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A tale of two polyhedra: two nested Archimedean metal-organic polyhedra, a rhombicuboctahedron (Co(48) cage) and a cuboctahedron (Co(24) cage), have been assembled from two types of cobalt dimers and two complementary ligands. Within the 3D covalent cubic array of outer Co(48) cages and framework lie encapsulated inner Co(24) cages that are linked into a separate "hidden" 3D framework., (Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A 6(5)8 CdSO4-type 3-D framework built by hexa-Cu" sandwiched polyoxotungstates [Cu(en)2]2-[Cu(deta)(H2O)]2[Cu6(en)2(H2O)2(B-alpha-GeW9O34)2] x 6H2O (1) (en = ethylenediamine and deta = diethylenetriamine) has been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrometry, thermogravimetric analysis and single-crystal X-ray diffraction. To the best of our knowledge, 1 represents the first 3-D TMSP with 6(5)-8 CdSO4 topology in polyoxometalate chemistry. Magnetic measurements performed on 1 indicate the occurrence of ferromagnetic interactions within the copper ions and the coupling constants can be determined.

Three new group IIIA metal phosphate–oxalate (MPO) compounds, namely [(CH3)2NH2]2[M2(HPO4)2(H2PO4)2(C2O4)] (M = Al (1), Ga (2)) and [(CH3)2NH2]2[In2(HPO4)2(H2PO4)2(C2O4)]·H2O (3), have been synthesized. Their crystal structures feature an anionic layer with the sql topology net. In particular, 1 displays a proton conductivity (σ) of 9.09 × 10−3 S cm−1 at 85 °C and under 98% relative humidity, which is the highest among MPOs. This study not only endows the main group metal-based MPO family with new members, but also contributes to further understanding of the structure-directing roles of amines and provides a feasible idea for improving the proton conductivity of MPOs. [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]

Abstract: Two new Dawson-based phosphotungstates (H2en)0.5H[Cu(en)2(H2O)]2{[Cu(en)2](α 1-P2W17CuO61)}·8H2O (1) (en=ethylenediamine) and [4,4′-H2bpy]2{[Cu(4,4′-bpy)3][Cu(4,4′-bpy)4(H2O)2]2[Cu(4,4′-bpy)][α-P2W18O62]2}·6H2O (2) (4,4′-bpy=4,4′-bipyridine) have been hydrothermally synthesized and structurally characterized. 1 crystallizes in the triclinic space group P−1 with a=11.7626(17), b=13.246(2), c=29.350(5)Å, α=87.355(5), β=79.583(5), γ=66.993(3)°, V=4138.3(11)Å3, Z=2, GOF=1.089, R 1=0.0563 and wR 2=0.1505, whereas 2 belongs to the orthorhombic space group Iba2 with a=22.277(8), b=47.04(2), c=22.153(8)Å, V=23215(17)Å3, Z=4, GOF=1.051, R 1=0.0627 and wR 2=0.1477. 1 consists of a 1-D linear chain structure constructed from monocopperII-substituted Dawson polyoxoanions, while 2 represents the first 2-D sheet-like structure with a (4,4)-connected topological net built up from plenary Dawson-type polyoxoanions and CuII-4,4′-bpy complex cations in polyoxometalate chemistry. [Copyright &y& Elsevier]

A novel manganese oxyborate, K7{(BO3)[B12O18(OH)6]} · H2O (1), which is the first example showing the edge-sharing between boron and transition metal, has been solvothermally synthesized. The structure consists of [B12O20(OH)4] and [BO3] which are linked through unusual MnO5 polyhedron via vertexes and edges. This compound exhibits NLO properties and the intensity of the green light (frequency-doubled output: λ=532 nm) produced by 1 is as large as that of KDP. [Copyright &y& Elsevier]