiber membranes (NFMs) were prepared using electrospinning technology, where polyacrylonitrile (PAN) acts as a “glue” molecule facilitating the bonding of POMOF1 nanoparticles. The as−prepared samples were comprehensively characterized and exhibited obvious water stability, as well as rapid selective adsorption filtration performance towards cationic dyes. The 5 wt% POMOF1/PAN NFM possessed the highest removal efficiency of 96.7% for RhB, 95.8% for MB, and 86.4% for CV dyes, which realized the selective separation over 95% of positively charged dyes from the mixed solution. The adsorption mechanism was explained using FT−IR, SEM, Zeta potential, and adsorption kinetics model, which proved that separation was determined via electrostatic interaction, hydrogen bonding, and π–π interactions. Moreover, the POMOF1/PAN membrane presented an outstanding recoverable and stable removal rate after four cycles. This study provides a new direction for the systematic design and manufacture of membrane separation materials with outstanding properties for contaminant removal.

Polyoxometalate (POM) gel is well‐known but mostly with organic molecules. Pure inorganic POM gel, that is, a combination of a “POM anion and a metal cation,” is hardly known and unexplored area of materials research. When an aqueous solution of sodium tungstate is mixed with an aqueous solution of ferric chloride, the resulting suspension forms a straw‐color hydrogel. The behavior of this hydrogel W72Fe30HG has been studied by performing rheology studies. Dehydration of hydrogel at room temperature brings about the corresponding xerogel, characterization of which confirms that the xerogel is a W72Fe30 type giant Keplerate‐based POM compound [Fe(H2O)6]14[W72Fe30O252(H2O)72(OH)60]·166H2O (W72Fe30XG) and the basic building unit of the gel is W72Fe30 cluster. The xerogel is macroporous material characterized with 60 hydroxyl groups per formula unit and these hydroxyl groups are acidic in nature. Interestingly, the title xerogel W72Fe30XG, which is nothing but an inorganic acid and an inexpensive metal‐oxide‐based material, exhibits proton conduction in its solid state. The xerogel material shows super proton conductivity of 1.71 × 10−2 S cm−1 at 80 °C and 98% relative humidity with an activation energy (Ea) of 0.18 eV. A pure inorganic hydrogel W72Fe30HG, is reported for the first time in polyoxometalate gel chemistry. The corresponding xerogel material [Fe(H2O)6]14[W72Fe30O252(H2O)72(OH)60]·166H2O (W72Fe30XG), shows proton conductivity of 1.71 × 10−2 s cm−1 at 80 °C (98%relative humidity). Rheological studies of the relevant hydrogel reveal modest mechanical strength, and it exhibits electrical conductivity of 2.43 × 10−5 s cm−1 at an applied potential of 1.0 V.

Anderson-type ([XM6O24]n−) polyoxometalates (POMs) are a class of polymetallic-oxygen cluster inorganic compounds with special structures and properties. They have been paid extensive attention by researchers now, due to their chemical modification and designability, which have been widely applied in the fields of materials, catalysis and medicine. In contemporary years, the application of Anderson-type POMs in catalytic organic oxidation reaction has gradually shown great significance for the research of green catalytic process. In this paper, we investigate the application of Anderson-type POMs in organic synthesis reaction, and these works are summarized according to the different structure of POMs. This will provide a new strategy for further investigation of the catalytic application of Anderson-type POMs and the study of green catalysis.

A d[sup.10]-Cd cluster containing sandwich-type arsenotungstate [C[sub.3]H[sub.12]N[sub.2]][sub.6][Cd[sub.4]Cl[sub.2](B-α-AsW[sub.9]O[sub.34])[sub.2]] was synthesized and its structure characterized through elemental analyses, X-ray powder diffraction (XRPD), IR spectroscopy, X-ray photoelectron spectroscopy (XPS), and single-crystal X-ray diffraction. The X-ray analysis revealed that the molecular unit of the compound consists of a captivating tetra-Cd-substituted sandwich-type polyoxoanion, accompanied by six elegantly protonated 1,2-diaminopropane as counter ions. The further novelty of the tetranuclear cadmium cluster lies in its occupied chlorine atom sites. This makes it highly susceptible to coordinate reactions with nitrogen on polycyclic aromatic hydrocarbons, thereby exhibiting different fluorescent signals that facilitate the identification and detection of these carcinogenic substances in methanol.

Constructing redox semiconductor heterojunction photocatalysts is the most effective and important means to complete the artificial photosynthetic overall reaction (i.e., coupling CO₂ photoreduction and water photo-oxidation reactions). However, multiphase hybridization essence and inhomogeneous junction distribution in these catalysts extremely limit the diverse design and regulation of the modes of photogenerated charge separation and transfer pathways, which are crucial factors to improve photocatalytic performance. Here, we develop molecular oxidation—reduction (OR) junctions assembled with oxidative cluster (PMo12, for water oxidation) and reductive cluster (Ni₅, for CO₂ reduction) in a direct (d-OR), alternant (a-OR), or symmetric (s-OR) manner, respectively, for artificial photosynthesis. Significantly, the transfer direction and path of photogenerated charges between traditional junctions are obviously reformed and enriched in these well-defined crystalline catalysts with monophase periodic distribution and thus improve the separation efficiency of the electrons and holes. In particular, the charge migration in s-OR shows a periodically and continuously opposite mode. It can inhibit the photogenerated charge recombination more effectively and enhance the photocatalytic performance largely when compared with the traditional heterojunction models. Structural analysis and density functional theory calculations disclose that, through adjusting the spatial arrangement of oxidation and reduction clusters, the energy level and population of the orbitals of these OR junctions can be regulated synchronously to further optimize photocatalytic performance. The establishment of molecular OR junctions is a pioneering important discovery for extremely improving the utilization efficiency of photogenerated charges in the artificial photosynthesis overall reaction.

The hybrid materials that are created by supporting or incorporating polyoxometalates (POMs) into/onto metal–organic frameworks (MOFs) have a unique set of properties. They combine the strong acidity, oxygen-rich surface, and redox capability of POMs, while overcoming their drawbacks, such as difficult handling, a low surface area, and a high solubility. MOFs are ideal hosts because of their high surface area, long-range ordered structure, and high tunability in terms of the pore size and channels. In some cases, MOFs add an extra dimension to the functionality of hybrids. This review summarizes the recent developments in the field of POM@MOF hybrids. The most common applied synthesis strategies are discussed, together with major applications, such as their use in catalysis (organocatalysis, electrocatalysis, and photocatalysis). The more than 100 papers on this topic have been systematically summarized in a handy table, which covers almost all of the work conducted in this field up to now.

Dimensional regulation in polyoxometalates is an effective strategy during the design and synthesis of polyoxometalates-based high proton conductors, but it is not available to date. Herein, the precise regulation of dimensionality has been realized in an unprecedented gigantic molybdenum blue wheel family featuring pentagonal {(W)Mo 5 } motifs through optimizing the molar ratio of Mo/W, including [Gd 2 Mo 124 W 14 O 422 (H 2 O) 62 ] 38− (0D-{Mo 124 W 14 }, 1 ), [Mo 126 W 14 O 441 (H 2 O) 51 ] 70− (1D-{Mo 126 W 14 } n , 2 ), and [Mo 124 W 14 O 430 (H 2 O) 50 ] 60− (2D-{Mo 124 W 14 } n , 3 ). Such important {(W)Mo 5 } structural motif brings new reactivity into gigantic Mo blue wheels. There are different numbers and sites of {Mo 2 } defects in each wheel-shaped monomer in 1–3 , which leads to the monomers of 2 and 3 to form 1D and 2D architectures via Mo–O–Mo covalent bonds driven by {Mo 2 }-mediated H 2 O ligands substitution process, respectively, thus achieving the controllable dimensional regulation. As expected, the proton conductivity of 3 is 10 times higher than that of 1 and 1.7 times higher than that of 2 . The continuous proton hopping sites in 2D network are responsible for the enhanced proton conductivity with lower activation energy. This study highlights that this dimensional regulation approach remains great potential in preparing polyoxometalates-based high proton conductive materials.

Two inorganic–organic hybrid complexes based on bi-capped Keggin-type cluster, ([Cu[sup.II](2,2′-bpy)[sub.2]][sub.2][PMo[sup.VI] [sub.8]V[sup.V] [sub.2]V[sup.IV] [sub.2]O[sub.40](V[sup.IV]O)[sub.2]])[Cu[sup.I](2,2′-bpy)]∙2H[sub.2]O (1) and [Cu[sup.II](2,2′-bpy)[sub.2]][sub.2][SiMo[sup.VI] [sub.8.5]Mo[sup.V] [sub.2.5]V[sup.IV]O[sub.40](V[sup.IV]O)[sub.2]][Cu[sup.I] [sub.0.5](2,2′-bpy)(H[sub.2]O)[sub.0.5]] (2) (bpy = bipyridine), had been hydrothermally synthesized and structurally characterized by elemental analysis, FT-IR, TGA, PXRD and X-ray single-crystal diffraction analysis. Compound 1 consists of a novel 1-D chain structure constructed from [Cu[sup.I](2,2′-bpy)][sup.+] unit linking bi-supported POMs anion [Cu[sup.II](2,2′-bpy)[sub.2]][sub.2][PMo[sup.VI] [sub.8]V[sup.V] [sub.2]V[sup.IV] [sub.2]O[sub.40](V[sup.IV]O)[sub.2]][sup.−]. Compound 2 is a bi-capped Keggin cluster bi-supported Cu-bpy complex. The main highlights of the two compounds are that Cu-bpy cations contain both Cu[sup.I] and Cu[sup.II] complexes. Furthermore, the fluorescence properties, the catalytic properties, and the photocatalytic performance of compounds 1 and 2 have been assessed, and the results show that both compounds are active for styrene epoxidation and degradation and adsorption of Methylene blue (MB), Rhodamine B (RhB) and mixed aqueous solutions.