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An oxalate-assisted strategy was first developed for creating new polyoxotantalates (POTas). With this strategy, two brand-new POTa supramolecular frameworks based on uncommon dimeric POTa secondary building units (SBUs) were constructed and characterized. Interestingly, the oxalate ligand can not only serve as a coordination ligand to form unique POTa SBUs but also act as a key hydrogen bond acceptor to construct supramolecular architectures. Besides, the architectures show outstanding proton conductivity. The strategy opens up new opportunities for developing new POTa materials. [ABSTRACT FROM AUTHOR]

This work demonstrates a feasible strategy for the synthesis of new zeolite-like framework materials. With the strategy of using two different supertetrahedral clusters as secondary building units, two new heterometallic zeolite-like frameworks with isomeric structures but tunable topologies were first made. Besides, the porous nature and the proton conduction performance of the new materials were further studied. [ABSTRACT FROM AUTHOR]

A 4p–4f cluster incorporated polyoxometalate (POM), namely, H18{[(H4pic)4Eu10Se13O28(H2O)12](α-GeW9O34)4·40H2O (1-Eu, H4pic = isonicotinic acid), has been first synthesized and characterized. 1-Eu features an interesting four-shell structure, representing the largest Se-4f cluster incorporated POM known to date. Besides, 1-Eu exhibits excellent Lewis acid–base catalytic activity and reusablity in catalyzing the gram-scale dehydration condensation reaction of hydrazines and 1,3-diketones to synthesize polysubstituted pyrazoles. [ABSTRACT FROM AUTHOR]

Two inorganic–organic hybrid isopolyoxoniobates (1 and 2) based on new high-nuclearity {Nb54O151} clusters have been synthesized under hydrothermal conditions. In particular, the combination of the unique {Nb54O151} clusters with copper-amine complexes has led to rare helical nanotubes, which are further linked by alkali metal cations or copper-amine complexes into two 2D similar bamboo-raft-like layered networks (1 and 2), respectively. Compound 1 exhibits effective base-catalytic decomposition of chemical warfare agent simulants dimethyl methylphosphonate (DMMP) and diethyl cyanophosphonate (DECP). [ABSTRACT FROM AUTHOR]

A series of 3d–4f heterometallic cluster incorporated polyoxoniobates (PONbs) with different magnetic properties were first made and characterized. This work not only provides a promising strategy to make new heterometallic cluster incorporated PONbs but also demonstrates an ideal model to probe how transition-metal ions influence the magnetic property of PONbs. [ABSTRACT FROM AUTHOR]

3d–4f heterometallic supertetrahedral clusters with the formula of Ln4Zn6(μ6-O)L4(CH3COO)6(NO3)4(CH3OH)4(H2O)2 (1-Ln, Ln = Eu, Gd, Tb, H3L = 2-(hydroxymethyl)-2-(pyridin-4-yl)-1,3-propanediol) have been successfully introduced as stable secondary building units (SBUs) to construct new cluster-organic frameworks with tunable emission, demonstrating a promising strategy for developing new optical materials. [ABSTRACT FROM AUTHOR]

Nanoscale {Nb68O200} cages have been successfully employed as flexible and stable secondary building units to combine with bridging copper–amine complexes to construct two proton conductive polyoxoniobate frameworks, demonstrating a promising strategy for making new porous materials. [ABSTRACT FROM AUTHOR]

A series of POM-based all-inorganic open frameworks, H9[Ln9W8(μ4-O)12(μ2-O)24(H2O)24](SiW12O40)3·60H2O (1-Ln, Ln = La, Pr and Nd), have been fabricated and structurally characterized for the first time. The unique architectures are constructed from nanoscale four-shell Ln@W8@Ln8@(SiW12)6 clusters. Additionally, the porous nature of the frameworks has also been investigated. [ABSTRACT FROM AUTHOR]

Reported here is a lithium cubane based zeolitic framework possessing a multi-dimensional channel system. The unique design strategy of adopting the ditopic ligand 4-pyridinol leads to a rigid porous framework with high thermal stability. It has a BET surface area of 440.3 m2g−1and a H2uptake capacity of 108.7 cm3g−1at 77 K. [ABSTRACT FROM AUTHOR]

A tin(ii) tungstosilicate derivative K11H[Sn4(SiW9O34)2]·25H2O with four sandwiched Sn2+cations was prepared by reaction of SnCl2, KCl and Na10[α-SiW9O34]·xH2O. Visible-light photocatalytic H2evolution activity was observed with Pt nanoparticles as co-catalyst and methanol as sacrificial agent. [ABSTRACT FROM AUTHOR]

An unusual high-valent Sb(V)-based unit [SbL2]− (L = 2-(hydroxymethyl)-2-(pyridin-4-yl)-1,3-propanediol) was developed for the first time to combine with various cuprous-halide clusters for the construction of a brand-new class of heterometallic MOFs. This work not only promotes the limited development of Sb-based MOFs, but also provides a practical strategy for developing new types of composite materials. [ABSTRACT FROM AUTHOR]

The first two inorganic–organic hybrid three-dimensional (3D) polyoxotantalates (POTas) and the first two inorganic–organic hybrid 2D POTas have been obtained. All of these high-dimensional POTas are built from a new-type POTa dimeric cluster {Cu(en)(Ta6O19)}2/{Cu(enMe)(Ta6O19)}2 (en = ethylenediamine, enMe = 1,2-diaminopropane) bridged by copper complexes. Interestingly, extended POTas 1 and 3 can undergo single-crystal to single-crystal structural transformations triggered by water. [ABSTRACT FROM AUTHOR]

This work demonstrates a new Lindqvist-like [Fe III6 (μ6-O)L4Cl6]2− (Fe6, L = 2-(hydroxymethyl)-2-(pyridin-4-yl)-1,3-propanediol) cluster for the construction of a novel class of Fe-cluster organic frameworks. The novel Fe6 cluster can be used to build not only a homometallic MOF, but also a heterometallic MOF by introducing copper halide clusters to the reaction system. In particular, the heterometallic MOF achieved a skillful combination of Fe6 SBU and cuprous–halide clusters for the first time. Our synthesis strategy opens up an effective avenue to novel Fe-cluster-based MOF materials. [ABSTRACT FROM AUTHOR]

A nested Cu24@Cu72 copper–organic framework, [Cu5(bdc)4(ina)2(H2O)3]·solvent (1, H2bdc = 1,3-benzenedicarboxylic acid and Hina = isonicotinic acid) based on paddlewheel Cu2(COO)4 SBUs, has been synthesized. There are three types of cages with different sizes and shapes: Cu24-cage, Cu60-cage and Cu72-cage. The Cu72-cage, which is the highest-nuclearity Cu-cage reported to date, encapsulates a Cu24-cage to form a double-walled Cu24@Cu72 cage-within-cage structure. Dye adsorption studies reveal that compound 1 can rapidly and selectively adsorb cationic dyes. [ABSTRACT FROM AUTHOR]

A series of new Ln14-substituted polyoxometalates, H27Na16[(Ln14(H2O)W4(OH)O14)(WO4)4(GeW10O38)6]·nH2O (n≈ 86) (1-Ln, Ln = Eu, Gd, Tb, Dy, Ho, Er), which contain 14 Ln3+ and 6 {α(1,5)-[GeW10O38]12−} units, has been synthesized in one-pot reactions. As the first 14-Ln-containing polyoxometalates, the octahedron-shaped three-shell structure of the [(Ln14(H2O)W4(OH)O14)(WO4)4(GeW10O38)6]43− polyanion is made up of a W4 tetrahedron, a Ln14W4 tetrahedron and a Ge6W60 octahedron. Compound 1-Dy exhibits frequency dependent magnetic properties. Compounds 1-Eu, 1-Tb and 1-Dy exhibit the characteristic emission bands of the Ln3+ ion. [ABSTRACT FROM AUTHOR]

A cationic lanthanide metalloligand with 3 dangling carboxylate groups on its periphery co-assembles with nitrate into a porous thermochromic solid responsive to both external cations and anions, owing to the presence of exchangeable NO3− as well as cation cavities arising from cooperative orientation of free carboxylate groups. An especially interesting feature is the structural memory effect during crystallization exhibited by the metalloligand, even after dissolution and binding to secondary cations (Cu2+, Cd2+…). Moreover, the porous solid can undergo ion-exchange with various anions, leading to tunable thermochromic temperature and color range. [ABSTRACT FROM AUTHOR]

The use of 1H-1,2,4-triazole-3-thiol (H2trzS) has led to a rare inorganic–organic hybrid supramolecular nanotube built from novel Ni5-substituted polyoxotungstates, which presents interesting structural characteristics, high chemical stability, and proton-conducting properties. [ABSTRACT FROM AUTHOR]