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A novel nickel–vanadium bimetallic compound [Ni(H2O)2V2O6] (1) has been hydrothermally prepared and characterized by IR spectroscopy, elemental analysis, powder X-ray diffraction, thermogravimetric analysis, and X-ray single-crystal diffraction. Compound 1 exhibits an interesting purely inorganic 3D framework with a pair of entangled double helices, constructed by a {NiO4(H2O)2} octahedron and a {VO4} tetrahedron arranged alternately to each other. The magnetic behavior demonstrates the antiferromagnetic interactions transmitted by a pair of O–V–O bridges. Besides, luminescence measurements exhibit an intense broad emission maximum at λ≈ 525 nm owing to the O → V charge transfer within the {VO4} groups. [ABSTRACT FROM AUTHOR]

Four Ln-NDC coordination polymers [ Ln(NDC)(HNDC)(H2O)] ( Ln = La ( 1), Pr ( 2), Nd ( 3), Sm ( 4), H2NDC = 1,4-naphthalenedicarboxylic acid) were hydrothermally synthesized and structurally characterized by elemental analyses, IR spectroscopy, and single-crystal X-ray diffraction. Compounds 1- 4 are isomorphous, and their structures display a layer constructed from a Ln-organic chain and NDC2- ligand, in which the H2NDC ligands adopt two different acidity-dependent types and coordination modes: HNDC1- with μ-η1:η1 and NDC2- with μ-η1:η2:η1:η2. The 3D supramolecular networks of 1- 4 are mainly controlled by hydrogen bonds interactions. The magnetic susceptibilities of complexes 2- 4 reveal overall antiferromagnetic interactions between the LnIII ions. In addition, thermogravimetric analysis of compound 2 is described. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM PUBLISHER]

Abstract: Two new organic–inorganic hybrid compounds, {[Cu(2,2′-bipy)2]2(Hbpy)[α-AlW12O40]}·H2O (1) and {[H2en][CuI(4,4′-bipy)]3(α-AlW12O40)}·4H2O (2) (2,2′-bipy=2,2′-bipyridine, 4,4′-bipy=4,4′-bipyridine, py=pyridine, en=ethylene dimine) based on Keggin-type α-[AlW12O40]5− polyoxoaions and transition-metal organoamine subunits, have been hydrothermally synthesized and characterized by elemental analysis, IR spectroscopy, thermal gravimetric analysis (TG), and single-crystal X-ray diffraction. In addition, the electrochemical properties and photocatalytic activity of compound 1 were studied. The structural analysis reveals that 1 shows a 1D infinite chain structure constructed from [α-AlW12O40]5− polyoxoanions and {[CuII(2,2′-bipy)2][CuII(2,2′-bipy)(py)]}4+ fragments, in which the remarkable aspect is that [α-AlW12O40]5− polyoxoanion is modified in a fascinating symmetrical mode. Compound 2 displays an unprecedented 2D extended structure constructed from [α-AlW12O40]5− polyoxoanions and 4,4′-bipy-CuI-4,4′-bipy linear chains, in which three – chain belts formed by three linear chains arranged Cu parallel connect alternately with [α-AlW12O40]5− polyoxoanions. As far as we know, compounds 1 and 2 represent the first 1D and 2D extended hybrid materials constructed from 3d transition metals and polyoxotungstoaluminates linked through covalent bonds. [ABSTRACT FROM AUTHOR]

Two new inorganic-organic hybrid cobalt phosphomolybdates (Hdien)2[Co(dien)]2[Co(dien)(H2O)]2[CoMo12O24(HPO4)2(H2PO4)2(PO4)4(OH)6] ··· 5H2O (1) and (H2dien)2[Co(dien)]2[Co(H2O)2]2[CoMo12O24(HPO4)4(PO4)4(OH)6] ··· 7H2O (2) (dien = diethylenetriamine), involving molybdenum in the V oxidation state and covalently bonded transition metal complexes, have been prepared under mild hydrothermal conditions and structurally characterized by elemental analyses, IR spectra, TG analyses, and single-crystal X-ray diffraction. Compound 1 exhibits a one-dimensional (1D) chain framework, in which dien molecules adopt two kinds of coordination modes. Compound 2 shows a two-dimensional (2D) layer framework with three types of unusual tunnels. To the best of our knowledge, it is the first time [Co(dien)] units are directly incorporated into 1D and 2D skeletons of reduced molybdenum phosphates. The electrochemical properties of the two compounds were studied via the method of bulk-modified carbon paste electrodes. Furthermore, the magnetic properties of compound 2 are reported. [ABSTRACT FROM AUTHOR]

Abstract: A new compound, [Co(en)3]4[P2Mo5O23]2·9H2O, has been prepared under mild hydrothermal conditions and structurally characterized by elemental analyses, IR spectrum, and single-crystal X-ray diffraction. Yellow crystals crystallized in the triclinic space group with a=10.303(2) Å, b=11.871(2) Å, c=20.288(4) Å, α=99.46(3)°, β=96.39(3)°, γ=115.32(3)°, V=2165.9(8) Å3, Z=1 and R=0.0566. The compound consists of diphosphopentamolybdate clusters, [Co(en)3]3+ complexes, and water molecules, which are held together to generate a three-dimensional supramolecular network via hydrogen-bonding interaction. Interestingly, the three-dimensional supramolecular network contains cyclic water hexamers, which play an important role in the formation of the crystal. [Copyright &y& Elsevier]

Abstract: Two novel compounds, (H2bpy)0.5{[Ni(H2O)5][Ni(Hbpy)(H2O)4][Mo5P2O23]} 1 and (H2bpy)0.5{[Co(H2O)5][Co(Hbpy)(H2O)4][Mo5P2O23]} 2, have been prepared under mild hydrothermal conditions and structurally characterized by single-crystal X-ray diffraction. The two compounds are isostructural and crystallize in the triclinic space group with a=10.760(2)Å, b=10.771(2)Å, c=17.566(4)Å, α=98.56(3)°, β=96.66(3)°, γ=111.10(3)°, and Z=2 for the compound 1, and a=10.770(2)Å, b=10.815(2)Å, c =17.684(4)Å, α=98.96(3)°, β=96.41(3)°, γ=111.37(3)°, and Z=2 for the compound 2. Crystal structure analysis reveals that 1 and 2 are not only the first examples of polyoxometalate supported transition metal complexes constructed by diphosphopentamolybdate cluster and transition metal complex fragments but also the first examples of disupporting polyoxometalate compounds where two distinct transition metal complex fragments are supported on the polyoxoanion cluster. [Copyright &y& Elsevier]

Abstract: A unique composite hybrid material [Cu4(bpy)4(H2O)2(PO4)2](H3O)[PMo12O40] 1 (bpy=2, 2′-bipyridine) has been hydrothermally synthesized from the reaction of Na2MoO4·2H2O, H3PO4, Cu(MeCO2)2·H2O, 2, 2′-bpy and water. It has been characterized by elemental analysis, IR, TG, and single-crystal X-ray diffraction. Compound 1 is constructed from the organic–inorganic hybrid [Cu4(bpy)4(H2O)2(PO4)2]2+ cation and α-Keggin [PMo12O40]3- polyoxoanion, which represents the first example of a hybrid material that combines transition metal phosphate and polyoxometalate. [Copyright &y& Elsevier]

Two novel heteropolymolybdate, [H2bpy]2 [Hbpy] [PCuMo11O39]·H2O 1 and [H2bpy]2 [Hbpy] [PZnMo11O39]·2.75H2O 2, have been prepared under mild hydrothermal conditions and structurally characterized by single-crystal X-ray diffraction. The two compounds are isostructural and crystallize in the monoclinic space group P2(1)/n (No. 14) with a=13.440(3) Å, b=26.660(5) Å, c=15.240(3) Å, β=99.55(3)°, and Z=4 for the compound 1, and a=13.610(3) Å, b=26.781(5) Å, c=15.205(3) Å, β=100.40(3)°, and Z=4 for the compound 2. Compound 1 and 2 exhibit a zigzag chain structure in which Keggin anions are connected through a common oxygen atom. They are the first characterized compounds containing 1D chains of transition-metal substituted Keggin heteropolymolybdate. Other characterizations by elemental analysis, IR, EPR, TG, and XRPD are also described. [Copyright &y& Elsevier]

A novel compound, [Co(phen)3][V10O26]·H2O, was hydrothermally synthesized and characterized by single-crystal X-ray diffraction. This compound crystallizes in the orthorhombic space group Ccca with a=13.447(3), b=29.936(6), c=23.252(5) A˚, V=9360(3) A˚3, Z=8 and R=0.0285. Data were collected on a Rigaku R-AXIS RAPID IP diffractometer at 293 K in the range of 1.36<θ<24.99°. The structure of the compound consists of vanadium oxide layers, which are built up from the infinite VO4 chains by corners and edges sharing. The [Co(phen)3]2+ complexes occupy the interlayer space and contact each other via π−π stacking interactions of the phen groups to form infinite one-dimensional chains. [Copyright &y& Elsevier]

A novel layered vanadium arsenate [V4O7(HAsO4)2(o-phen)2] 1 (o-phen=o-phenanthroline) was synthesized by the hydrothermal reaction of V2O5, ZnCl2, Na2HAsO4·7H2O, o-phenanthroline (o-phen) and water. Its structure was determined by elemental analyses, ESR spectrum, XPS spectrum, TG analysis, IR spectrum and the single-crystal X-ray diffraction. Compound 1 crystallizes in monoclinic system, space group P2/c, a=10.122(2) A˚, b=9.867(2) A˚, c=15.367(3) A˚, β=102.83(3)°, V=1496.4(5) A˚3, Z=1, λ(MoKα)=0.71073 A˚, (R(F)=0.0397 for 3422 reflections). Data were collected on a Rigaku R-AXIS RAPID IP diffractometer at 293 K in the range of 2.06°<θ<27.48°. The title compound contains an unusual two-dimensional (2D) As–V–O layer with four-, six- and eight-membered rings. The chelating o-phen ligands project perpendicularly above and below the undulating layer. 1 represents the first example of 2D inorganic vanadium arsenate backbone grafted with the directly coordinated organic ligands. Furthermore, the 3D supermolecular architecture is formed by π–π stacking interactions of the o-phen groups between adjacent layers. [Copyright &y& Elsevier]

An one-dimensional mixed-valence molybdenum oxide [Mo3O8(2,2′-bipy)2] has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. Red-brown crystals crystallized in the monoclinic system, space group P2(1)/n, a=9.3674(19), b=16.994(3), c=13.956(3) A˚, β=102.66(3)°, V=2167.7(8) A˚3, Z=4 and R=0.0515. The title compound exhibits an infinite one-dimensional chain with organonitrogen donors of 2,2′-bipy groups coordinated directly to the molybdenum oxide framework, where the binuclear units of edge-sharing {MoO4N2} octahedra are linked by {MoO4} tetrahedra through corner-sharing oxygen atoms. Other characterizations by elemental analysis, IR, and thermal analysis are also described. [Copyright &y& Elsevier]

Three new cage-like mixed-valent polyoxovanadates [Ni(1,10′-phen)3]2[V10O26] 1, [Zn(2,2′-bipy)3]3[V15O36Cl]·3H2O (2) and [Co(2,2′-bipy)3]3[V15O36Cl]·3H2O (3) have been hydrothermally synthesized for the first time and characterized by elemental analyses, IR, EPR spectra, TG analyses and single crystal X-ray diffraction. The polyoxoanion of 1 exhibits an interesting empty ellipsoidal [VIV 2VV 8O26]4− ‘host’ shell, while the oxo vanadium clusters of 2 and 3 possess a spherical [VIV 8VV 7O36Cl]6− cage with a Cl− ion encapsulated. The structure-directing role of organic templates (1,10′-phen and 2,2′-bipy) on the formation of the polyoxoanion structures is discussed. [Copyright &y& Elsevier]

A new bimetallic cluster complex with the formula [{Co(phen)2}2V4O12]·H2O was synthesized from the hydrothermal reaction of V2O5, H2C2O4, Co(NO3)2, 1,10-phenanthroline (phen), (C4H9)4NOH and water. The compound crystallizes in an orthorhombic system with space group Pbcn and unit cell parameters a=19.106(3) A˚, b=15.250(3) A˚, c=16.321(2) A˚, V=4755.4(13) A˚3, Z=4 and R=0.0318. The bimetallic cluster complex [{Co(phen)2}2V4O12]·H2O is composed of a discrete V4O124− cluster covalently attached to two [Co(phen)2]2+ fragments and the discrete hexanuclear bimetallic clusters of [{Co(phen)2}2V4O12]·H2O are further extended into interesting three-dimensional supermolecular arrays via π–π stacking interactions of phen groups. Other characterizations by elemental analysis, IR, and thermal analysis are also described. [Copyright &y& Elsevier]

Owing to the exponential growth of the human population and the rising food demand, identifying sustainable antimicrobials for higher agricultural productivity becomes essential. In this study, hydrothermal precipitation for synthesizing versatile nanostructured zinc oxide particles (nZnOs), including nanorods (1D), nanoplatelets (2D), and multibranched flower-like particles (3D), was achieved by controlling pH values of source precursors and growth time. Hydrothermal synthesis is an eco-friendly process without the requirement of hazardous organic solvents. The antimicrobial properties of these nZnO particles were evaluated on different soil-borne plant pathogens. These pathogens are serious limiting factors in agriculture. Results indicate that multibranched flower-like ZnO (3D nZnO) showed more remarkable, reliable, and stable antifungal activity compared with other nZnOs. The scanning electron microscopy results also demonstrated significant mechanical damage to pathogens that caused by the branches of flower-like particles from 3D nZnO. Moreover, results of photodegradation and environmental resistance of the synthesized nZnOs revealed their potentials to reduce hazardous chemical pesticides and the eco-friendliness. This work is the first to compare the antimicrobial (i.e., antifungal) properties of various nZnOs and their applications in agriculture. Our results suggest that multibranched flower-like ZnO can be served as promising candidates of green antimicrobials with multiple modes of action in sustainable agriculture. Image 1 • Versatile nanostructured nZnO were synthesized through hydrothermal synthesis by controlling pH values. • The improvement of hydrothermal synthesis is an eco-friendly process. • Multibranched flower-like ZnO showed significant inhibition to soil-borne fungal pathogens Fusarium oxysporum. • Versatile nZnOs also showed a notable feature for reducing hazardous chemicals. [ABSTRACT FROM AUTHOR]

A novel one-dimensional vanadium(V)-organic coordination polymer [{VO2(2,2′-bipy)}2(tp)]∞ (1) has been hydrothermally synthesized from the reaction of V2O5, 2,2′-bipyridine, and terephthalate. It has been characterized by IR, XPS, TGA and single-crystal X-ray diffraction. Its structure is constructed from dimers of edge-sharing vanadium(V) octahedra with covalently bonded 2,2′-bipy ligands, linked through bicarboxylate tp ligands into an infinite zigzag chain. Extensive hydrogen-bond contacts and strong π–π interactions lead to a layered framework of the solid of 1. [Copyright &y& Elsevier]

An organic–inorganic hybrid molybdenum phosphate, Na2[{Mn(phen)2(H2O)} {Mn(phen)2}3{MnMo12vO24 (HPO4)6(PO4)2(OH)6}]·4H2O (phen=1,10-phenanthroline), involving molybdenum present in V oxidation state and covalently bonded transition metal coordination complexes, has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. Deep brown–red crystals are formed in the triclinic system, space group P1¯, a=16.581(1) A˚, b=18.354(1) A˚, c=24.485(2) A˚, α=80.589(1)°, β=71.279(1)°, γ=67.084(1)°, V=6493.8(8) A˚3, Z=2, λ(MoKα)=0.71073 A˚ (R(F)=0.0686 for 29,053 reflections). Data were collected on a Bruker Smart Apex CCD diffractometer at 293 K in the range of 1.76<θ<28.06° using ω–2θ scans technique. The structure of the title compound may be considered to be based on {Mo6O12(HPO4)3(PO4)(OH)3} units bonded together with {Mn(phen)2} subunits into a two-dimensional network. Two types of tunnels are observed in the solid of the title compound. [Copyright &y& Elsevier]

A novel manganese phosphomolybdate, [H3N(CH2)4NH3](H3O)2{[Mn(phen)2]4[MnMov12O30(HPO4)6(H2PO4)2]}·4H2O 1, has been hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction. The crystal data: triclinic, P1¯, a=14.172(7) A˚, b=16.547(2) A˚, c=16.679(3) A˚, α=62.881(12)°, β=73.83(3)°, γ=88.81(3)°. X-ray crystallography shows that the [Mn(phen)2] fragments are covalently bonded to the [Mn(Mo6P4)2] dimers leading to a one-dimensional chain with rectangular cavities occupied by tetramethylene-diamine cations and water molecules. [Copyright &y& Elsevier]

{[Cd(en)2] [Cd(en)]2Ge8V12 (OH)8}2{ [Cd(en)(H2O]2}·en·2H2O is hydrothermally prepared from an aqueous mixture of NaVO3, GeO2, CdCl2, H2C2O4, en, and KOH (autoclave, pH 10.2, 150 °C, 4 d, 44% yield). [ABSTRACT FROM AUTHOR]

Abstract: A new compound 1 (phen=phenanthroline) has been synthesized under hydrothermal conditions and characterized by IR, TG analysis and single-crystal X-ray diffraction. The study of the magnetic property of compound 1 exhibits the presence of antiferromagnetic interactions. Compound 1 crystallizes in the monoclinic system, space group P21/c, a =21.843(4)Å, b =16.566(3)Å, c =21.025(4)Å, α =90°, β =100.26(3)°, γ =90°, V =7486(3)Å3, Z =2. The basic building unit in compound 1 is the [PMo12V2O42] cluster. The most remarkable structural feature of 1 is that there exist two distinct [PMo12V2O42] clusters. One is covalently linked by [Co(phen)2] complexes to form 2D covalent layer, the other supports two [Co(phen)2(H2O)] complexes forming a 2D supramolecular network. Such two different kinds of layers are further stacked to form a novel 3D supramolecular framework. [Copyright &y& Elsevier]

Abstract: Four new three-dimensional materials built from reduced molybdenum(V) phosphates as building blocks and transitional metal (Co, Zn and Cd) complexes as linkers, (Hbpy)2[Co(bpy)(H2O)]2[Co(H2PO4)2 (HPO4)6(MoO2)12(OH)6] (1), [Co(H2O)4]2[Co(Hbpy)(H2O)]2[Co(bpy)][Co(HPO4)4(PO4)4(MoO2)12(OH)6]·6H2O (2), Na2[Zn(Hbpy)(H2O)2]2[Zn(Hbpy)]2[Zn(HPO4)2(PO4)6(MoO2)12(OH)6]·4H2O (3), (H2bpy)2[Cd(bpy)(H2O)]2[Cd(bpy)(H2O)2]2[Cd(HPO4)4(PO4)4(MoO2)12(OH)6]·2H2O (4) (bpy=4,4′-bipyridine), have been synthesized and characterized by elemental analyses, IR, TG, and single crystal X-ray diffraction. The 3-D framework of 1 is constructed from Co[P4Mo6]2 dimers bonded together with [Co(bpy)] n coordination polymer chains. In compound 2, the Co[P4Mo6]2 dimers are linked by both [Co(bpy)] complex chains and the cobalt dimers to form a 3-D framework. Compounds 1 and 2 represent the first examples of reduced molybdenum(V) phosphates decorated with transition metal complexes chains. The 3-D framework of 3 is constructed from Zn[P4Mo6]2 dimers bonded together with [Zn(bpy)] coordination complexes and [Zn(bpy)(H2O)2] complexes. In compound 4, the Cd[P4Mo6]2 dimers are coordinated with [Cd(bpy)(H2O)] and [Cd(bpy)(H2O)2] complexes to construct a 3-D structure. To our best knowledge, it is the first time that linear ligand 4,4′-bpy molecules have been grafted into the backbone of reduced molybdenum phosphates. Furthermore, the magnetic properties of compounds 1 and 2 are reported. [Copyright &y& Elsevier]

Abstract: Two new one-dimensional reduced molybdenum (V) phosphates, [Zn(phen)2][Zn(phen)2(H2O)][Zn(HPO4)8[(MoO2)6(OH)3]2]·H2O (1) and [Co(phen)3][Co(phen)2(H2O)(H2PO4)][KNa(H2O)2][Co(H2O)2][Co(phen)2][Co(H2PO4)2(HPO4)3(PO4)3[(MoO2)6(OH)3]2]·5H2O (2) (phen=1,10-phenanthroline), have been synthesized and characterized by elemental analyses, IR, TG, and single crystal X-ray diffraction. Compound 1 is built up of Zn[P4Mo6]2 cluster as the structural motif covalently linked by [Zn(phen)2] complex subunits to yield unusual one-dimensional chains, which are further in close contact forming two-dimensional supramolecular layers via π–π stacking interactions. In compound 2, Co[P4Mo6]2 clusters are connected by [Co(phen)2], [Co(H2O)2] and [KNa(H2O)2] fragments through covalent bonds, forming an unusual one-dimensional chain. Interestingly, both [Co(phen)3] complex and [Co(phen)2(H2O)(H2PO4)] cobalt phosphate are presented as charge-compensating cations and contact each other via π–π stacking interactions to form a supramolecular chain, then the supramolecular chains link two neighboring chains that contain [P4Mo6] via hydrogen-bonding interactions to form a two-dimensional supramolecular layer. Furthermore, the fluorescent activity of compound 1 is reported. [Copyright &y& Elsevier]

Abstract: A novel reduced polyoxometalate derivative [Cu(2,2′-bipy)2][PMoVI 8MoV 4O40{Cu(2,2′-bipy)}2.5]·H2O 1 has been hydrothermally synthesized and characterized by IR and XPS spectra, TG analysis and single-crystal X-ray diffraction. Compound 1 crystallizes in the monoclinic system, space group P21/c, a=21.620(4)Å, b=19.070(4)Å, c=17.810(4)Å, β=109.99(3)°, V=6901(2)Å3, Z=4. The result of structure determination shows that the reduced α-Keggin polyoxoanion [PMoVI 8MoV 4O40]7− is capped by two divalent Cu atoms through four bridging oxo groups on two opposite {Mo4O4} faces or pits and supports a half {Cu(2,2′-bipy)} complex via the surface bridging oxygen atoms. [Copyright &y& Elsevier]

A new vanadium phosphate [C2N2H10]{(VO)(VO2)[V(OH2)](PO3.5)4}·H2O 1 has been hydrothermal synthesized and structurally characterized by the single-crystal X-ray diffraction. Compound 1 crystallizes in the monoclinic system, space group P2(1)/c, a=12.3096 A˚, b=11.7570 A˚, c=12.6334 A˚, β=98.103°, V=1810.10A˚3, Z=2, λ(Mo Kα)=0.71073 A˚, R=0.0781 with 4105 reflections. Compound 1 exhibits a three-dimensional (3-D) open-framework structure, which consists of a novel {V3O16} trimer linked by four {PO4} tetrahedra. Furthermore, four such {V3P4O18} structural unit are connected together to form an interesting 10-mumber ring via corner-sharing mode. [Copyright &y& Elsevier]

A novel organic–inorganic hybrid vanadium oxide [V4O10(o-phen)2], involving all vanadium atoms present in +5 oxidation, has been hydrothermally synthesized and characterized by elemental analysis, IR, UV-vis, ESR, XPS spectra and TG-DTA thermal analysis. The single-crystal X-ray diffraction shows that the red-brown crystal is formed in the triclinic system, space group P1¯, a=9.782(2), b=6.5124(14), c=19.765(4) A˚, α=89.94(2)°, β=100.66(2)°, γ=89.86(2)°. The title compound exhibits an infinite one-dimensional ladder-type tetravanadate skeleton with organonitrogen donors of o-phenanthroline ligands coordinated directly to the vanadium oxide framework. [Copyright &y& Elsevier]