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Abstract: A series of new polyoxometalates based on [Ni6(μ3-OH)3(H2O)6(en)3(B-α-PW9O34)] (en=ethylenediamine) clusters capped by different tripodal alcohol ligands have been hydrothermally synthesized and characterized by IR, TGA and single-crystal X-ray diffraction, respectively. The experimental results indicate that the tripodal alcohol ligands can substitute three hydroxyl groups located on the axial positions of the Ni6 cluster to form new polyoxometalates with different substituted modes. [Copyright &y& Elsevier]

• The recent advancements of all-inorganic POM cages, including their assembly methodologies, classification and related applications are summarized. • The advantages of using POM clusters as SBUs to construct all-inorganic POM cages are summarized. • Feasible synthetic strategies for further development of all-inorganic POM cages are presented. • Understanding the structure–property/application relationships of all-inorganic POM cages. • The current challenges in the design and fabrication of all-inorganic POM cages as well as the great potential in this area are discussed. Searching for suitable methods to construct all-inorganic cage materials by using polyoxometalates (POMs) as secondary building units (SBUs) has been of great interest, because such materials not only exhibit fascinating cage-shaped structures and unique physicochemical properties derived from both cage architectures and POM clusters, but also have promising and practical applications in areas of molecule separation, guest recognition, molecular reactors, photocatalysis, environmental protection, and so on. In this review, the recent development in all-inorganic POM-based cage materials is summarized, including their assembly methods, structures, properties, and related applications. Moreover, the current challenges in the design and assembly of all-inorganic POM cages as well as the development potential of this area also discussed. [ABSTRACT FROM AUTHOR]

Two new inorganic frameworks HLa(H 2 O)5[La(H 2 O)6]2[La(H 2 O)2(GeW11O39)]2·7H 2 O ( 1 ) and HK(H 2 O)La 3 (H 2 O) 15 [La(H 2 O) 3 (GeW 11 O 39 )] 2 ·38H 2 O ( 2 ) based on 1:1 type lanthanide-substituted polyoxometalates (LSPs) have been synthesized under hydrothermal reactions. Compounds 1 and 2 are characterized by single-crystal X-ray diffraction analysis, thermogravimetry analysis, infrared spectroscopy and X-ray powder diffraction analysis. Interestingly, Compounds 1 and 2 can be selectively obtained by simply controlling the reaction temperatures under similar conditions. Both 1 and 2 are three-dimensional structures built from lanthanide-substituted polyoxoanions [La(H 2 O) n (GeW 11 O 39 )] 5 − building blocks. Furthermore, the ion-conducting properties of 1 and 2 were investigated. [ABSTRACT FROM AUTHOR]

[Display omitted] • The developments of POM-templated silver clusters are reviewed. • The syntheses, structures, properties and applications of POM-templated silver clusters are summarized. • The structure–property/application relationships of POM-templated silver clusters are discussed. • The development prospects and the current challenges for POM-templated silver clusters are discussed. • The suggestions for the further development of POM-templated silver clusters are presented. The search for feasible strategies to construct high-nuclear silver clusters has been attracting continuous interests because such materials not only exhibit aesthetic structures and fascinating properties, but also show promising applications in photoluminescence, antibiosis materials, photochromism, nano-materials, and electron transfer/communication materials. Anions are well-known as templates to direct the formation of silver clusters and control the shapes, sizes, and functions of the final products. As a unique class of anionic metal-oxo species, polyoxometalates (POMs) have been widely employed as templates in the syntheses of many intriguing silver clusters. In this review, the advances in POM-templated high-nuclear silver clusters in the past decade are summarized. Additionally, the different templating effects between POMs and simple inorganic anions are discussed. Actually, POMs can do much more than templates for the formation of diverse high-nuclear silver architectures, they also are significant in stabilizing the final products, functionalizing the composite clusters, and so on. Based on the current development in this area, the present challenges and perspectives for such materials are also presented. We hope that this review will be of reference value to accelerate the further development of silver clusters. [ABSTRACT FROM AUTHOR]

[Display omitted] • The developments of all-inorganic POM-based frameworks including their syntheses, structures, properties and related applications are summarized. • The structure–property/application relationships of all-inorganic POM-based frameworks are summarized. • Feasible synthetic strategies for further development of all-inorganic POM-based frameworks are presented. • The development prospects and the current challenges for all-inorganic POM-based frameworks are discussed. Polyoxometalates (POMs) are an intriguing class of compounds that have been extensively studied due to their unique structures and diverse properties. In the past years, the synthesis of POM-based all-inorganic open frameworks has attracted increasing attention due to their potential applications in various fields, such as in electrode, magnetic, and catalytic materials. This review not only provides a comprehensive survey on POM-based all-inorganic open frameworks, including their structures, properties, and potential applications, but also discusses the current challenges in this field and provides an outlook for future research directions. [ABSTRACT FROM AUTHOR]

The first two tetra-Sc-substituted polyoxotungstates H 2 K 2 Na 2 [Sc 4 (H 2 O) 10 ( B -β-SbW 9 O 33 ) 2 ]·21H 2 O (1) and H 20 K 2 Na 6 [Sc 4 (C 2 O 4 ) 4 ( B -β-SbW 9 O 33 ) 2 ][Sc 4 (H 2 O) 2 (C 2 O 4 ) 4 ( B -β-SbW 9 O 33 ) 2 ]·64H 2 O (2) have been synthesized and characterized by IR spectroscopy, AC impedance measurements, TG, PXRD, and single-crystal X-ray diffractions. Compound 1 represents an isolated inorganic sandwich-type dimeric POM constructed from two trilacunary Keggin [ B -β-SbW 9 O 33 ] 9 − moieties and four Sc 3 + ions, while compound 2 shows an extended organic–inorganic hybrid POM which composes of two kinds of distinct tetra-Sc-substituted polyoxotungstate building units and oxalate ligands. Notably, these two compounds also are the first Sc-containing polyoxotungstates based on trilacunary Keggin [ B -β-SbW 9 O 33 ] 9 − clusters. Electrochemical study showed that compound 2 has good proton conductivity. [ABSTRACT FROM AUTHOR]

Polyoxoniobate [GeNb 18 O 54 ] 14 − and polyniobotungstate [Nb 3 W 3 O 19 ] 5 − are firstly found to co-crystallize at the same crystal to form a rare organic–inorganic hybrid polyoxometalate H[Cu(en) 2 (H 2 O)] 8 [Cu(en) 2 (H 2 O) 2 ] 2 {K 4 [Cu(en) 2 ] 2 [Cu(en) 2 (GeNb 18 O 54 )] 2 }[Nb 3 W 3 O 19 ]·32H 2 O ( 1 ). Interestingly, in 1 , the crescent-shaped polyoxoanions [GeNb 18 O 54 ] 14 − can form dimeric secondary building units (SBUs) {[GeNb 18 O 54 ] 2 [K 2 (H 2 O) 5 ] 2 } via the linkage of K + cations. These dimeric SBUs can be further bridged by copper complexes to generate 1D infinite double strand chains with completely different isolated polyoxoanions [Nb 3 W 3 O 19 ] 5 − filling the gaps between chains. [ABSTRACT FROM AUTHOR]

A series of novel 4s–4f heterometallic cluster substituted polyoxometalates (POMs) with formula of H 9 Na 12 K 2 [K 3 Ln 4 (NO 3) 2 (GeW 10 O 37) 2 (Ge 2 W 18 O 66)]·34H 2 O (1-Ln) (Ln = Dy, Ho, Er) have been hydrothermally made by adopting a trilacunary [A-α-GeW 9 O 34 ]10− as a precursor. 1-Ln represent the first examples of metal-substituted POM clusters based on mixed POM fragments including dilacunary [α-GeW 10 O 37 ]10− and multilacunary open Well-Dawson [Ge 2 W 18 O 66 ]16− fragments. • Novel 4s–4f heterometallic substituted POMs have been prepared and characterized. • The compounds contain mixed Keggin/ open Well-Dawson POM fragments. • The Luminescent properties of these compounds were systematically studied. • The work enriches the diversity of heterometallic metal cluster substituted POMs. • This work provides a new route for making new POMs based on mixed POM units. By adopting a trilacunary [A-α-GeW 9 O 34 ]10− as a precursor under hydrothermal conditions, a series of novel 4s–4f cluster substituted polyoxometalates (POMs) containing two types of in situ generated lacunary POM fragments have been made. These compounds were characterized by single-crystal X-ray diffractions, powder X-ray diffractions, infrared spectroscopy, thermogravimetric analyses, respectively. Structural analyses indicate that these compounds constructed from a seven-nuclearity K-O-Ln (Ln = Dy, Ho, Er) heterometallic cluster stabilized by mixed dilacunary Keggin [α-GeW 10 O 37 ]10−/multilacunary open Wells-Dawson [Ge 2 W 18 O 66 ]16− fragments. Furthermore, the solid luminescent properties of the compounds at room temperature were studied. [ABSTRACT FROM AUTHOR]