A three-dimensional organic–inorganic hybrid solid constructed from novel Mo–O–Zn bimetallic oxide networks linked via 3-amino-1,2,4-triazole

A novel three-dimensional organic–inorganic hybrid solid [Zn₃(3atrz)₂(H₂O)₂(MoO₄)₂]_n (1) (3atrz = 3-amino-1,2,4-triazole) constructed from two-dimensional Mo–O–Zn bimetallic oxide networks was prepared under hydrothermal condition and characterized. Unprecedented {Zn₆Mo₆} 12 metal central-membered inorganic rings together with novel {Zn₆(3atrz)₆} metal–organic coordination rings exist in this structure.     

Organic–inorganic hybrid oxides: Structure and magnetic properties of [{Cu(terpy)}2Mo6O17(H2O)(O3PCH2NH2CH2PO3)2] · H2O,a bimetallic oxide constructed from novel {Mo6O17(H2O)(O3PCH2NH2CH2PO3)2}4− clusters

The hydrothermal reaction of MoO₃, CuSO₄ · 5H₂O, 2,2′:6′:2″-terpyridine (terpy) and bis-N,N-(methylphosphonic acid) amine (H₂O₃PCH₂NHCH₂PO₃H₂) provided blue crystals of the bimetallic oxide [{Cu(terpy)}₂Mo₆O₁₇(H₂O)(O₃PCH₂NH₂CH₂PO₃)₂] · H₂O (1 · H₂O). The three-dimensional structure of 1 is constructed from {Mo₆O₁₇(H₂O)(O₃PCH₂NH₂CH₂PO₃)₂}⁴⁻ clusters linked through {Cu(terpy)}²⁺ subunits. The cluster consists of three pairs of edge-sharing {MoO₆} octahedra linked through corner-sharing interactions into a {Mo₆O₆} ring. One phosphonate ligand spans the diameter of the ring, bridging four molybdenum sites and leaving at a pendant {PO} group at each terminus. The second diphosphonate ligand exploits one {–PO₃} unit to cap the hexamolybdate ring and bridge all six molybdenum sites while the second {–PO₃} terminus bridges two molybdenum sites, leaving a pendant {PO} unit. Crystal data: C₃₄H₄₅Cu₂Mo₆N₈O₃₅P₄: monoclinic, P2₁/n, a = 11.9431(7) Å, b = 17.382(1) Å, c = 27.524(2) Å, β = 90.429(1)°, V = 5713.7(6) Å³, Z = 4, D_calc = 2.270 g cm⁻³, R₁ = 0.0466.     

Molybdenum-oxygen anionic chain grafted by Cu-phen complex. Synthesis,crystal structure and properties

An unreported inorganic-organic hybrid compound [Cu(phen)(H₂O)₂(Mo₃O₁₀)] (1) was hydrothermally synthesized and characterized with elemental analysis, IR spectroscopy, thermal analysis, luminescent spectroscopy, magnetic measurement. The crystal structure was determined with X-ray single-crystal diffraction. Compound 1 has a 1-D chain structure constructed by {Mo₃O₁₀}^2 − units via edge-sharing and [Cu(phen)(H₂O)₂]^2 + fragments grafting the chain from two sides via the coordination of the terminal oxygen atom of the MoO₆ octahedra to Cu^2 + ion. The coordination of phen to Cu^2 + ion increases the molecular rigidity so that an emission peak at 500 nm was observed and assigned to the phosphorescent n–π* and π–π* transition from ligand-centered triple state. In compound 1 Cu(II) exhibits an antiferromagnetic exchange.     

Synthesis and crystal structures of two new inorganic–organic hybrid polyoxomolybdate complexes: [Himi]4[{Co(imi)2(H2O)2}Mo7O24] · 4H2O and [Zn(imi)4]2[(imi)2Mo8O26] · 6H2O

The two new inorganic–organic hybrid polyoxomolybdate complexes [Himi]₄[{Co(imi)₂(H₂O)₂}Mo₇O₂₄] · 4H₂O (1) and [Zn(imi)₄]₂[(imi)₂Mo₈O₂₆] · 6H₂O (2) (imi = imidazole) have been prepared by conventional aqueous solution synthesis. Compound 1 consists of heptamolybdate anions [Mo₇O₂₄]⁶⁻ covalently linked by [CoN₂O₄]²⁺ octahedra into one-dimensional zigzag-shaped chains. The zigzag-shaped chains are further linked together via the hydrogen-bonding interactions to form a 2D supramolecular framework. Compound 2 is build up of an imidazole-coordinated octamolybdate anion, two imidazole coordinating zinc cations and lattice water molecules to form a three-dimensional framework via complex hydrogen-bonding.     

Coordination of the carboxylate of the functionalized Strandberg anion in a three dimensional covalence framework

[H₃O]₂[{Cu₆(bipy)₁₀(H₂O)₄}{Cu₂(bipy)₂(H₂O)₄}{(HO₂CC₂H₄PO₃)Mo₅O₁₅(O₂CC₂H₄PO₃)}₂{(HO₂CC₂H₄PO₃)₂Mo₅O₁₅}₂]·30H₂O (1) was obtained from aqua solution. In 1 the linkage between bipy and Cu^2 + ions creates a layer with rhombus channel and an isolated chain. [(HOOCC₂H₄PO₃)₂Mo₅O₁₅]^4 – anions act as tridentate and tetradentate ligands, connecting the layers and the chains into a three dimensional covalent framework through the oxygen atoms of carboxylate groups and of MoO₆ octahedra.     

Hydrothermal synthesis,structure and properties of two new phosphomolybdates based on Strandberg-type {P2Mo5O23}6 − building units

Two inorganic–organic hybrid compounds based on Strandberg-type phosphomolybdates (abbreviated as {P₂Mo₅O₂₃}^6 −) complexes [H₃O]₂[Cu₂(Pyim)₂(H₂O)₃][P₂Mo₅O₂₃] · 6H₂O (1) and [Cu₃(Pyim)₃(H₂O)₄][P₂Mo₅O₂₃] · 7H₂O (2) were successfully synthesized at different pH values under hydrothermal conditions. Both 1 and 2 are based on the {P₂Mo₅O₂₃}^6 − clusters connected by copper complexes to generate one dimensional chain. The magnetic analyses of compounds 1 and 2 indicate antiferromagnetic interactions between copper ions.     

Synthesis,structure and magnetic properties of a copper molybdate hybrid inorganic/organic solid with a novel 10-connected three-dimensional network topology

Hydrothermal reaction of CuCl₂, MoO₃, and 4,4′-dipyridylketone (4,4′-dpk) afforded green crystals of the mixed metal oxide phase {[Cu₂(MoO₄)₂(4,4′-dpk)(H₂O)]·H₂O}_n (1). According to single-crystal X-ray diffraction, {Cu₂O₂} dimers link into 1-D {Cu₂O₂(μ-H₂O)}_n chains via bridging aqua ligands. These chains form [Cu₂(MoO₄)₂(H₂O)]_n slabs via linkage through tetrahedral molybdate anions. In turn, the copper molybdate slabs are pillared through tethering 4,4′-dpk ligands into a 10-connected three-dimensional lattice with an unprecedented 3¹²4³⁰5²6 topology. Variable temperature magnetic data above 140 K were fit to the Curie–Weiss law, with C = 0.17 cm³ K/mol Cu and Θ = 70 K, indicating likely ferromagnetic coupling within the dinuclear kernels of 1; low temperature data points towards the possibility of interdimer antiferromagnetic interactions.     

A novel 2, 6-connected inorganic-organic 3-D open framework based on {As2Mo18} with photocatalytic property and anticancer activity

A new inorganic-organic open framework based on Wells-Dawson arsenomolybdate, {Ag(diz)₂}₃[{Ag(diz)₂}₃(As₂Mo₁₈O₆₂)]∙H₂O (1) (diz = 1,2-diazole) has been hydrothermally synthesized and characterized by elemental analysis, IR, TG, UV, XRD, and single-crystal X-ray diffraction. In compound 1, each {As₂Mo₁₈} cluster uses six terminal oxygen atoms on 'equator' position to attract peripheral six {Ag(diz)₂} linkers, which are further connected by six Dawson clusters located on two different planes via unique equator-to-equator interlaced ways to form a unprecedented 3D network with {8¹² ∙ 12³}{8}₃ topology. Compound 1 represents the highest covalent connectivity of 3-D Dawson arsenomolybdate, which exhibits merit photocatalytic properties for degradation of refractory dyes Azon Phloxine (AP) under UV light. In addition, compound 1 has a potent inhibition effect on proliferation of Human gastric adenocarcinoma cells (SGC-7901).     

Hydrothermal synthesis,crystal structure and electrochemical behavior of two new isomorphic layered vanadates: [M(dpa)V3O8.5] (M = Cu(II) 1 and Zn(II) 2; dpa = 2,2′-dipyridylamine)

Two new isomorphic vanadates, [M(dpa)V₃O_8.5] (M = Cu²⁺ 1, Zn²⁺ 2; dpa = 2,2′-dipyridylamine) have been synthesized hydrothermally. X-ray crystal analysis reveals that vanadates 1 and 2 exhibit a layered structure constructed from {V₃O_8.5}^2? layers inlaid with [M(dpa)]²⁺ subunits. The {V₃O_8.5}^2? layers consist of ribbon-like chains of edge sharing {VO₅} square pyramids bridged through {V₂O₇} fragments. Electrochemical measurement shows that lithium ions are reversibly intercalated and deintercalated in vanadate 1.     

A novel polyoxometalate-based metal-organic compound constructed from an unprecedented [Ag8(Hpyttz)4(H2pyttz)2] cluster and an in-situ [VW12O40]3 − anion

A novel polyoxometalate (POM)-based metal-organic compound constructed from a multinuclear Ag^I cluster and Keggin-type [VW₁₂O₄₀]^3 − anion, [Ag₄(Hpyttz)₂(H₂pyttz)][HVW₁₂O₄₀]·3H₂O (1) (H₂pyttz = 5′-(pyridin-4-yl)-1H,2′H-3,3′-bi(1,2,4-triazole), was hydrothermally synthesized and characterized by IR spectroscopy, TG analysis, powder and single-crystal X-ray diffraction. In compound 1, [VW₁₂O₄₀]^3 − (VW₁₂) was in-situ transformed from [SiW₁₂O₄₀]^4 − anion. Eight Ag^I ions were connected by six Hpyttz/H₂pyttz ligands with three coordination modes forming an unprecedented [Ag₈(Hpyttz)₄(H₂pyttz)₂] cluster, which connected with six VW₁₂ anions to construct a 2-D double-layer (3,6)-connected network with {4³}₂{4⁶.6⁶.8³} topology. Moreover, the photocatalytic activity of 1 has been investigated.     

Two Keggin polyoxoanion-based hybrids composed of CuI/tbz segments: Syntheses,structures and electrochemical properties

Two Keggin polyoxoanion-based hybrid compounds composed of Cu^I/tbz segments [Cu^I₂(tbz)₂][Cu^I(tbz)₂(PMo^VI₁₀Mo₂^VO₄₀Cu^I₂)] (1) and [Cu^I₂(tbz)₃][Cu^I (tbz)₂](PW₁₂O₄₀) (2), have been hydrothermally synthesized. In compound 1, a 3D supramolecular framework with 2D channels is constructed from a novel cap-to-cap {Cu^I(tbz)₂(PMo^VI₁₀Mo₂^VO₄₀Cu^I₂)}^2 −_n chain via hydrogen bonding and π–π interactions, in which {Cu^I₂(tbz)₂}^2 + segments are incorporated. Compound 2 is composed of one discrete PW₁₂ polyoxoanion, one {Cu^I(tbz)₂}⁺ segment and one {Cu^I₂(tbz)₃}^2 + segment, displaying a 3D supramolecular structure through hydrogen bonding and π–π interactions. The results indicate that the polyoxoanions and configurations of tbz ligand play the key roles in the self-assembly processes. The electrochemical properties of compounds 1 and 2 have been investigated.     

A novel oxidation state Keggin-type isopolyoxomolybdate (C3H5N2)4H[MoVI0.5MoVI12O40]: Synthesis,structural characterization and electrocatalytic properties

A new oxidation state Keggin-type isopolyoxomolybdate, (C₃H₅N₂)₄H[Mo^VI_0.5Mo^VI₁₂O₄₀]·H₂O (1), was synthesized and structurally characterized by single crystal X-ray crystallography, spectroscopy, and further characterized by IR spectroscopy, UV–vis spectra, ESI-MS and thermogravimetric analysis. All the Mo atoms in the [[Mo^VI_0.5Mo^VI₁₂O₄₀]]^5 − anion are Mo^6 +, which was confirmed by the X-ray photoelectron spectroscopy(XPS), bond valence sum (BVS), and UV–vis spectra. Electrospray ionization mass spectrometry (ESI-MS) results suggest that {Mo₁₂O₄₀} and {Mo₁₃O₄₀} fragments coexist in compound 1. Compound 1 demonstrated good electrocatalytic activity for nitrite and hydrogen peroxide reduction.     

A new rhombic 2D interpenetrated organic-inorganic hybrid material base on [HxAs2Mo6O26](6 − x)− polyoxoanion and Co-btb complexes

The new compound based on unconventional arsenomolybdate: {Co(btb)(H₂O)₂}₂{H₂As₂Mo₆O₂₆}·2H₂O (btb = 1,4-bis(1,2,4-triazol-1-y1)butane) (1) has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction analysis, elemental analyses, IR, XPS, UV–vis-NIR and TG. Compound 1 consists of [H₂As₂Mo₆O₂₆]^4 − polyoxoanion and {Co-btb} complexes, the polyoxoanion as a tetradentate node coordinated with the Co^2 + ions forming the rhombic 2D interpenetrated layer structure, which is further extended the 3D topological structure with symbol {4⁶ · 6² · 8¹⁶ · 12⁴}{4⁹ · 6⁶}²{4}² by weak interaction. It shows obvious photocatalytic activities for the degradation of methylene blue (MB) and rhodamine-B (RhB). In addition, the electrocatalytic activity upon the reduction of nitrite also has been studied.     

Synthesis,crystal structure,characterization and magnetic property of a new organophosphonate-based polyoxovanadate

A novel organophosphonate-based polyoxovanadate, Cs_1·5Na_3.5[H{V₃(H₂O)O₃}{O₃PC- (OH)(CH₃)PO₃}₃]·15H₂O (1) has been synthesized and further investigated by single-crystal X-ray diffraction analysis, IR spectrum, UV–vis spectroscopy, X-ray powder diffraction, thermogravimetric analysis and X-ray photoelectron spectroscopy. Single-crystal X-ray analysis reveals that compound 1 crystallizes in the triclinic space group P-1 with a = 9.506(3) Å, b = 15.150(5) Å, c = 17.915(6) Å, V = 2437.9(14) ų and Z = 2. Compound 1 exhibits a ring-shaped cluster with three branches of the 1-hydroxyethane 1, 1-diphosphonic acid [HEDP = H₂O₃P(OH)C(CH₃)PO₃H₂] ligands. Furthermore, the magnetic property of compound 1 has also been studied.     

A three-dimensional zincic molybdenum (V) phosphate with helical channel: Synthesis,structure, and electrochemical properties

A new reduced zincic molybdophosphate, (H₂bpp)₃[Zn₃Mo₁₂^VO₂₄(OH)₆(H₂O)₂(HPO₄)₆(PO₄)₂]·2H₂O 1 (bpp = 1,3-bis(4-pyridyl)propane) has been hydrothermally synthesized and characterized by elemental analysis, IR, TG, and single-crystal X-ray diffraction. Compound 1 crystallizes in the tetragonal space group I 41/a c d with a = 31.8033(4) Å, b = 31.8033(4) Å, c = 34.5593(8) Å, V = 34955.0(10) ų, and Z = 16 and exhibits a 4,6-connected 3-D framework with (3².8⁴)(3⁴.4².8³.9⁵.10) topology. The basic building blocks of [Zn(2)(Mo₆P₄)₂] are linked through [Zn(3)O₆] octahedra and [Zn(1)O₄] tetrahedra to construct 1-D chains along four different directions. Such 1-D chains are further connected by [Zn(1)O₄]²⁺ linkers to form a 3-D intricate framework with helical channels occupied by protonated bpp and water molecules. Additionally, the electrochemical property of the 1-CPE has been studied in detail.     

The synthesis and characterization of a new butterfly-like polyoxometalate: K5Na2[Mo9V3O38]·9H2O

A new butterfly-like compound K₅Na₂[Mo9V₃O₃₈]·9H₂O 1 has been synthesized in aqueous solution and characterized by elemental analysis, IR spectroscopy, TG analysis, UV–vis spectroscopy, X-ray photoelectron spectroscopy (XPS), cyclic voltammogram and single-crystal X-ray diffraction analysis. Compound 1 is a new butterfly-like molybdodivanadate composed by Mo (VI) and V (V) with the Mo/V ratio 3:1, the polyoxoanion [Mo₉V₃O₃₈ ]^7? can be described as two {MMo₄O₁₈} (M = Mo/V) units connected by one {V₂O₈} core. The photocatalyst property of compound 1 has been investigated, which shows a good photocatalyst for degradation of RhB.     

A multifunctional reduced molybdophosphate-based 3D metal–organic framework induced by a rigid triazole and a flexible bis(triazole) mixed ligand

A novel reduced molybdophosphate-based metal–organic framework (MOF) Zn[(MoO₂)₆(HPO₄)₂(PO₄)₂(OH)₃]₂[Zn₂(L¹)][Zn(HL²)₂]₂·10H₂O (1) (L¹ = 1,6-bis(1,2,4-triazol-1-yl)hexane, L² = 1,2,4-triazol) has been hydrothermally synthesized and structurally characterized. Compound 1 is constructed from the [Zn(P₄Mo₆)₂]-based 2D layer and μ₂-bridging L¹ ligands, which shows a (2,3,8)-connected three-dimensional framework with {{4·6²}2{4⁴·6²·8¹⁸·12⁴}{4}²} topology. 1 represents the first 3D P₄Mo₆-based MOF constructed by mixed N-donor ligands. The electrocatalytic and photocatalytic activities of compound 1 have been investigated.     

Ladder-like metal diphosphonates exhibiting field-induced magnetic transitions

Two new isomorphous phosphonates M(ahbdpH₂) · H₂O [M = Mn (1), Co (2); ahbdpH₄ = 4-amino-1-hydroxybutane-1,1-diphosphonic acid, C₄H₁₃NO₇P₂] have been hydrothermally synthesized. Both exhibit a ladder-like chain structure in which the edge-shared {MO₆} octahedra are linked by {CPO₃} tetrahedra through corner-sharing. The double chains are connected through extensive hydrogen bonds among amino groups, phosphonate oxygen atoms and lattice water molecules, hence generating a three-dimensional network. Magnetic measurements reveal that both experience field-induced magnetic transitions at low temperature.     

A dual shell-like heptadecanuclearity [Gd5Ni12] cluster with ferromagnetic interaction and large magnetocaloric effect

A new dual shell-like heptadecanuclearity [Gd₅Ni₁₂(Pro)₉(CMP)₆(μ₃-OH)₉(μ₂-OH)₃(H₂O)₃] · Cl₆ · 23H₂O (1) cluster with proline (HPro) and N-carboxymethyl-l-proline (H₂CMP) as coligands has been successfully synthesized and characterized. The compound consists of rare trigonal bipyramid {Gd₅} core and triangular orthobicupola {Ni₁₂} outer shell. The magnetic studies reveal that 1 shows ferromagnetic interactions and a large magnetocaloric effect (22.4 J kg^− 1 K^− 1, ΔH = 7 T).     

A novel transition-metal-linked hexaniobate cluster with photocatalytic H2 evolution activity

A novel transition-metal (TM) complex based on Lindqvist polyoxoniobate K₁₀[(Nb₆O₁₉)Cr^III(H₂O)₂]₂·28H₂O (1) has been synthesized by a new two-pot synthesis strategy and structurally characterized by single crystal X-ray diffraction analysis, IR spectrum, UV–vis spectroscopy, XRPD and TG analysis. Compound 1 crystallizes in the C2/m space group with a = 32.143(19) Å, b = 10.030(6) Å, c = 12.878(8) Å, β = 110.611(9)°, and V = 3886(4) ų. X-ray structure analysis reveals that polyanion [(Nb₆O₁₉)Cr^III(H₂O)₂]₂^10 − (1a) represents the first example of two nuclear dimeric polyoxoniobate, in which two Lindqvist anions [Nb₆O₁₉]⁸ are sandwiched by two {Cr^III(H₂O)₂} groups. Further, 1 exhibits photocatalytic H₂ evolution activity.