Synthesis,Structure and Characterization of [Cu(2,2′-bpy)_2][{Cu(2,2′-bpy)_2}_2W_(12)O_(40)(H_2)]·4H_2O

An organic-inorganic compound [Cu(2,2′-bpy)2][{Cu(2,2′-bpy)2}2W12O40(H2)]·4H2O (Mr = 4048.00) was prepared from the hydrothermal reaction of Na2WO4·2H2O, CuCl2·2H2O, 2,2′-bipyridine (2,2′-bpy) and H2O at 160 ℃ for 4 days. The compound crystallizes in the monoclinic system, space group P21/n with a = 18.9196(8), b = 20.4212(8), c = 21.8129(9) , β = 96.992(3)°, V = 8365.0(6) 3, Dc = 3.214 g/cm3, Z = 4, μ(MoKα) = 17.269 mm-1 and F(000) = 7324. Of the 119837 total reflections, 17315 were unique (Rint = 0.0489). The final R = 0.0385 and wR = 0.0770 for 11142 observed reflections with I > 2σ(I). Single-crystal X-ray diffraction reveals that the structure is composed of [{Cu(2,2′-bpy)2}2W12O40(H2)]2- anions, discrete [Cu(2,2′-bpy)2]2+ cations and lattice water molecules, and the anion is made up of a {W12O40(H2)}6- α-Keggin core decorated with two {Cu(2,2′-bpy)2}2+ groups through bridging oxygen atoms.     

Synthesis, crystal structure and properties of a new organic-inorganic hybrid Dawson-like polyoxotungstate [Co(2,2′-bpy)_3]_2[Co(2,2′-bpy)_2Cl][Co(2,2′-bpy)_2]H_2- [SbW_(18)O_(60)]·4H_2O

A new organic-inorganic hybrid polyoxometalate based on Dawson-like polyoxotungstate anion [SbW18O60]9, formulated [Co(2,2′-bpy)3]2[Co(2,2′-bpy)2Cl][Co(2,2′-bpy)2]H2[SbW18O60]·4H2O (2,2′-bpy= 2,2′-bipyridine) has been synthesized from Sb2O3, Na2WO4, CoCl2, and 2,2′-bipyridine materials by hydrothermal method, and which was characterized by elemental analyses, IR, XPS, EPR, TG, and X-ray single crystal diffraction. Structure analysis shows that the polyoxoanion self-assembled under hydrothermal conditions consists of a Dawson-like polyoxotungstate cluster anion [SbW18O60]9 en- capsulating a pyramidal {SbO3} group within the {W18} cluster cage. EPR spectra show that the high-spin octahedral CoII and low-spin CoII ions coexist in the title compound. Magnetic properties in- dicate that the compound is antiferromagnetic.     

Hybrid Tungstocuprate [Cu(2,2′-bpy)_3]_2H_4[CuW_(12)O_(40)]·6H_2O Based on Keggin Polyoxoanion [CuW_(12)O_(40)]~(6-) with Cu~Ⅱas Heteroatom

A novel hybrid tungstocuprate(Ⅱ) [Cu(2,2′-bpy)3]2H4[CuW12O40]·6H2O(2,2′-bpy=2,2′-bipyridine) was synthesized via hydrothermal method and characterized using elemental analyses, IR, UV, XPS, TG-DSC, EPR, and X-ray single crystal diffraction. The structural analysis shows that the complex consists of an unusual Keggin-type polyoxoanion [CuW12O40]6- and a pair of chiral complex cations [Cu(2,2′-bpy)3] together with four protons and six crystallization water molecules, and the Keggin polyoxoanion is connected with [Cu(2,2′-bpy)3] via multiple C—H…O hydrogen bonds resulting in a dimer.     

Synthesis,Structure and Electrochemical Property of a Supramolecular Compound（H2en）2[Cu（en）2（H3O）2][Mo8O28]

A supramolecular compound(H2en)2[Cu(en)2(H3O)2][Mo8O28](en=ethylenediamine) was hydrothermally prepared and confirmed by elemental analysis and TG analysis.Single-crystal X-ray analysis reveals that the crystal crystallizes in the triclinic system,space group P1 with a=9.4635(4),b=9.8645(5),c=10.9794(5),α=69.2050(10),β=72.3730(10),γ=78.4510(10)o,Mr=1559.55,V=908.24(7)3,Z=1,Dc=2.851 g/m3,F(000)=749,μ=3.350 mm-1,S=1.000,the final R=0.0217 and wR=0.0567.The compound consists of(H2en)2+,[Mo8O28]8-anion and [Cu(en)2(H3O)2]2+ cations and constructs a 3D supramolecular structure through hydrogen bonds between the nitrogen atoms from en of [Cu(en)2(H3O)2]4+ fragments and the terminal oxygen atoms from the [Mo8O28]8-polyoxoanions.The electrochemical behavior of this compound has been studied in detail based on a solid bulk modified carbon paste electrode of compound(CPE).     

New Inorganic-organic Hybrid Tetravanadate: Preparation, Characterization and Application in Chemically Modified Electrode

A new inorganic-organic hybrid tetravanadate [Co(2,2′-bpy)3]2V4O12·11H2O(1) has been prepared and characterized. X-Ray diffraction study reveals that compound 1 contains classical cluster anions [V4O12]4–, coordinated cations [Co(2,2′-bpy)3]2+ and eleven water molecules, in which an interesting decamer water cluster is formed. The hybrid nanoparticles were firstly used as a bulk-modifier to fabricate a chemically modified paste electrode (1-CPE). The electrochemical behavior and electrocatalysis of 1-CPE ha...     

Synthesis and Structure Investigation of a Transition Metal Ion Bridging Bis(diphosphopentamolybdates),[H_2BIIM]_3[HBIIM]_4[Mn(H_2O)_4(P_2Mo_5O_(23))_2]·7H_2O

A novel transition metal ion bridging bis(diphosphopentamolybdates) has been synthesized and characterized by elemental analysis,IR spectrum,UV spectrum and single-crystal X-ray diffraction.The single-crystal structure analysis shows that the compound consists of seven charge-compensating 2,2'-biimidazole cations (BIIM=2,2'-biimidazole) and one dumbbell-like [Mn(H2O)4(P2Mo5O23)2]10-heteropolyanion which is constructed by two [P2Mo5O23]6-clusters bridged through one [Mn(H2O)4]2+ cation.     

{(n-Bu4N)2[Mo2O2S6Cu6Br4(4,4'-bipy)3]·0.5H2O}n的合成与晶体结构

Cluster coordination polymer {(n-Bu4N)2[Mo2O2S6Cu6Br4(4,4'-bipy)3]·0.5H2O)}n (4,4'-bipy=4,4'-bipyridine),has been synthesized and characterized by X-ray crystallography. The polymeric anion {[Mo2O2S6Cu6Br4(4,4'-bipy)3]2-}n is composed of secondary building units (SBUs) [MoOS3Cu3], Br atoms and 4,4'-bipy ligands. Two secondary building units [MoOS3Cu3] and a double parallel 4,4'-bipy ligands form an octanuclear rectangular metallamacrocycle with the dimension of 1.13×0.39 nm2, which is further connected by single bridging 4,4'-bipy ligands to form a 1D zigzag structure. Crystal data for compound 1: C62H97N8O2.50S6Br4Cu6Mo2,M=2 079.68, Triclinic, P1, a=0.982 40 (10) nm, b=1.293 70(10) nm, c=1.737 4(2) nm, α=97.810(10)°,β=101.390(10)°,γ=108.520(10)°, V=2.005 1(4) nm3, Z=2, Dc=1.722 g·cm-3, F(000)= 1039,μ (Mo Kα)=4.055 mm-1, the final R=0.040 7, wR2=0.097 2. CCDC: 236407.     

Hydrothermal Synthesis and Crystal Structure of a Manganese(II) Coordination Polymer with 1,1′-Biphenyl-2,2′,6,6′-tetracarboxyl Acid and 2,2′:6,2′′-Terpyridine Ligands

The title compound {[Mn(H2BPTC)(tpy)(H2O)]·(H2O)3}n (1, H4BPTC = 1,1′- biphenyl-2,2′,6,6′-tetracarboxylic acid, tby = 2,2′:6,2′′-terpyridine) has been synthesized by the hydrothermal reaction, and its structure was determined by X-ray diffraction and characterized by elemental analysis, IR spectrum and thermogravimetric analysis. The crystal is of monoclinic, space group P21/c with a = 10.971(2), b = 20.776(4), c = 14.332(3) , β = 109.25(3)o, MnC31H27N3O12, Mr = 688.50, V = 3084.1(10) 3, Dc = 1.483 g/cm3, F(000) = 1420, μ = 0.498 mm-1, S = 1.066 and Z = 4. The final refinement gave R = 0.0447 and wR = 0.1103 for 5107 observed reflections with I > 2σ(I). The title complex has a {[Mn(H2BPTC)(tpy)(H2O)]}n chain structure, and the hydrogen bonding interactions make it more stable. Each chain is further connected to the adjacent ones through π···π, C-H···π and rich hydrogen bonds to form a metal-organic coordination polymer.     

Synthesis and Crystal Structure of a 2-D Hydrogen-bonded Supramolecular Network {[Cu_4(OH)_4(2,2'-bpy)_4(bqdc)]·2ClO_4}_n

The title compound {[Cu4(OH)4(2,2'-bpy)4(bqdc)]·2ClO4}n 1 (bqdc = 2,2'-biquino- line-4,4'-dicarboxylic acid) has been synthesized by hydrothermal method. Its crystal structure is of triclinic, space group P1 with a = 7.6561(5), b = 12.4652(8), c = 15.7501(10) , α = 80.0480(10), β = 87.7900(10), γ = 74.0800(1)o, V = 1423.65(16) 3, Z = 2, C30H23ClN5O8Cu2, Mr = 744.06, Dc = 1.736 g/cm3, μ = 1.651 mm─1, F(000) = 754, the final R = 0.0421 and wR = 0.1163 for 4973 observed reflections with I > 2σ(I). In 1, tetra-copper chair-like clusters of [Cu4(OH)4(2,2'-bpy)4]4+ are connected by bqdc ligands to form one-dimensional chains, which are further connected by hydrogen bonds to generate a two-dimensional supramolecular network .     

Solvothermal Synthesis and Structure Studies of a Mixed-valence Oxochloromolybdenum Complex

Emerald green crystals of a new mixed-valence oxochloromolybdenum complex,Mo(OH)2(2,2′-bipy)Cl2.[MoO(2,2′-bipy)Cl3]2, were obtained in an attempt to synthesize the Mo-S cluster compounds under solvothermal conditions. The title compound was characterized by EPR and X-ray single-crystal diffraction techniques. Crystallographic data: orthorhombic, space group Fdd2, a = 12.684(1), b = 21.518(2), c = 29.096(3)A, Mr = 1103.97, V= 7941(1)A^3, Z= 8, Dc =1.843 g/cm^3,μ= 1.514 mm^-1, F(000) = 4304, R = 0.0654 and wR = 0.1544 for 1944 observed reflections with 1 ≥/ 2σ(I). The compound consists of two different neutral molecules, Mo^IV-(OH)2(2,2′-bipy)Cl2 and MoVO(2,2′-bipy)Cl3. Both Mo^IV and Mo^V ions are in a distorted octahedral environment. The Mo(1)^IV atom is surrounded by two Cl^- ions and two O atoms from OH^- and two N atoms from a 2,2′-bipy ligand. The Mo(2) atom is surrounded by three Cl^- ions, one O^2- anion and two N atoms from another 2,2“-bipy ligand. The bipyridine occupies two cis-equatorial sites, while the Cl^- ions are located at the axial and equatorial positions.     

1D Polyoxometalate‐based Inorganic‐Organic Hybrid Derived from ß‐Octamolybdate — Synthesis and Crystal Structure of [CoII(2, 2′‐bipy)2]2[Mo8O26]

A polyoxometalate‐based inorganic–organic hybrid compound [Co^II(2, 2′‐bpy)₂]₂[Mo₈O₂₆] ( 1 ) was synthesized by hydrothermal methods and structurally characterized by IR spectrum, TG analysis and X‐ray diffraction. The compound crystallizes in the monoclinic system, space group P2₁/n, a = 10.0681(2), b = 16.4467(2), c = 15.7838(3) Å, β = 100.046(1)°, V = 2573.52(8) ų, Z = 2. The structure of 1 is built up from β‐[Mo₈O₂₆]^4? subunits covalently linked via [Co^II(2, 2′‐bpy)₂]²⁺ fragments into a infinite 1D {[Co^II(2, 2′‐bpy)₂]₂[Mo₈O₂₆]}_∞ polymer.     

Modified polyoxometalate: a novel monocapped bi‐supporting and reduced α‐Keggin structure {PMo12O40[Cu(2,2′‐bpy)]}[Cu(2,2′‐bpy)(en)(H2O)]2

A novel modified polyoxometalate, {PMo₁₂O₄₀[Cu(2,2′‐bpy)]}[Cu(2,2′‐bpy)(en)(H₂O)]₂ [2,2′‐bpy is 2,2′‐bipyridyl (C₁₀H₈N₂) and en is ethylenediamine (C₂H₈N₂)], has been synthesized hydrothermally and structurally characterized by elemental analysis, TG, IR, XPS and single‐crystal X‐ray diffraction. The structural analysis reveals that the compound contains the reduced Keggin polyanion [PMo₁₂O₄₀]^6? as the parent unit, which is monocapped by [Cu(2,2′‐bpy)]²⁺ fragments via four bridging O atoms on an {Mo₄O₄} pit and bi‐supported by two [Cu(2,2′‐bpy)(en)(H₂O)]²⁺ coordination cations simultaneously. There exist strong intramolecular π–π stacking between the capping and supporting units, which play a stabilizing role during the crystallization of the compound. Adjacent POM clusters are further aggregated to form a three‐dimensional supramolecular network through noncovalent forces, hydrogen bonding and π–π stacking interactions. In addition, the photocatalytic properties were investigated in detail, and the results indicated that the compound can be used as a photocatalyst towards the decomposition of the organic pollutant methylene blue (MB).     

catena‐Poly­[[heptakis­(di­methyl­form­amide‐κO)­di‐μ4‐oxo‐tetra‐μ3‐oxo‐hexa­deca‐μ2‐oxo‐tetra­oxo­lan­than­um(III)­octamolybdenum(IV)]‐μ‐sodium(I)]

The title compound, [NaLaMo₈O₂₆(C₃H₇NO)₇]_n, contains infinite chains of [Mo₈O₂₆]⁴⁻ units supporting di­methyl­form­amide‐coordinated La^III cations and linked by Na⁺ cations. The lanthanum center adopts a nine‐coordinate geometry and the Na atom is sandwiched between two β‐[Mo₈O₂₆]⁴⁻ units.     

New organic–inorganic frameworks incorporating iso‐ and heteropolymolybdate units and a 3,3′,5,5′‐tetramethyl‐4,4′‐bi‐1H‐pyrazole‐2,2′‐diium multiple hydrogen‐bond donor

Poly[bis(3,3′,5,5′‐tetramethyl‐4,4′‐bi‐1H‐pyrazole‐2,2′‐diium) γ‐octamolybdate(VI) dihydrate], {(C₁₀H₁₆N₄)₂[Mo₈O₂₆]·2H₂O}_n, (I), and bis(3,3′,5,5′‐tetramethyl‐4,4′‐bi‐1H‐pyrazole‐2,2′‐diium) α‐dodecamolybdo(VI)silicate tetrahydrate, (C₁₀H₁₆N₄)₂[SiMo₁₂O₄₀]·4H₂O, (II), display intense hydrogen bonding between the cationic pyrazolium species and the metal oxide anions. In (I), the asymmetric unit contains half a centrosymmetric γ‐type [Mo₈O₂₆]⁴⁻ anion, which produces a one‐dimensional polymeric chain by corner‐sharing, one cation and one water molecule. Three‐centre bonding with 3,3′,5,5′‐tetramethyl‐4,4′‐bi‐1H‐pyrazole‐2,2′‐diium, denoted [H₂Me₄bpz]²⁺ [N...O = 2.770 (4)–3.146 (4) Å], generates two‐dimensional layers that are further linked by hydrogen bonds involving water molecules [O...O = 2.902 (4) and 3.010 (4) Å]. In (II), each of the four independent [H₂Me₄bpz]²⁺ cations lies across a twofold axis. They link layers of [SiMo₁₂O₄₀]⁴⁻ anions into a three‐dimensional framework, and the preferred sites for pyrazolium/anion hydrogen bonding are the terminal oxide atoms [N...O = 2.866 (6)–2.999 (6) Å], while anion/aqua interactions occur preferentially viaμ₂‐O sites [O...O = 2.910 (6)–3.151 (6) Å].     

Poly[diaqua(μ‐4,4′‐bipyridine‐κ2N:N′)bis(μ‐cyanido‐κ2C:N)bis(cyanido‐κC)nickel(II)copper(II)]: a metal–organic cyanide‐bridged framework

The structure of the title compound, [NiCu(CN)₄(C₁₀H₈N₂)(H₂O)₂]_n or [{Cu(H₂O)₂}(μ‐C₁₀H₈N₂)(μ‐CN)₂{Ni(CN)₂}]_n, was shown to be a metal–organic cyanide‐bridged framework, composed essentially of –Cu–4,4′‐bpy–Cu–4,4′‐bpy–Cu– chains (4,4′‐bpy is 4,4′‐bipyridine) linked by [Ni(CN)₄]²⁻ anions. Both metal atoms sit on special positions; the Cu^II atom occupies an inversion center, while the Ni^II atom of the cyanometallate sits on a twofold axis. The 4,4′‐bpy ligand is also situated about a center of symmetry, located at the center of the bridging C—C bond. The scientific impact of this structure lies in the unique manner in which the framework is built up. The arrangement of the –Cu–4,4′‐bpy–Cu–4,4′‐bpy–Cu– chains, which are mutually perpendicular and non‐intersecting, creates large channels running parallel to the c axis. Within these channels, the [Ni(CN)₄]²⁻ anions coordinate to successive Cu^II atoms, forming zigzag –Cu—N[triple‐bond]C—Ni—C[triple‐bond]N—Cu– chains. In this manner, a three‐dimensional framework structure is constructed. To the authors' knowledge, this arrangement has not been observed in any of the many copper(II)–4,4′‐bipyridine framework complexes synthesized to date. The coordination environment of the Cu^II atom is completed by two water molecules. The framework is further strengthened by O—H...N hydrogen bonds involving the water molecules and the symmetry‐equivalent nonbridging cyanide N atoms.     

Monodentate Coordination of 4,4′‐Bipyridine Leading to a Supramolecular Network – Synthesis and Crystal Structure of [H2bpp][{Cu(Hbpy)2}{α‐HP2W18O62}]·4H2O

The new supramolecular compound [H₂bpp][{Cu(Hbpy)₂}{α‐HP₂W₁₈O₆₂}]·4H₂O ( 1 ) (bpy = 4,4′‐bipyridine, bpp = 1,3‐bis(4‐pyridyl)propane) was synthesized hydrothermally and characterized byelemental analysis, IR spectroscopy, thermogravimetric analysis and single‐crystal X‐ray diffraction. In compound 1 , the cationic fragment [Cu(Hbpy)₂]⁺ connects to the Dawson anion through a coordinating Cu←O bond, and the copper atom is coordinated by another polyoxoanion through a weak covalent bond with a Cu1–O26 distance of 2.879(2) Å, forming a polymeric chain. The bpy ligand in [Cu(Hbpy)₂]⁺ adopts a monodentate coordination mode, the other nitrogen atom of the bpy ligand is protonated. The protonated Hbpy⁺ acts as hydrogen‐bond donor and constructs a two‐dimensional double‐sheet supramolecular network involving the one‐dimensional chains through the hydrogen bonds. The H₂bpp²⁺ ion connects twoα‐HP₂W₁₈O₆₂^6– clusters from two supramolecular networks through hydrogen bonds and creates a three‐dimensional supramolecular architecture. The thermal decomposition of 1 happens over a wide temperature range (450–800 °C), which indicates that it might include complicated oxidation–reduction processes.     

Assembly of a New 3D Octamolybdate‐based Compound: Using the Flexible Bis(triazole) ligand with a –(CH2)6– Spacer

Through utilizing the flexible bis(triazole) ligand 1, 6‐bis(1, 2, 4‐triazol‐1‐yl)hexane (btx), a new octamolybdate‐based compound, [Cu₂(btx)₄(β‐Mo₈O₂₆)] · H₂O ( 1 ), was synthesized under hydrothermal conditions. It was characterized by single‐crystal X‐ray diffraction, elemental analyses, IR spectroscopy, thermogravimetric analysis, and cyclic voltammetry. In compound 1 , the [β‐Mo₈O₂₆]^4– anion acts as a bi‐connected inorganic linkage to connect the Cu‐btx moieties. The Cu1‐btx moiety linked by the [β‐Mo₈O₂₆]^4– anions exhibits a 2D layer, while the Cu2‐btx moiety also shows a similar 2D layer. Furthermore, these two 2D moieties construct a 3D framework through sharing the same N7‐containing btx ligands.     

Synthesis and Characterization of Two New Transition‐Metal Complex Salts of the Wells‐Dawson Polyanion

Two new transition‐metal (TM) complex salts of the Wells‐Dawson polyanion: [Cu(2,2′‐bpy)₃]₂[Cu(2,2′‐bpy)₂]₂[P₂W₁₈O₆₂] ( 1 ) and [2,2′‐bpy]₈[Fe(2,2′‐bpy)₃]₈[P₂W₁₈O₆₂]₄·9H₂O ( 2 ) (2,2′‐bpy = 2,2′‐bipyridine), have been synthesized under hydrothermal conditions by using pre‐prepared α‐K₆P₂W₁₈O₆₂·15H₂O as a precursor. Crystal data for compound 1 : monoclinic, space group C2/c, a = 20.722(4) Å, b = 21.988(4) Å, c = 29.614(6) Å, β = 104.32(3)°, V = 13074(5) ų, Z = 4; for compound 2 : triclinic, space group , a = 15.804(3) Å, b = 27.519(6) Å, c = 27.566(6) Å, α = 72.71(3)°, β = 89.94(3)°, γ = 89.90(3)°, V = 11447(5) ų, Z = 1. Compounds 1 and 2 have been characterized by single‐crystal X‐ray diffraction, IR spectra, thermogravimetric analysis, XPS spectra and cyclic voltammetry. The two compounds were used as solid bulk modifiers to fabricate bulk‐modified carbon paste electrodes ( 1 ‐, 2 ‐CPE). The electrochemical behaviors of 1 ‐, 2 ‐CPE have been studied in detail. The redox behavior of the parent Wells‐Dawson type cluster was maintained completely in compounds 1 and 2 .     

A Bicapped α‐Keggin Unit‐Supported Transition Metal Complex: Hydrothermal Synthesis and Characterization of [Cu(en)2(H2O)]2[Cu(en)2]0.5[Mo8V7O42{Cu(en)2}]

A new metal‐oxo cluster supported transition metal complex, [Cu(en)₂(H₂O)]₂[Cu(en)₂]_0.5[Mo^VI₈V^IV₆V^VO₄₂{Cu(en)₂}], has been synthesized under hydrothermal conditions. Its structure was determined by single‐crystal X‐ray diffraction. The compound crystallizes in the triclinic system, space group (No. 2), a = 12.245(5), b = 12.669(5), c = 20.949(8) Å, α = 77.120(13), β = 78.107(17), γ = 65.560(14)°, V = 2860(2) ų, Z = 2. The metal‐oxo cluster contains a novel bicapped a‐Keggin structure unit and a [Cu(en)₂]²⁺ unit covalently bonded to the [Mo₈V₇O₄₂]^7? cluster.     

A New Polynuclear Copper‐Complex‐Substituted Tungstoarsenate(V)

A new polynuclear copper‐complex‐substituted dimeric tungstoarsenate(V), H₂[{Cu(2,2′‐bpy)}₈(H₂O)₂(AsW₉O₃₄)₂] · 12H₂O ( 1 ) (2,2′‐bpy = 2,2′‐bipydine), was synthesized hydrothermally and its structure was determined by single‐crystal X‐ray diffraction. The title compound has Ci symmetry and consists of two trilacunary Keggin anions [α‐AsW₉O₃₄]^9– supported by eight copper complex cations. The compound was also characterized by IR and fluorescence spectroscopy, TG analysis, and magnetic measurements. The emission spectrum of the compound in solid‐state exhibits a redshift relative to those of Na₈[A‐HAsW₉O₃₄] · 11H₂O and the free ligand 2,2′‐bpy. Magnetic measurements of the compound indicate competing ferro‐ and antiferromagnetic intramolecular coupling among the Cu^II atoms in the cluster anion.