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Atomically precise low‐nuclearity (n<10) silver nanoclusters (AgNCs) have garnered significant interest due to their size‐dependent optical properties and diverse applications. However, their synthesis has remained challenging, primarily due to their inherent instability. The present study introduces a new feasible approach for clustering silver ions utilizing highly negative and redox‐inert polyoxoniobates (PONbs) as all‐inorganic ligands. This strategy not only enables the creation of novel Ag‐PONb composite nanoclusters but also facilitates the synthesis of stable low‐nuclearity AgNCs. Using this method, we have successfully synthesized a small octanuclear rhombic [Ag8]6+ AgNC stabilized by six highly negative [LiNb27O75]14− polyoxoanions. This marks the first PONb‐protected superatomic AgNC, designated as {Ag8@(LiNb27O75)6} (Ag8@Nb162), with an aesthetically spherical core–shell structure. The crystalline Ag8@Nb162 is stable under ambient conditions, What's more, it is water‐soluble and able to maintain its molecular cluster structure intact in water. Further, the stable small [Ag8]6+ AgNC has interesting temperature‐ and pH‐dependent reversible fluorescence response, based on which a multiple optical encryption mode for anti‐counterfeit technology was demonstrated. This work offers a promising avenue for the synthesis of fascinating and stable PONb‐protected AgNCs and sheds light on the development of new‐type optical functional materials. [ABSTRACT FROM AUTHOR]

Atomically precise low‐nuclearity (n<10) silver nanoclusters (AgNCs) have garnered significant interest due to their size‐dependent optical properties and diverse applications. However, their synthesis has remained challenging, primarily due to their inherent instability. The present study introduces a new feasible approach for clustering silver ions utilizing highly negative and redox‐inert polyoxoniobates (PONbs) as all‐inorganic ligands. This strategy not only enables the creation of novel Ag‐PONb composite nanoclusters but also facilitates the synthesis of stable low‐nuclearity AgNCs. Using this method, we have successfully synthesized a small octanuclear rhombic [Ag8]6+ AgNC stabilized by six highly negative [LiNb27O75]14− polyoxoanions. This marks the first PONb‐protected superatomic AgNC, designated as {Ag8@(LiNb27O75)6} (Ag8@Nb162), with an aesthetically spherical core–shell structure. The crystalline Ag8@Nb162 is stable under ambient conditions, What's more, it is water‐soluble and able to maintain its molecular cluster structure intact in water. Further, the stable small [Ag8]6+ AgNC has interesting temperature‐ and pH‐dependent reversible fluorescence response, based on which a multiple optical encryption mode for anti‐counterfeit technology was demonstrated. This work offers a promising avenue for the synthesis of fascinating and stable PONb‐protected AgNCs and sheds light on the development of new‐type optical functional materials. [ABSTRACT FROM AUTHOR]

Only rarely have polyoxometalates been found to form core–shell nanoclusters. Here, we succeeded in isolating a series of rare giant and all‐inorganic core–shell cobalt polyoxoniobates (Co−PONbs) with diverse shapes, nuclearities and original topologies, including 50‐nuclearity {Co12Nb38O132}, 54‐nuclearity {Co20Nb34O128}, 62‐nuclearity {Co26Nb36O140} and 87‐nuclearity {Co33Nb54O188}. They are the largest Co−PONbs and also the polyoxometalates containing the greatest number of Co ions and the largest cobalt clusters known thus far. These molecular Co−PONbs have intriguing and atomically precise core–shell architectures comprising unique cobalt oxide cores and niobate oxide shells. In particular, the encapsulated cobalt oxide cores with different nuclearities have identical compositions, structures and mixed‐valence Co3+/Co2+ states as the different sized Co−O moieties of the bulk cubic‐spinel Co3O4, suggesting that they can serve as various molecular models of the cubic‐spinel Co3O4. The successful construction of the series of the Co−PONbs reveals a feasible and versatile synthetic method for making rare core–shell heterometallic PONbs. Further, these new‐type core–shell bimetal species are promising cluster molecular catalysts for visible‐light‐driven CO2 reduction. [ABSTRACT FROM AUTHOR]

Compounds with redox activities have appealing applications in catalytic, electronic and magnetic properties, but the redox inert of polyoxoniobates (PONbs) significantly limits their applications for a long time. In this work, we are able to integrate organophosphate and lanthanide cluster into PONb to create the first family of inorganic‐organic hybrid organophosphate‐Ln‐PONb composite clusters. These novel species not only present the first family of redox active PONbs that can be reduced to form long‐lived "heteropoly blues" under ambient conditions, but also a new photochromic system. More importantly, the analyses of the electronic configurations and photochromic properties for a series of designed proof‐of‐concept PONbs models allow us to discover a D‐f‐A electron transfer mechanism, that is, photoinduced electron is transferred from a photosensitive organophosphate electron donor (D) to the NbV electron acceptor (A) through the unoccupied 4 f‐orbitals of Ln (f). This work paves the way for developing diverse PONb‐based redox materials and expanding the possibility of the applications of PONbs in the redox chemistry. [ABSTRACT FROM AUTHOR]

Only rarely have polyoxometalates been found to form core–shell nanoclusters. Here, we succeeded in isolating a series of rare giant and all‐inorganic core–shell cobalt polyoxoniobates (Co−PONbs) with diverse shapes, nuclearities and original topologies, including 50‐nuclearity {Co12Nb38O132}, 54‐nuclearity {Co20Nb34O128}, 62‐nuclearity {Co26Nb36O140} and 87‐nuclearity {Co33Nb54O188}. They are the largest Co−PONbs and also the polyoxometalates containing the greatest number of Co ions and the largest cobalt clusters known thus far. These molecular Co−PONbs have intriguing and atomically precise core–shell architectures comprising unique cobalt oxide cores and niobate oxide shells. In particular, the encapsulated cobalt oxide cores with different nuclearities have identical compositions, structures and mixed‐valence Co3+/Co2+ states as the different sized Co−O moieties of the bulk cubic‐spinel Co3O4, suggesting that they can serve as various molecular models of the cubic‐spinel Co3O4. The successful construction of the series of the Co−PONbs reveals a feasible and versatile synthetic method for making rare core–shell heterometallic PONbs. Further, these new‐type core–shell bimetal species are promising cluster molecular catalysts for visible‐light‐driven CO2 reduction. [ABSTRACT FROM AUTHOR]

Compounds with redox activities have appealing applications in catalytic, electronic and magnetic properties, but the redox inert of polyoxoniobates (PONbs) significantly limits their applications for a long time. In this work, we are able to integrate organophosphate and lanthanide cluster into PONb to create the first family of inorganic‐organic hybrid organophosphate‐Ln‐PONb composite clusters. These novel species not only present the first family of redox active PONbs that can be reduced to form long‐lived "heteropoly blues" under ambient conditions, but also a new photochromic system. More importantly, the analyses of the electronic configurations and photochromic properties for a series of designed proof‐of‐concept PONbs models allow us to discover a D‐f‐A electron transfer mechanism, that is, photoinduced electron is transferred from a photosensitive organophosphate electron donor (D) to the NbV electron acceptor (A) through the unoccupied 4 f‐orbitals of Ln (f). This work paves the way for developing diverse PONb‐based redox materials and expanding the possibility of the applications of PONbs in the redox chemistry. [ABSTRACT FROM AUTHOR]

Cup‐shaped molecules are of great interest due to their appealing architectures and properties. Compared with widely studied calixarenes, polyoxometalate‐based cup‐shaped molecules currently remain a virgin land waiting for exploration. In this work, we report the first discovery of two giant cup‐shaped inorganic–organic hybrid polyoxoniobates (PONbs) of {Cu12Nb120} and {Cd16Nb128}. The former integrates three tricyclic Nb24 clusters and a hexacyclic Nb48 cluster into a cup‐shaped molecule via a Cu12 metallacalixarene, while the latter unifies two tricyclic Nb24 clusters and a brand‐new pentacyclic Nb40 cluster into another cup‐shaped molecule via a hybrid Cd16 unit. With 132 and 144 metal centers, {Cu12Nb120} and {Cd16Nb128} show the largest two inorganic–organic hybrid PONbs known to date. [ABSTRACT FROM AUTHOR]

Cup‐shaped molecules are of great interest due to their appealing architectures and properties. Compared with widely studied calixarenes, polyoxometalate‐based cup‐shaped molecules currently remain a virgin land waiting for exploration. In this work, we report the first discovery of two giant cup‐shaped inorganic–organic hybrid polyoxoniobates (PONbs) of {Cu12Nb120} and {Cd16Nb128}. The former integrates three tricyclic Nb24 clusters and a hexacyclic Nb48 cluster into a cup‐shaped molecule via a Cu12 metallacalixarene, while the latter unifies two tricyclic Nb24 clusters and a brand‐new pentacyclic Nb40 cluster into another cup‐shaped molecule via a hybrid Cd16 unit. With 132 and 144 metal centers, {Cu12Nb120} and {Cd16Nb128} show the largest two inorganic–organic hybrid PONbs known to date. [ABSTRACT FROM AUTHOR]

In this work, two rare high‐dimensional polyoxoniobates with formulas of H9[Cu(en)(H2O)2][Cu(en)2]8[Dy(H2O)4]3[Nb24‐O69(H2O)3]2 ⋅ 36H2O (1) and H9K[Cu(en)2(H2O)]5[Cu(en)2]4‐[Eu(H2O)4]3[Nb24O69(H2O)3]2 ⋅ 2en ⋅ 45H2O (2) have been obtained under hydrothermal conditions. These extended materials are constructed from lanthanide‐incorporated triangular‐prism‐like polyoxoniobate secondary building units (SBUs) {[Ln(H2O)4]3[Nb24O69(H2O)3]2} (Ln=Dy, Eu). 1 and 2 represent the first examples of high‐dimensional polyoxometalate materials based on such lanthanide‐incorporated triangular‐prism‐like polyoxoniobate SBUs. Furthermore, the proton conduction property and the luminescent emission of these materials were evaluated. [ABSTRACT FROM AUTHOR]

The combination of polyoxoniobates (PONbs) with 3d metal ions, azoles, and organoamines is a general synthetic procedure for making unprecedented PONb metal complex cage materials, including discrete molecular cages and extended cage frameworks. By this method, the first two PONb metal complex cages K4@{[Cu29(OH)7(H2O)2(en)8(trz)21][Nb24O67(OH)2(H2O)3]4} and [Cu(en)2]@{[Cu2(en)2(trz)2]6(Nb68O188)} have been made. The former exhibits a huge tetrahedral cage with more than 120 metal centers, which is the largest inorganic–organic hybrid PONb known to date. The later shows a large cubic cage, which can act as building blocks for cage‐based extended assembly to form a 3D cage framework {[Cu(en)2]@{[Cu2(trz)2(en)2]6[H10Nb68O188]}}. These materials exhibit visible‐light‐driven photocatalytic H2 evolution activity and high vapor adsorption capacity. The results hold promise for developing both novel cage materials and largely unexplored inorganic–organic hybrid PONb chemistry. [ABSTRACT FROM AUTHOR]

Abstract: A protein‐sized (ca. 4.2×4.2×3.6 nm3) non‐biologically derived molecule {Nb288O768(OH)48(CO3)12} (Nb288) containing up to 288 niobium atoms has been obtained, which is by far the largest and the highest nuclearity polyoxoniobate (PONb). Particularly, in terms of metal nuclearity number, Nb288 is the second largest cluster so far reported in classic polyoxometalate chemistry (V, Mo, W, Nb, and Ta). Nb288 can be described as a giant windmill‐like cluster aggregate of six nanoscale high‐nuclearity PONb units {Nb47O128(OH)6(CO3)2} (Nb47) joined together by six additional Nb ions. Interestingly, the 47‐nuclearity Nb47 units generated in situ can be isolated and bridged by copper complexes to form an inorganic–organic hybrid three‐dimensional PONb framework, which exhibits effective catalytic activity for hydrolyzing nerve agent simulant of dimethyl methylphosphonate. The unique Nb47 cluster also provides a new type of topology to very limited family of Nb‐O clusters. [ABSTRACT FROM AUTHOR]

A series containing the highest nuclearity polyoxoniobate (PONb) nanoclusters, ranging from dimers to tetramers, has been obtained. They include one 114-nuclear {Li8⊂Nb114O316}, one 81-nuclear {Li3K⊂Nb81O225}, and one 52-nuclear {H4Nb52O150}. The Nb nuclearity of these PONbs is remarkably larger than those of all known high-nuclearity PONbs (≤32). Furthermore, the introduction of 3d Cu2+ ions can lead to the generation of extended inorganic-organic hybrid frameworks built from novel, high-nuclearity, nanoscale heterometallic PONb building blocks {H3Cu3Nb78O222} or {H3Cu4(en)Nb78O222}. These building blocks also contain the largest number of Nb centers of any heterometallic PONbs reported to date. The synthesis of new-type PONbs has long been a challenging subject in PONb chemistry. [ABSTRACT FROM AUTHOR]

The first series of niobium-tungsten-lanthanide (Nb-W-Ln) heterometallic polyoxometalates {Ln12W12O36(H2O)24(Nb6O19)12} (Ln=Y, La, Sm, Eu, Yb) have been obtained, which are comprised of giant cluster-in-cluster-like ({Ln12W12}-in-{Nb72}) structures built from 12 hexaniobate {Nb6O19} clusters gathered together by a rare 24-nuclearity sodalite-type heterometal-oxide cage {Ln12W12O36(H2O)24}. The Nb-W-Ln clusters present the largest multi-metal polyoxoniobates and a series of rare high-nuclearity 4d-5d-4f multicomponent clusters. Furthermore, the giant Nb-W-Ln clusters may be isolated as discrete inorganic alkali salts and can be used as building blocks to form high-dimensional inorganic-organic hybrid frameworks. [ABSTRACT FROM AUTHOR]

A unique {SiNb 18 O 54 }-based framework was prepared and characterized. The compound is very stable, and can selectively absorbs crystal violet from aqueous solution. Additionally, the proton-conduction property of the compound was also studied. • A novel polyoxoniobate framework based on crescent-like {SiNb 18 O 54 } clusters has been made. • The compound shows good thermal/chemical stabilities under various conditions. • The compound can selectively absorb crystal violet from aqueous solution. • The proton-conduction property of the compound was studied. A novel inorganic-organic hybrid polyoxoniobate framework based on crescent-like {SiNb 18 O 54 } building blocks and [Cu(en)]2+/K+ (en = ethylenediamine) linkers has been successfully made under hydrothermal condition. The compound is very stable under various conditions, and can selectively absorb crystal violet from aqueous solution. Additionally, the proton-conduction property of the compound was also studied. [ABSTRACT FROM AUTHOR]

Exploring noble‐metal‐free, highly active and durable catalysts is vital to get to grips with the energy and environmental issues. Herein, we first dexterously design and synthesize a class of ternary Nb6/CZS/g‐CN photocatalysts for the removal of hexavalent chromium Cr (VI) and organic dye pollutant (MO) from wastewater under visible‐light irradiation. A heterojunction Nb6–1/CZS/g‐CN loaded with 0.01 g K7HNb6O19 showed excellent photocatalytic performance, with the MO photodegradation efficiency of 94% in 1 h and the Cr (VI) (150 mg/l) photoreduction efficiency as high as 91% in 2 hr. The main active species were deemed to be O2.‐. Additionally, the as‐prepared ternary heterojunction exhibits superior hydrogen evolution reaction (HER) rate. A heterojunction Nb6–4/CZS/g‐CN loaded with 0.5 g K7HNb6O19 exhibited the highest H2 evolution rate as high as 1777.86 μmol h−1 g−1 under visible‐light illumination, which is increased to 5.7 and 2.7 times that of bare CZS and biphase heterojunction CZS/g‐CN. These findings afford a new class of promising low‐cost photocatalyst bodying for its huge potential value in sustainable energy development and wastewater treatment. [ABSTRACT FROM AUTHOR]