A feasible route to approach 3D POM-based hybrids: utilizing substituted or reduced Keggin anions with high charge density.

Five new hybrid compounds based on Keggin polyanions, Ag(+)/Cu(+) ions and 1,3-bis(1,2,4-triazol-1-yl)propane (btp) molecules have been hydrothermally synthesized. In [Ag(5)(btp)(4)(H(2)O)(2)][PCuW(11)O(39)]·2H(2)O (1), [Ag(4.33)Na(0.67)(btp)(4)(H(2)O)(2)][PMnMo(11)O(39)]·H(2)O (2) and [Cu(4)(btp)(4)Na(H(2)O)(2)][PMnMo(11)O(39)]·2H(2)O (3), the neighboring mono-substituted Keggin clusters are alternately connected via sharing oxygen atoms to form an unusual Keggin-based transition-metal monosubstituted chain, in which the Keggin cluster serves as a decadentate ligand and grafts ten metal atoms representing the highest connected number for Keggin cluster and forming a 3D framework. In [Ag(5)(btp)(4)][PW(VI)(10)W(V)(2)O(40)] (4) and [Ag(5)(btp)(4)][PMo(VI)(10)Mo(V)(2)O(40)] (5), two-electron reduced Keggin clusters as hexadentate linkages are inserted in the rhomboid-like tunnels of the Ag-btp framework and connect with the framework via six Ag-O bonds to achieve 3D motifs, which are new and rare examples of heteropoly blue based hybrid compounds. The successful synthesis of the five high-dimensional structures may provide a feasible route for us to approach 3D polyoxometalate-based hybrids by using substituted Keggin anions and heteropoly blues with high charge density. Furthermore, photocatalytic experiments indicate that both 1 and 4 have good activities for photocatalytic degradation of RhB under UV irradiation. The luminescent properties of compounds 1-5 in the solid state were also investigated.

Tailoring microstructures of isopolymolybdates: regular tuning of the ligand spacer length and metal coordination preferences.

Four new isopolymolybdate compounds based on two kinds of isomers, [Cu(I)(2)bte][a-Mo(3)O(10)] (1), [Cu(I)(2)btp][b-Mo(3)O(10)].H(2)O (2), [Cu(II)(bte)(1.5)(H(2)O)][gamma-Mo(8)O(26)](0.5) (3) and [Cu(II)(btp)(2)(H(2)O)][beta-Mo(8)O(26)](0.5).2H(2)O (4) [bte = 1,2-bis(1,2,4-triazol-1-yl)ethane, btp = 1,3-bis(1,2,4-triazol-1-yl)propane], were obtained under hydrothermal conditions, indicating that isopolymolybdate clusters can be tailored by regular tuning of the spacer length of the flexible ligands and the metal coordination preferences. In compound 1, wave-like a-[Mo(3)O(10)](2-) chains intersect with [Cu(I)(2)bte](2+) chains by sharing Cu(I) cations, forming a 3D framework. Compound 2, with a similar 3D structure but different ligand (btp) to 1, is based on linear b-[Mo(3)O(10)](2-) chains. In compound 3, gamma-[Mo(8)O(26)](4-) chains insert into the rectangular windows of parallel [Cu(II)(2)bte](4+) sheets and connect them via four Cu(II)-O bonds, leading to a 3D framework. Compound 4 is an unusual 2D-->3D polycatenated array of a [Cu(II)(btp)(2)(H(2)O)][beta-Mo(8)O(26)] pillar-layered framework. The thermal stability and luminescent properties of compounds 1-4 were investigated in the solid state.

A polyoxometalate-encapsulated 3D porous metal-organic pseudo-rotaxane framework.

A novel compound, [Cu(bimb)](2)(HPW(12)O(40)) x 3 H(2)O (bimb = 1,4-bis(imidazol-1-ylmethyl)biphenyl) with a polyoxometalate-encapsulated 3D metal-organic pseudo-rotaxane framework that can be described as a 2-fold dianet topology showing well-defined 1D nano-scale tunnels, has been synthesized hydrothermally, and its de-/rehydration behavior has been investigated.

Assemblies of copper bis(triazole) coordination polymers using the same keggin polyoxometalate template.

Four inorganic-organic hybrid compounds, [Cu(I)(4)(bte)(4)(SiW(12)O(40))] (1), [Cu(II)(2)(bte)(4)(SiW(12)O(40))].4H(2)O (2) [bte = 1,2-bis(1,2,4-triazol-1-yl)ethane], [Cu(I)(4)(btb)(2)(SiW(12)O(40))].2H(2)O (3), and [Cu(II)(2)(btb)(4)(SiW(12)O(40))].2H(2)O (4) [btb = 1,4-bis(1,2,4-triazol-1-yl)butane], were hydrothermally synthesized through use of the same Keggin polyoxometalate as the template and tuning the molar ratio of the bis(triazole) ligand to the Cu(II) ion. The ratio of the bis(triazole) ligand to Cu(II) has a crucial influence on the structures of this series. Single-crystal X-ray diffraction analyses indicate that compound 1 is constructed by tetranuclear ring-connecting chains and polymerized [Cu(bte)](+) chains, between which SiW(12) anions are inserted to form a three-dimensional (3D) structure. Compound 2 shows a (4(4).6(2)) two-dimensional grid sheet. The discrete SiW(12) anions are sandwiched by the sheets, just like "hamburgers". Compound 3 presents channel-like [Cu(2)(btb)](2+) polymerized chains, which are further connected by SiW(12) anions to construct a 3D framework. Compound 4 exhibits a (6(6)) 3D Cu-btb framework with hexagonal channels, into which the tetradentate SiW(12) anions are incorporated. The thermal stabilities of the compounds are discussed.