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A new organic-inorganic hybrid compound [H2biim]5.5[La0.35 ⊂ P6MoV4MoVI14O73]·10H2O (1) (biim = biimidazole) has been synthesized and characterized by IR, UV–Vis, XRD, XPS, elemental analysis, X-ray diffraction analysis and fluorescent spectrum analysis. Compound 1 exhibits a 3D supramolecular channel structure based on {La0.35Mo18P6O73} clusters through O┄O supramolecular interactions with biim molecules and water molecules locating in the channels through N H⋯O and O H⋯O hydrogen bonds. The photocatalytic activities of compound 1 for decompositions of rhodamine B (RhB) and methylene blue (MB) under the UV irradiation has also been investigated.

Three new compounds {[Ni(biim)(dipic)(H2O)][PSb2IIIMo6VMo6VIO40]·(Hbiim)}·1.5H2O (1); [(HTEA)(TEA)0.75]2 [PSb2IIIMo5V Mo7VIO40](2), (TEA)]2[HPSb2IIIMo4VMo8VIO40](3) (dipic = 2, 6- pyridine carboxylic acid, biim = 2, 2-biimidazole, TEA = triethylamine) have been synthesized under mild hydrothermal condition and structurally characterized by physico-chemical and spectroscopic methods. Single crystal X-ray diffraction analysis reveals that compound 1 represents new example formed by {PSb2Mo12O40} and transition metal mixed-organic-ligand complexes (TMMCs). The compounds 1–3 all exhibit novel 3D supermolecular channel structures through complex hydrogen bonds and strong O┄O supermolecular interactions. The photocatalytic activities of compounds 1–3 for decomposition of rhodamine B (RhB) and methylene blue (MB) under UV irradiation have also been investigated.

Three new supramolecular compounds [Cu0.5(H3O)2](H2prz)1.5[Mo5P2O23]·H2O (1); [4,4′-bpy]2[4,4′-H2bpy][H4Mo5P2O23]·4H2O (2); [4,4′-Hbpy][4,4′-bpy][H3Mo5P2O23]·2H3O (3); (pyz = pyrazine, bpy = 4,4′-bpyridine) have been hydrothermally synthesized and characterized by IR, UV-Vis spectroscopy, X-ray photoelectron spectroscopy (XPS), powder XRD analyses, TG analyses, cyclic voltammogram analyses, elemental analyses and single crystal X-ray diffraction analyses. Single crystal X-ray diffraction analysis reveals that there are multipoint hydrogen-bonding interactions in compounds 1–3. The structural features of the three compounds are that distinct one-dimensional (1D) chains are firstly formed, then the chains extend to form novel two-dimensional (2D) networks, finally unprecedented three-dimensional (3D) supramolecular host-guest structures were generated by Strandberg-type polyoxometaltes (POMs) and transition metal coordination complexes (TMCs) or organic ligands, and small organic guest molecules are exactly entrapped in void spaces via H-bonding interactions. The formations of the three distinct 3D supramolecular hybrid materials demonstrate the important role of H-bonds (non-covalent bond) in the construction of high dimensional architectures. Compounds 2–3 also show outstanding photocatalysis properties.

Two compounds [Cu(biim)]2(TEA)2[HPW12O40]·H2O (1); [Cu(im)2](im)[H2PMo12O40] (2), (biim = 2,2′-biimidazole, im = imidazole, TEA = triethylamine) have been hydrothermally synthesized and characterized by IR, XPS, XRD, UV-Vis, fluorescent spectra analysis, elemental analysis, X-ray diffraction analysis, cyclic voltammetric measurement and single crystal X-ray diffraction analysis. Single crystal X-ray diffraction analysis reveals that compounds 1–2 represent new examples formed by polyoxoanions, transition metal coordination complexes (TMCs) and organic amines. Compound 1 exhibits a 3-D supermolecular structure of which layers A and C are stacked alternatively, while compound 2 first shows a 1-D chain structure with an –A↑–A↓–A↑–A↓ linking mode, then along a, b and c axis, respectively exhibits different beautiful 2-D supramolecular networks via hydrogen bond interactions.The photodegradation properties of compounds 1–2 have been investigated.

Two new organic–inorganic hybrid compounds, [Cu(phen)(prz)]2[PMoV1MoVI7VIV2VV4O42]·4H2O (1) and [Ag2(phen)4]2[PMoV1MoVI7VIV2VV4O42] (2) (phen = 1,10-phenanthroline, prz = pyrazine), have been synthesized and characterized by IR, XPS, XRD, UV–vis, fluorescent spectra analyses, elemental analyses, X-ray diffraction analyses, TG analyses, and cyclic voltammetric measurements. Both compounds are formed by Keggin POM cores and transition metal fragments. Compound 1 exhibits an unprecedented 1-D chain structure constructed from [PMoV1MoVI7VIV2VV4O42]4− and [Cu(phen)(prz)]2+ in the –A–B↑–C–B↓– linking mode. Compound 2 shows a supramolecular structure formed by [PMoV1MoVI7VIV2VV4O42]4− and [Ag2(phen)4]2+.

Two new hybrid compounds, [Cu(1)(phen)(H2O)][Cu(2)(phen)(H2O)]([Cu(3)]0.25(H2O)][P2Mo5O23]·3.75H2O (1) and [Cu(en)2]1.5[P2Mo5O23]2·(enH2)3·2H2O (2) (phen = 1,10-phenanthroline, en = ethylenediamine), have been hydrothermally synthesized and characterized by IR, UV–Vis spectroscopy, X-ray photoelectron spectroscopy (XPS), powder XRD analyses, TG analyses, cyclic voltammogram analyses, elemental analyses, and single crystal X-ray diffraction analyses. Single crystal X-ray diffraction analyses reveal that the two compounds have a 1-D chain structure formed by Strandberg-type POMs and TMCs with –A–B–C–B–A–B–C–B– linking mode, then further extend into a 2-D layer structure through π⋯π or hydrogen bond interactions.

Two new compounds, namely [Cu 4 (4,4′-bpy) 4 ][SiW 12 O 40 ]·6H 2 O ( 1 ) and [Cu 2 (4,4′-bpy) 2 ][SiMo 12 O 40 ]·(H 2 4,4′-bpy) ( 2 ) (bpy = bipyridine), have been hydrothermally synthesized and characterized by IR, UV–Vis, X-ray photoelectron spectroscopy (XPS), powder XRD, elemental analyses and single crystal X-ray diffraction. The two compounds represent new examples of compounds constructed from Keggin polyanions, metal ions and organic ligands. Compounds 1 and 2 both contains Cu(4,4′-bpy) n n+ infinite chains and [SiM 12 O 40 ] 4− anions (M = W for 1 and M = Mo for 2 ). However, the structures of compounds 1 and 2 are thoroughly different. The Cu(4,4′-bpy) n n+ infinite chains and [SiW 12 O 40 ] 4− anions in compound 1 are connected into a 2-D layered framework structure, and the Cu(4,4′-bpy) n n+ infinite chains and [SiMo 12 O 40 ] 4− anions in compound 2 are linked into a 1-D ladder-like structure.

Two new compounds [Cu(enMe) 2 ][Cu(enMe) 2 (H 2 O)][SiMo V 6 Mo VI 6 Sb 2 O 40 ] ( 1 ) and [Ni(en) 2 ] 2 [SiMo V 6 Mo VI 6 Sb 2 O 40 ] ( 2 ) (enMe = 1,2-diaminopropane, en = 1,2-ethylenediamine) have been hydrothermally synthesized and characterized by IR, UV–Vis spectroscopy, X-ray photoelectron spectroscopy (XPS), powder XRD analyses, elemental analyses and single crystal X-ray diffraction. The two compounds represent the first examples of hybrids based on bi-antimony capped Keggin polyanions {SiMo 12 Sb 2 O 40 } and different transition metal coordination complexes.

Four new organic–inorganic hybrid compounds based on bicapped Keggin polyoxometalate {PMo12Sb2O40}: [H24,4′-bpy][PMo12Sb2O40]·6H2O (1), [Him]2[PMo12Sb2O40]·H2O (2), [H3(DABCO)2][PMo12Sb2O40]·2H2O (3) and [Mn(phen)3][PMo12Sb2O40] (4) (bpy = bipyridine, im = imidazole, DABCO = 1,4-diazabicyclo[2,2,2]octane, phen = phenanthroline) have been prepared hydrothermally and characterized by IR, UV–Vis spectroscopy, X-ray photoelectron spectroscopy (XPS), powder XRD analyses, elemental analyses, fluorescence analysis and single crystal X-ray diffraction analyses. The four compounds are new examples of hybrid compounds based on bicapped Keggin polyoxometalate {PMo12Sb2O40}. Compound 1, 2 and 3 are constructed from {PMo12Sb2O40} anions and different organic moieties, respectively. Compound 4 is formed by combining {PMo12Sb2O40} anions and manganese coordination complexes.

A new compound [Mo8V7O42][Cu(2,2′-bpy)2]2[Cu(2,2′-bpy)]·2H3O (1) has been synthesized under hydrothermal conditions and characterized by IR, UV–vis spectrum, elemental analysis, XRD, ESR, XPS, X-ray diffraction analysis and magnetic property study. Single-crystal X-ray structure analysis indicates that the compound 1 is a novel Keggin polyoxoanion tri-supported mixed-valent transition metal coordination complex.

A polyoxometalate [Co(phen)3][Co(en)3][Co(en)2(H2O)2][Co(en)2]0.5[ O40(VIVO)2] · 6H2O (1) (en = ethylenediamine, phen = 1,10-phenanthroline) has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction, IR, electron paramagnetic resonance, X-ray photoelectron spectroscopy, elemental analyses, and thermogravimetry. The structure is an interesting 3-D supramolecular network containing bi-capped Keggin-type molybdenum–vanadium clusters with transition metal complexes generated in situ under mild hydrothermal conditions. Compound 1 contains four different counteractions being coordinated complexes of cobalt. The magnetic properties of 1 have also been studied in the temperature range of 4–300 K, and its magnetic susceptibility obeys the Curie–Weiss law, showing ferromagnetic coupling.

Two compounds based on polyoxometalates, (4,4′-H2bpy)7(4,4′-Hbpy)[ ]2[ ] ·10H2O (1) and (4,4′-H2bpy)6(4,4′-bpy)[ ]2 · 18H2O (2), have been prepared under hydrothermal conditions and characterized by IR, XPS spectra, TG analyses, and single crystal X-ray diffraction. Both compounds consist of 4,4′-bipyridine units and polyoxometalates: [ ]5− for 1 and [ ]6− for 2. In addition, 1 contains both Keggin-type and disordered Keggin-type anions, while 2 contains a (H2O)10 water cluster.

A novel modified POM [ H 4 PMo 7 V Mo 5 VI O 40 Sb 2 III ] (im)2·2H2O (im = imidazole) (1) has been hydrothermally synthesized from the system Sb2O3–H3PMo12O40–H2C2O4–im and characterized by elemental analysis, IR, UV–Vis, XPS, TGA and single crystal X-ray diffraction. The highly reduced polyoxoanion [ PMo 7 V Mo 5 VI O 40 Sb 2 III ] 4 - represents the first example of bi-antimony capped α-Keggin phosphomolybdate, in which the Sb atoms exhibit novel Ψ-rhombic pyramidal {SbO4E} hemidirected coordination geometry with coordination number 4.

Two new polyoxometalates [HN(C2H5)3]3[PMo12O40] (1) and [NH2(C2H4NH3)2]2[Mo5P2O23] (2) have been hydrothermally synthesized and characterized by IR, UV-Vis, XPS spectra, TG analyses, and single crystal X-ray diffraction. Crystal data for 1: monoclinic, space group C2/c, a = 24.651(5) A, b = 10.822(2) A, c = 22.413(5) A, β = 120.37(3)°, and V = 5158.7(18) A3; for 2: triclinic, space group P-1, a = 9.821(2) A, b = 9.948(2) A, c = 14.687(3) A, α = 95.490(3)°, β = 98.870(3)°, γ = 95.710(3)°, and V = 1401.7(5) A3. The crystal structure analyses reveal complex hydrogen bonds in both 1 and 2 in 3-D supramolecular arrays constructed from different polyoxoanions and organic ligands.

A novel compound PMo 10 VI V 4 IV O 42 Co(Phen) 2 ( H 2 O ) 2 PMo 10 VI V 4 IV O 42 Co(Phen) 2 2 · 2 OH - · 4 , 4 -bpy 1 which represents the missing link between the discrete POMs and the POMs as building blocks in extended structure has already been hydrothermally synthesized and characterized by elemental analysis, IR, UV–Vis, XPS spectrum, TG analysis and single-crystal X-ray diffraction analysis. The study of the magnetic susceptibility of the compound 1 demonstrates the presence of ferromagnetic interactions.

Two supramolecular compounds [Fe(2,2′-bipy)3]2[ (Cl)] · 4.67H2O (1) and [Ni(enMe)3]2[ (Cl)] · 2H2O (2) have been prepared under hydrothermal conditions and characterized by elemental analyses, IR, TGA, ESR, magnetic properties, and single crystal X-ray diffraction analyses. Crystal data for 1: tetragonal, I-42d, a = 13.6043(19), b = 13.6043(19), c = 50.544(10) A, V = 9354(3) A3; for 2: hexagonal, P6(3)/m, a = 12.6046(12), b = 12.6046(12), c = 22.563(5) A, V = 3104.4(7) A3. Compound 1 is constructed from cations [Fe(2,2′-bipy)3]3+, polyoxovanadates [ (Cl)]6−, and water molecules. Compound 2 is composed of cations [Ni(enMe)3]2+, clusters [ (Cl)]8−, and water molecules. There are hydrogen-bonding interactions between polyoxovanadates, organic moieties, and/or water molecules in 1 and 2, forming different 2-D layered networks.

A novel polyoxometalate { P 2 V W 18 VI Ni 4 ( H 2 O ) 2 O 68 [ Ni ( en ) 2 ( H 2 O ) ] 2 } [ Ni ( en ) 3 ] 2 [ Ni ( en ) 2 ( H 2 O ) 2 ] · 14 H 2 O (1) has been hydrothermally synthesized and characterized by elemental analysis, IR spectrum, ESR spectrum and single crystal X-ray diffraction analysis. It is a novel Weakley-type POM supported transition metal coordination complex, also it contains a novel (H2O)14 water cluster in the structure. The study of the magnetic susceptibility of 1 demonstrates the presence of ferromagnetic interactions.

Two new polyoxometalates [ Ni ( phen ) 3 ] [ Ni ( en ) 3 ] [ Ni ( en ) 2 ( H 2 O ) 2 ] [ Ni ( en ) 2 ] 0.5 [ PW VI 7 W V 2 V IV 3 O 40 ( V IV O ) 2 ] · 6 H 2 O (1) and [ Ni ( phen ) 3 ] 2 [ Ni ( en ) 2 ] Na [ PW VI 7 W V 2 V IV 3 O 40 ( V IV O ) 2 ] · 8 H 2 O (2) (en=ethylenediamine, phen=1,10-phenanthroline) have been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction, IR, EPR, XPS, elemental analysis and thermogravimetry. Their structures exhibit interesting 3D supramolecular networks, and contain new bicapped (pseudo-) Keggin-type tungsten–vanadium cluster and the template transition-metal complexes (TMCs) being generated in situ under mild hydrothermal conditions. Interestingly, compound 1 contains four different kinds of nickel complex countercations.

A new compound [(BW 12 O 40 )Cd(2,2′-bpy) 2 (H 2 O)][Cd(2,2′-bpy) 3 ] 1.5 ·0.5H 2 O ( 1 ) has been hydrothermally synthesized and characterized by IR, UV–Vis, XPS spectrum, TG, XRD, elemental analysis and single crystal X-ray diffraction analysis. Crystal structure analysis reveals that 1 is the first Keggin polyoxoanion supported cadmium coordination complex.

A novel polyoxometalate [PW11O39Ni(4,4′-Hbpy)]·(4,4′-H2bpy)2·3H2O (1) has been hydrothermally synthesized and characterized by IR, XPS, TG, elemental analysis and single-crystal X-ray diffraction analysis. Crystal structure analysis reveals that 1 is a novel metal coordination fragment derivative of the classic Keggin polyanion.

A novel compound [P2W18M3O68][Cu(en)(2)](4)center dot 7H(2)O center dot 2OH(-) (M = 0.5W + 0.5Cu) 1 which contains the first example of extended structure constructed from Knoth-type sandwich polyoxoanions and transition metal coordination complexes has been hydrothermally synthesized and characterized by elemental analysis, IR spectrum, UV-Vis spectrum and single-crystal X-ray diffraction analysis. Crystal data for 1: triclinic, space group, P-1, a = 13.2718(7) angstrom, b = 13.6432(8) angstrom, c = 25.7307(15) angstrom, alpha = 104.7340(10)degrees, beta = 96.7630(10)degrees, gamma = 90.0330(10)degrees, V = 4472.2(4) angstrom(3), Z = 2. Structure solution and refinement based on 1090 parameters gave R1 (wR2) = 0.0409 (0.0993). (C) 2009 Elsevier B.V. All rights reserved.