An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

Reactions of lacunary polyoxometalate (POM), transition-metal (TM), and lanthanide-metal (Ln) cations with the assistance of additional small organic molecules under hydrothermal conditions led to the formation of a group of metal-POM frameworks (MPFs) with nanospaces: [Cu(enMe)(2)](13){Ln(SiW11O39)(2)}(2)center dot xH(2)O [Ln = Ho3+ (compound 1), Dy3+ (compound 2), Eu3+ (compound 3), Er3+ (compound 4), Sm3+ (compound 5), Pr3+ (compound 6); x = 18 for 1, 5, 6; x = 20 for 2, 3, 4; enMe = 1,2-diaminopropane). Single-crystal X-ray diffraction analyses reveal that all the compounds are composed of two monovacant POMs, which are linked by one Ln(3+) ion into a dimeric structure. The dimeric structure acts as an inorganic polydentate ligand coordinated with Cu2+ ions, which results in 3D MPFs with two channels. As the individual components integrated in the MPF materials posess fluorescent and magnetic properties, the luminescence properties and magnetic behavior of the resulting MPFs were measured.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

The sodalite-type metal–organic framework constructed from heterometallic alkali metal/V secondary building units with large internal cavity was firstly obtained. The organic amine cations within the channels can be replaced by transition metal ions through a cation exchange process, and subsequent gas adsorption measurements confirm the permanent porosity.

A novel hybrid network based on octamolybdate building unit, Cu(5)(I)LBBTZ(3)H(2)O [beta-(MoMo7O26)-Mo-V-O-VI] [1, BBTZ = 1,4-bis(1,2,4-triazol-1-ylmethyl) benzene], has been synthesized under ionothermal conditions and structurally characterized by single crystal X-ray diffraction. Compound 1 is a rarely self-penetration network constructed by three dimensional(3D) poly-rings networks and (4,4) 2D layers, in which the two interpenetrating parts were united together through Cu2 and Cu1 centers. Further, the infrared (IR) spectrum, thermogravimetric(TG) analysis and photocatalytic studies were also performed to authenticate the identities of the title compound. Photocatalytic study revealed that compound 1 was active for photocatalytic 112 evolution under UV irradiation.

POMs sorgen für Poren: Eine Ionothermalsynthese führte zu porösen offenen Gerüsten auf Polyoxometallat(POM)-Basis, deren Strukturen beim Erwärmen bis 300 °C unverändert bleiben. Die sperrigen Tetrabutylammonium-Kationen in den Nanokanälen können außerdem gegen Übergangsmetallionen ausgetauscht werden. Gasadsorptionsmessungen bestätigen die permanente Porosität.

A new polyoxometalate-based inorganic-organic hybrid material, H5Ag(Bbi) (1.5)(Bbi)(2) [P2W18O62] (1) (Bbi = 1,1-(1,4-butanediyl)-bis(imidazole)), has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction, elemental analyses, IR spectroscopy, and thermogravimetric analysis. In 1, adjacent [P2W18O62](6-) (short for P2W18) anions are connected through Ag by equatorially positioned terminal oxygen atoms to generate a 1-D chain. Adjacent chains were further connected through Ag and two-coordinated Bbi ligands into a (6, 3)-layer, which are extended to 3-D supermolecule nets through H bonds. The photo-and electro-catalytic properties of 1 have been studied.

A 12-connected metal-organic framework based on an unprecedented cyclic Cu-12 cluster with a large internal cavity has been prepared, and its cation exchange property was determined.

Two new {P8W48} wheel-based compounds, Na12Li16{[Cu(H2O)]2[Cu4(OH)4(H2O)8]2P8W48O184}·55H2O (1), and K4Na24Li10{(MoO2)2(P8W48O184)}·61H2O (2) have been synthesized by a conventional aqueous solution method, and characterized by UV, IR, TG analysis, XPRD, 31P NMR, XPS, single-crystal X-ray diffraction analyses, magnetic study and electrochemistry study. In compound 1, a wheel-type {P8W48} containing two {Cu4} clusters and two isolated Cu cations results in a 10-Cu-containing polyoxotungstate, which represents the first {P8W48}-based compound trapping two transition metal (TM) clusters in its inner cavity. Further, the polyoxoanion was connected by Na+ and Li+ cations into a 3D framework. Compound 2 is a 2-Mo-containing {P8W48}-based polyoxotungstate. Magnetic study indicates that antiferromagnetic interactions exist in compound 1.

Three hybrid networks based on octamolybdate building units, Cu(I)(8)BBTZ(6)[(α-Mo(8)O(26))(β-Mo(8)O(26))] (1), (Cu(I)BBTZ)(4)[Mo(7)Cu(II)O(24)(H(2)O)(2)]·6H(2)O (2), and Cu(II)Cu(I)(2)BBTZ(5)[β-Mo(8)O(26)] (3) (BBTZ = 1,4-bis(1,2,4-triazol-1-ylmethyl)benzene), have been synthesized under ionothermal conditions and structurally characterized by single-crystal X-ray diffraction. 1 exhibits a rare 3D three-fold self-penetration network (SPN) structure, in which the interpenetrating polymer networks (IPN) formed by α-Mo(8)O(26) units, Cu(I) ions and BBTZ ligands are united by β-Mo(8)O(26) units. 2 shows a classic 10(3)-utp net built by transition-metal monosubstitution octamolybdate β-Mo(7)CuO(26), Cu(I) and BBTZ ligands. 3 displays an interesting interpenetrating network (IPN) structure formed by 2D poly-rings layers and 3D NaCl topology framework. IR, TG, and electrochemical studies were also conducted to further authenticate the identities of these compounds. Photocatalytic investigation indicates that compounds 1-3 are active for photocatalytic H(2) evolution under UV irradiation.

Two classic polyozornetalate-based compounds, (H2BBI)(3) center dot [P2W18O62] center dot H2O (1), H-2(H2BBI)(2) center dot [P2W18O62] center dot 2H(2)O(2) [BBI = 1, 1-(1,4-butanediyl)-bis(imidazole)], were synthesized under different solvents. The structures of the two compounds were characterized by elemental analysis, single crystal X-ray diffraction and FTIR spectra. Compound 1 was constructed into a novel 3D supermolecule through bridge and terminal oxygen atoms of Dawson type anions, and free water molecules. Compound 2 crystallized in chiral space group P1 through changing the spatial arrangement of the organic ligand BBI molecules with changing the solvent. The photocatalysis properties of the two compounds were also studied.

Two new multi-copper-containing polyoxotungstates [Cu(en)(2)(H2O)(2)] [Cu(en)(2)](4), [Cu(en)(2)(H2O)] [Cu-4(H2O)(2)(SiW9O34)(2)]center dot 7H(2)O (1) and [Cu(en)(2)(H2O)](2) [Cu(en)(2)](4) [CuSiW11O39](2)center dot 7H(2)O (2) were hydrothermally synthesized. The diffraction analysis reveals that compound 1 represents the organic-inorganic hybrid based on the sandwich-type polyoxometalates linked by transition-metal coordination cations. The framework of 2 has a two-dimensional net-texture structure with vacancies in it, and the 2D layers are arranged in a parallel-staggering fashion to form a 3D supermolecules framework. It represents a 3D organic-inorganic hybrid based on the bimolecular Keggin polyoxometalates.

By adjusting the molar ratio of the reactants H3PO4 and Na2MoO4, four new metal-organic frameworks, namely, CoH(bix)(4)[(PMo8V4O40)-V-VI-O-V((VO)-O-IV)(2)] (1), (H(2)bix)(2)(NaHP2Mo5O23)center dot 2H(2)O(2), H-2(bix)(4)[Cd(H2O)(4)][Cd(HPO4)(4)(H2PO4)(4)(MoO2)(12)(OH)(6)]center dot 10H(2)O (3) and (H(2)en)(3)(Co3P4Mo4O28) (4) (bix 1,4-bis(imidazol-1-ylmethyl) benzene, en 1,2-ethylenediamine), have been hydrothermally prepared and characterized by elemental analyses, IR spectroscopy, TG analyses, and single-crystal X-ray diffraction. Compound 1 consists of straight chains based on pseudo-Keggin (PMo8V4O40)-V-VI-O-V((VO)-O-IV)(2)](3-) polyanions and [CoH(bix)4](3+) complex fragments, which are further connected into a three-dimensional (3D) open framework by hydrogen bonding interactions between polyanions and organic bix ligands. Compound 2 shows 3D supramolecular networks constructed from weak interactions between free biprotonated bix, water and oxygen atoms of polyanions [P2Mo5O23](6-). In compound 3, [Cd(HPO4)(4)(H2PO4)(4)(MoO2)(12)(OH)(6)](4-) polyanions are linked by [Cd(H2O)(4)](2+) cations to build one-dimensional (1D) chains. Then weak interactions between free bix ligands, water and oxygen atoms of the polyanions extend these 1D chains to 3D supramolecular frameworks. Compound 4 exhibits open-framework structures. Interestingly, it also shows 1D left and right-handed helical chains and 2D (6,3)-layers. The molar ratio of the reactants H3PO4 and Na2MoO4 influence the transformation of the phosphomolybdate clusters in compounds 1-4. The electrochemistry and photocatalysis properties of these compounds have also been investigated in this paper.

One new polyoxometalate compound H-3(Tea)(Bmim)(3)[P2W18O62]center dot 3H(2)O (Tea = triethylamine, Bmim = 1-methyl-3-ethylimidazole) (1) and three new polyoxometalate-based metal organic frameworks (PMOFs) Cu-II(Bbi)(1,5)(H(2)Bbi)(2)[P2W18O62] (Bbi = 1,1-(1,4-butanediyl)-bis(imidazole)) (2), Cu-2.5(II)(Mimin)(HMimin)(Bbi)(3)[P2W18O62]center dot 3H(2)O (Mimin = methylimidazol) (3), and Cu-II(Bbtz)(H(2)Bbi)(H(2)Btp)[P2W18O62] (Bbtz = 1,4-bis(triazol-1-ylmethyl)benzene, Btp = 1,3-Bis(1,2,4-triazol-1-yl)propane) (4) have been synthesized under ionothermal conditions using an ionic liquid (IL) [Bmim]Br (Bmim = 1-ethyl-3-methylimidazole) as solvent. Their structures were determined by single crystal X-ray diffraction. Compound 1 possesses a one-dimensional (ID) supramolecular chain-like structure constructed from [P2W18O62](6-) anions, Bmim, Tea, and water molecules. Compound 2 has a two-dimensional (2D) (6,3)-layer structure built by [P2W18O62](6-) anions, copper ions, and Bbi ligands. Compounds 3 and 4 are three-dimensional (3D) PMOFs with novel (6.8.10)(4.6.8(3).10)(4.6.8(3).12) and classic (6(5).8)(6(5).8)-cds topologies, respectively. Compounds 2-4 represent the first examples of PMOFs synthesized by the ionothermal method. The successful synthesis of compounds 2-4 suggests that ionothermal synthesis will be a very promising synthetic technique for assembling new PMOFs. Additionally, the properties of the four compounds have been studied in detail.

A new sandwich-type phosphotungstate compound, H3(Emim)7[Ni4(Mim)2(PW9O34)2]·4H2O, was successfully synthesized. We used the ionothermal method with 1-ethyl-3-methyl imidazolium bromide ([Emim]Br) ionic liquids (ILs) to synthesize the compound. We characterized the material using X-ray diffraction, elemental analysis, infrared spectroscopy, thermogravimetric analyses, electrochemistry and photocatalysis. The crystal state of the sandwich-type phosphotungstate was: Monoclinic; space group C2/c; a = 35.584(7) ; b = 14.513(3) ; c = 24.423(5) ; α = 90.000°; β= 101.38(3)°; γ= 90.000°; V = 12365(4) 3; and Z = 4. The polyoxoanion of the sandwich-type phosphotungstate is two methylimidazole molecules and a modified sandwich-type hybrid tungstophosphate [Ni4(Mim)2(PW9O34)2]10-. In the packing arrangement, the adjacent hybrid polyoxoanions of the compound are connected through C-H-O hydrogen bonds between the dissociative [Emim]+ cations and the surface oxygen atoms of the polyoxoanions. This structure forms a three-dimensional open-framework.

A new inorganic–organic hybrid complex, Na2[{Ag10(NC5H4COO)8(H2O)6}(SiW12O40)] (1), has been successfully synthesized from [SiW12O40]4− anions, Ag+ ions and 1,3-bis(4-pyridyl)propane under hydrothermal conditions and characterized by elemental analyses, IR spectroscopy, TG analyses, and single-crystal X-ray diffraction. In complex 1, each [SiW12O40]4− anion connects with six Ag atoms and in turn each Ag atom links to three [SiW12O40]4− anions, leading to a (6,3) layer. Such (6,3) layers are arranged in parallel and further linked by [Ag(H2O)(NC5H4COOH)2]− fragments to generate a 3D framework. The most striking feature in this work is that 1,3-bis(4-pyridyl)propane converses to isonicotinic acid in the synthetic reaction of 1, which may be induced by the combined function of Ag+ ion and polyoxometalate.

Three new Fe-containing MOFs, H3O[Fe5(BTC)3(OAc)2(DMF)2]·H2O 1, [FeNa(m-BDC)2]·NH2(CH3)2 2 and [N(CH3)4]2[Fe3(HBTC)(BTC)2(H2O)]·5.5H2O 3 (BTC=1,3,5-benzenetricarboxylate, m-BDC=1,3-benzene-dicarboxylate), have been synthesized from the solvothermal reactions of iron salts and carboxylate ligands. The framework of 1 is constructed from two kinds of secondary building units (SBUs): the sinusoidal chain of iron octahedra SBU [Fe2(COO)6]n2n− and paddle-wheel SBU [Fe2(COO)4(DMF)]. Compound 1 represents the first example of Fe-containing MOFs constructed from two kinds of SBUs. The framework of 2 is built from zigzag-chain SBUs [FeNa(COO)6]n3n− and m-BDC linkers. The framework of 3 is formed by linear tri-nuclear iron SBUs [Fe3(COO)8(H2O)]2− and triangular BTC linkers. To our knowledge, the Fe-containing sinusoidal chain SBU in 1, zigzag-chain SBU in 2 and linear tri-nuclear iron SBU in 3 are found in Fe-containing MOFs for the first time. Magnetic investigation indicates the present of antiferromagnetic exchange interaction within the iron units of compounds.

Three new organic–inorganic hybrid complexes based on the Wells–Dawson polyoxoanion, namely (H2bpp)[Ni2(bpp)2(H2O)4(P2W18O62)]·H2O 1, [Cu6(Hbpy)6(bpy)3(P2W18O62)2]·2H2O 2 and (Him)5[Cu(im)2(P2W18O62)]·4H2O 3 [bpp = 1,3-bis (4-pyridyl) propane, bpy = 4,4′-bipyridine, im = imidazole] have been synthesized and characterized. Complex 1 exhibits a three-dimensional (6, 3)-connected framework with anatase topology constructed from [α-P2W18O62]6− clusters and [Ni(bpp)]2+ fragments. Each [α-P2W18O62]6− anion links to six nickel atoms through six terminal oxygen atoms from four polar and two equatorial WO6 octahedra, which shows a novel coordination mode of a Wells–Dawson cluster with a transition-metal atom. Complex 2 displays an interesting one-dimensional double-chain structure built from [α-P2W18O62]6− clusters and [Cu2(bpy)(Hbpy)2]2+ fragments. To our knowledge, complex 2 represents the first double-chain organic–inorganic hybrid complex based on a Wells–Dawson-type cluster. Complex 3 possesses a one-dimensional zigzag chain structure constructed from [α-P2W18O62]6− anions and [Cu(im)2]+ units through weak Cu···O interactions.

Cd(OAc)(2)center dot 2H(2)O and MnCl2 center dot 4H(2)O were separately introduced to the mixture of MoO3, H3PO4 and bpy. Two new reduced molybdenum phosphate [P4Mo6O28(OH)(3)](9-) ({P4Mo6}) extended inorganic-organic hybrid supramolecular networks (H(2)bpy)(2)[Cd(H2O)](3)[Cd(HPO4)(6)(PO4)(2)(OH)(6)(MoO2)(12)]center dot 5H(2)O (1) and (H(2)bpy)(3)[Mn(H2O)(2)](2)[Mn (HPO4)(6)(PO4)(2)(OH)(6)(MoO2)(12)]center dot 10H(2)O (2) have been synthesized under hydrothermal techniques. Here, compounds 1 and 2 have been characterized by elementary analyses, IR, TG, and single crystal X-ray diffraction. Compound 1 crystallized in the triclinic, space group P (1) over bar, a=1.1877(2) nm, b=1.348 5(3) nm, c=1.410 8(3) nm, alpha=106.87(3)degrees, beta =108.09(3)degrees, gamma = 107.92(3)degrees, V = 1.848 3(6) nm(3), Z = 1; Compound 2 crystallized in the triclinic, space group P (1) over bar, a = 1.196 8(2) nm, b = 1.335 4(3) nm, c = 1.462 0(3) nm, alpha = 77.58(3)degrees, beta = 67.97(3)degrees, gamma = 76.12(3)degrees, V = 2.082 2(7) nm(3), Z = 1. The polyanion of compound 1 [Cd(H2O)](3)[Cd(HPO4)(6)(PO4)(2)(OH)(6)(MoO2)(12)](2-) is composed of Cd[P4Mo6](2) dimer and tri-nuclear {Cd-3} linkers, which are connected together to form inorganic chains. The polyanion [Mn(H2O)(2)](2)[Mn(HPO4)(6)(PO4)(2)(OH)(6)(MoO2)(12)](3-) of compound 2 exhibits a 2D inorganic layer, consisting of Mn[P4Mo6](2) units linked by the Mn2+ ions. These two kinds of inorganic extended structures are further linked with Hydrogen bonds of protonated bpy to construct different 3D supramolecular networks. Simultaneously, the electrochemical property of compound 2 has been explored. CCDC: 661669, 1; 661670, 2.