Synthesis and characterization of nickel phosphonopropionate hybrid materials

Hydrothermal reaction of nickel acetate with 3-phosphonopropionic acid and 4,4′-bipyridine resulted in two novel phosphonate compounds Ni(HO₃PC₂H₄COO)(4,4′-bpy)(H₂O) · 0.5(4,4′-bpy) (bpy = bipyridine) (I) and Ni(O₃PC₂H₄COOH)(4,4′-bpy)(H₂O)₃ · H₂O (II). Single-crystal X-ray studies reveal that self-assemblies between the ligands and metal ion result in layer (I) and chain (II) structures. Magnetic measurement of I indicate there are ferromagnetic couplings between adjacent Ni²⁺ ions (C = 1.29 cm³ mol⁻¹ K and θ = 2.25 K).     

Self-assembly and guest binding of nickel(II) macrocyclic complex with pentyl groups and cis,cis-1,3,5-cyclohexanetricarboxylic acid

Reaction of the nickel(II) macrocyclic complex 1 including pendant pentyl groups in MeCN/H₂O mixed solvent with deprotonated cis,cis-1,3,5-cyclohexanetricarboxylic acid (CTC^3 −) resulted in two-dimensional (2-D) coordination polymer [Ni(C₁₈H₄₂N₆)]₃[C₆H₉(COO)₃]₂·6H₂O·6CH₃CN (2). The crystal structure of 2 indicates that each nickel(II) macrocyclic unit binds two CTC^3 − ions in trans position and each CTC^3 − ion coordinates three nickel(II) macrocyclic complexes to form a 2-D layer with hexagonal motif. The dried solid of 2 differentiates MeOH, EtOH, and PhOH in toluene solvent with the K_f values of 1.38, 2.11, and 6.68 M^− 1, respectively.     

pH-controlled the formation of 4-sulfocalix[4]arene-based 1D and 2D coordination polymers

Three manganese/4-sulfocalix[4]arene complexes, namely, {H[(C₂₈H₂₀O₁₆S₄)Mn(H₂O)₄Mn_0.5(H₂O)₂]}_n ·6nH₂O (1), {NH₄[(C₂₈H₂₀O₁₆S₄)Mn(H₂O)₄Mn_0.5(H₂O)₂]}_n · 5nH₂O (2), [(C₂₈H₂₀O₁₆S₄)Mn₂(H₂O)₈]_n · 6nH₂O (3), have been synthesized under different pH conditions. Complex 1, which exhibits a one-dimensional (1D) structure, is formed at [H⁺] = 2.0 mol L⁻¹. Reaction at pH 4 leads to another one-dimensional (1D) coordination polymer of 2. At pH 5, a two-dimensional (2D) coordination polymer of complex 3 is formed, showing clearly structural effects on pH response.     

Two organic–inorganic hybrid materials based on the penta-nuclear {MMn4} (M = W and Mo) heterometallic clusters and Schiff-base ligands

Two organic–inorganic hybrid compounds with the formula {[Mn^III(Salen)(H₂O)]₄MoO₄}·Cl₂·16H₂O (1) and {[Mn^III(Salen)(H₂O)]₄WO₄}·(CH₃COO)₂·11H₂O (2) (Salen = Di-[2-hydroxyl-3-methoxyl-benzaldehyde] ethylenediamine) have been synthesized and structurally characterized by IR, UV–vis spectroscopy, TG analysis and single crystal X-ray diffraction. Structural analysis revealed that compounds 1 and 2 consist of a [MoO₄]^2 − or [WO₄]^2 − building unit and four {[Mn^III(Salen)(H₂O)]⁺ metal–organic moieties, respectively. In the crystal structure, the [MoO₄]^2 − or [WO₄]^2 − tetrahedra coordinated with four Mn^III ions, resulting in the penta-nuclear heterometallic tetrahedra cluster compounds, which were rarely observed in the Mn-Salen system. Magnetic study revealed that there was antiferromagnetic coupling in the two compounds.     

Different hydrolytic stabilities of some C,N-chelated germanium alkoxides

C,N-intramolecularly coordinated germanium(IV) methoxides Ar₃GeOMe (1) and (Ar′)₂Ge(OMe)₂ (2) [where Ar = [2-(Me₂NCH₂)C₆H₄]⁻, Ar′ = [2-(DipN = CH)C₆H₄]⁻, Dip = 2,6-(i-Pr)₂C₆H₃] were prepared by the reaction of the lithium precursors ArLi and Ar′Li with Ge(OMe)₄ in appropriate molar ratio. While the diorganogermanium(IV) compound 2 is air-stable specie, triorganogermanium(IV) compound is surprisingly smoothly hydrolyzed by air-moisture to corresponding triorganogermanol Ar₃GeOH (3). Studied compounds were characterized by the help of multinuclear NMR spectroscopy and in the case of 2 and 3 using single-crystal X-ray diffraction analysis.     

Amine-directed structural studies of four zinc metal-organic frameworks based on a novel phosphonocarboxylate ligand

A novel phosphonocarboxylic ligand, 4′-phosphonobiphenyl-3,5-dicarboxylic acid (H₄pbpdc), was synthesized to construct 4 zinc compounds, namely, {[Zn₃(pbpdc)₂·2R}_n (R = C₅H₁₂N for 1, C₄H₁₀N for 2 and C₆H₁₆N for 3) and {[Zn₂pbpdc]·C₆H₁₈N₃}_n(4), which were characterized by X-ray crystallography, elemental analysis, FTIR and TG. Structures 1 ~ 3 have the same 3-dimensional (3-D) frameworks with point symbol of {4.6.7³.8}₂{4².6.7².8}₂{4².6².7.8}₂{4².6².7²}. Structure 4 is constructed from a 6-connected metallic cluster and 3-connected phosphonocarboxylic building units resulting in a topology of flu-3,6-C2/c. The luminescent properties of compounds 1 ~ 4 and organic ligand were studied.     

Two novel 3D 3d–4f polymers with triethylenetetraaminehexaacetic acid: Syntheses,structures, and magnetic properties

Two novel 3d–4f polymers [La(H₂O)₄][M₂TTHA(SCN)₂] · H₃O⁺ (M = Ni(1), Cu(2), H₆ TTHA = triethylenetetraaminehexaacetic acid) were synthesized and characterized by X-ray single-crystal diffraction, elemental analysis, IR and magnetic properties. Two complexes show 3D framework, comprising an unusual infinite 1D chain based on heterometallic La₂M₂ rings (M = Ni(1), Cu(2)).     

Three novel bismuth-based coordination polymers: Synthesis,structure and luminescent properties

Three novel bismuth-based coordination polymers, [(CH₃)₂NH₂][Bi(pdc)(bdc)]·2DMF, [(CH₃)₂NH₂][Bi(tdc)₂]·1.5DMF and [Bi(bpdc)₂H₂O]·xGuest (compounds 1–3) (H₂pdc = 3,5-pyridinedicarboxylic acid, H₂bdc = 1,4-benzenedicarboxylic acid, H₂tdc = 2,5-thiophenedicarboxylic acid, H₂bpdc = 4,4′-biphenyldicarboxylic acid), have been successfully synthesized under solvothermal conditions and characterized by single crystal X-ray diffraction. Compounds 1 and 2, which are constructed by 9-coordinated or 8-coordinated Bi^3 +, feature three-dimensional structures with hms and dia topology, respectively. However, 5-coordinated Bi^3 + based compound 3 is a two-dimensional layered structure. Compound 1 can tune emissive performance by doping different lanthanide ions Tb^3 +, Eu^3 + and Dy^3 +. Furthermore, detection of nitro explosives is investigated. All of the compounds are characterized by elemental analysis, IR spectrum and thermogravimetric analysis.     

1-D networks formed by metal⋯sulfur van der Walls contacts: Novel tetrazole–thiolato Pd(II) and Pt(II) complexes

Pd(II)– and Pt(II)–azido complexes, [M(N₃)(PMe₃)₂(C–L)] {LH = 2-(2′)-thienyl pyridine; M = Pd (1), Pt(2)}, which contain σ-bonded heterocycles (L), were treated with aryl isothiocyanate (Me₂C₆H₃–NCS) to afford the corresponding Pd(II) and Pt(II) tetrazole–thiolato complexes, trans-{M[SCN₄(2,6-Me₂C₆H₃)](PMe₃)₂(C–L)} {M = Pd (3), Pt (4)}. Complexes 3 and 4 have a 1-D helical network formed by the intermolecular M?S van der Waals contacts.     

The first anion template cubic cyanometallate cage and its 3,5-dimethyltris(pyrazolyl)methane iron(II, III) tricyanide building blocks

Several 3,5-dimethyltris(pyrazolyl)methane iron(II, III) tricyanide building units have been prepared and characterized. Treatment of K[(HC(3,5-Me₂Pz)₃)Fe^II(CN)₂](K⁺1^-) with Fe^II(H²O)⁶(BF⁴)² affords a new anion template cubic cyanometallate cage [(BF₄) ⊂ {Fe^II(H₂O)}₄{(HC(3,5-Me₂Pz)₃)Fe^II (CN)₃}₄](BF₄)³ 3.     

Multiple functions of amines in the synthesis of anionic,cationic, and neutral indium oxalates

Three new indium oxalates, formulated as H₃dpta·In(C₂O₄)(H₂O)₃·2SO₄ (1), In(qd)(C₂O₄)_1.5·1.5H₂O (2), and H₂bpp·In₂(C₂O₄)₄ (3) in which dpta = dipropylenetriamine, qd = quinoxaline-2,3(1H,4H)-dione, and bpp = 1,3-bis(4-piperidyl)propane, were prepared in the presence of different amines. These compounds have cationic, neutral, and anionic frameworks, respectively. Topological analyses reveal that compound 2 has an hcb net, while compound 3 has a dia net. The photoluminescent property of compound 2 was also investigated.     

Binuclear, 2D grid and 3D interlocking coordination polymers based on 1,2,4,5-benzenetetracarboxylic acid and 4,4′-azobispyridine

Three new nickel(II) complexes [Ni₂(btec)(azopy)₂(H₂O)₈]·2H₂O (1), {[Ni(H₂btec)(azopy)(H₂O)₂]·(azopy)}_n (2) and {[Ni₄(btec)₂(azopy)₃(H₂O)₁₀]·8H₂O}_n (3) (H₄btec = 1,2,4,5-benzenetetracarboxylic acid; azopy = 4,4′-azobispyridine) have been synthesized by tuning the reaction temperature and the metal–ligand ratio. They were characterized by single-crystal X-ray diffraction and elemental analysis. 1 shows a binuclear structure, 2 exhibits a 2D grid, and 3 features an interesting 3D framework with (6³)(4.6²)(4².6².8²) topology formed by two types of interlocked 2D layers.     

Ligand substitution in sandwich-type complexes of germanotungstates: Syntheses,crystal structures and magnetic properties

Two new sandwich-type germanotungstates K₂H₂{Zn(en)₂}{Zn(en)₂}₂{(GeW₉O₃₄)₂Zn₄(Hen)₂}·17H₂O (1) and K₂H₂{Ni(en)₂}{Ni(en)₂}₂{(GeW₉O₃₄)₂Ni₄(Hen)₂}·12H₂O (2) (en = ethylenediamine) have been hydrothermally synthesized. The polyanions of the two compounds are composed of a [Ge₂W₁₈M₄(Hen)₂O₆₈]^10? (M = Zn, Ni) group decorated by two [M(en)₂(H₂O)]²⁺ units. The luminescence of compound 1 exhibits an intense UV radiation emission maximum at λ ≈ 449 nm upon excitation of 372 nm. The magnetic investigation of compound 2 demonstrates the presence of ferromagnetic interactions between the Ni²⁺ ions of the Ni₄O₁₄(Hen)₂ clusters in 2.     

A Michael-type reaction between acrylato ions and ethylenediamine coordinated to Ni(II). Synthesis,crystal structure and magnetic properties of [Ni2(EDDP)2(H2O)2] · 2H2O (H2EDDP = ethylenediamine-N,N-dipropionic acid)

The reaction between NiCO₃ · Ni(OH)₂, acrylic acid and ethylenediamine in a 2:4:1 molar ratio affords the binuclear complex, [Ni₂(EDDP)₂(H₂O)₂] · 2H₂O 1. The organic ligand, EDDP^2? (the dianion of the ethylenediamine-N,N-dipropionic acid ligand), results from the addition of one amine group to the carbon–carbon double bonds of two acrylato ions. The crystal structure of 1 consists of neutral centrosymmetric entities, with the nickel ions connected by two carboxylato groups, each one acting as a monoatomic bridge. The intramolecular Ni?Ni distance is 3.212 Å. The metal ions exhibit an octahedral geometry. The cryomagnetic investigation of 1 reveals an antiferromagnetic coupling of the nickel(II) ions (J = ?21.8 cm^?1, H = ?JS_Ni1S_Ni2).     

Formation of three-dimensional supramolecular water architectures containing 1D water chains via dianion templating

A three-dimensional supramolecular water architectures: [Ni(phen)₃](C₁₀H₁₆O₄) · (C₁₀H₁₈O₄)_0.5 · 11H₂O (1) [phen = 1,10-Phenanthroline, C₁₀H₁₆O₄ = sebacic dianion, C₁₀H₁₈O₄ = sebacic acid] has been synthesized and characterized by IR, elemental analysis, thermogravimetric analysis, and single-crystal X-ray diffractions. 1D water chains behave as pillars to join these water sheets to make an overall three-dimensional supramolecular architecture by hydrogen-bonding interactions.     

Fluorescent selectivity for small molecules of two coordination polymers based on a tetracarboxylate ligand

Two coordination polymers [Cd(tptc)_0.5(4,4′–bibp)]_n (1) and {[Zn₃(Htptc)₂(phen)₂]·1.5H₂O}_n (2) (H₄tptc = terphenyl-3,3″,5,5″-tetracarboxylic acid, 4,4′-bibp = 4,4′-bis(imidazolyl)biphenyl, and phen = 1,10-phenanthroline) were synthesized under solvothermal conditions. Complex 1 displays a 3D structure with a Schläfli symbol of {4⁴.6²}{4⁸.6²⁰}. Complex 2 possesses a 2D layer network, incorporating [Zn₃(COO)₆] second building units (SBUs), which is packed into a 3D supramolecular architecture by π ⋯ π interactions. Both of them exhibit strong luminescence characteristics. It is worth to note that complexes 1 and 2 show potential application to detect small organic molecules.     

A new organic-inorganic hybrid based on dimeric [Mn2V22O64]10 − polyoxoanion as catalyst for oxidation of sulfides

A new organic-inorganic hybrid compound constructed from [Mn₂V₂₂O₆₄]^10 − units, H₆[(C₆H₄NO₂Cu(H₂O)₄)]₂[Mn₂V₂₂O₆₄]·28H₂O 1, has been synthesized and characterized by single-crystal X-ray diffraction, IR, powder X-ray diffraction (XPRD) and TG. Compound 1 is composed of dimeric [Mn₂V₂₂O₆₄]^10 − polyoxoanions, metal-organo fragments [(C₆H₄NO₂Cu(H₂O)₄)]^2 + and lattice water molecules. Moreover, a three-dimensional supramolecular structure is formed in 1 by the extensive hydrogen bond interaction among the terminal oxygen atoms of [Mn₂V₂₂O₆₄]^10 − anions, the coordinated waters of Cu^2 + ions and crystal water molecules. Compound 1 exhibits remarkable catalytic activity for the heterogeneous oxidation of sulfides under mild condition.     

Synthesis and properties of an unexpected trinuclear copper(I) complex supported by diphenylphosphinomethane

The reaction of CuCl₂·2H₂O, diphenylphosphinomethane (dppm), and tetracyanoethylene (TCNE) affords one unexpected trinuclear copper(I) complex, [Cu^I₃(dppm)₃(μ₃-Cl)₂]·[TCMA] 1 (TCMA: tricyanoacrylmethylate, a new compound deriving from TCNE). Structural study shows that three copper atoms are connected by dppm ligands bridging each edge to form a Cu₃P₆ unit. At room temperature, 1 appears photoluminescence at 447 nm. And 1 also can electrocatalyze hydrogen generation from acetic acid with a turnover frequency (TOF) of 99.9 mol of H₂ per mole of catalyst per hour at an overpotential of 941.6 mV.     

Self-assembly of an organo-palladium molecular basket that encapsulates cobalticarborane anion in water

Two [M₃L₃]^6 +-type organo-palladium(II) macrocyclic host molecules, {[(phen)Pd]₃(4,7-phen)₃}(NO₃)₆, 1·6NO₃⁻; {[(dtod-phen)Pd]₃(4,7-phen)₃}(NO₃)₆, 2·6NO₃⁻, (where M = (4,7-phen)Pd, (dtod-phen)Pd; 4,7-phen = 4,7-phenanthroline (L), phen = 1,10-phenanthroline, dtod-phen = 5,6-di(1′,4′,7′,10′-tetraoxododecanoxy)-1,10-phenanthroline), have been synthesized by metal-directed self-assembly in aqueous solution. These basket-shaped hosts bearing syn, syn, syn orientations and their anion complexes, have been fully characterized by ¹H NMR, cold-spray ionization mass spectrometry (CSI-MS) and in the case of basket-shaped host 1*PF₆⁻ by X-ray single-crystal diffraction analysis. On the basis of anion binding structure within the cavity of 1, the molecule basket 2 possessing a hydrophobic inner cavity expanded with hydrophilic polyethyleneglycol chains was successfully designed for encapsulating one giant anion [(C₂B₉H₁₁)₂Co]⁻ in water and the host–guest interaction was studied by ¹H NMR titration and CSI-MS.     

Syntheses,crystal structures,and magnetic studies of two cobalt(II) coordination polymers based on concurrent ligand extension

An ether bridged tetracarboxylic acid ligand, 5-(3′,4′-Dicarboxylphenoxy)-isophthalic acid (H₄L) was used to construct two Co(II) coordination polymers in presence of different nitrogen donor ligands such as 4,4′-bipyridine (4,4′-bpy) and 4,4′-bis(pyrid-4-yl)biphenyl (bpbp). The products formed under hydrothermal conditions are formulated as [Co₂L(4,4′-bpy)₂(H₂O)₃]_n (1) and {[Co(bpbp)₂(H₂L)]·H₂O}_n (2). The compounds were characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis, and powder X-ray diffraction (PXRD) measurement. Compound 1 shows an intriguing (3,4,5)-connected 3D framework with a point symbol of (4² · 6² · 8²)(4² · 6⁵ · 8³)(6² · 8). Compound 2 is an unusual 3D supramolecular framework generated by the one-dimensional [Co(bpbp)(H₂L)]_n polymer chain. The magnetic properties of compounds 1 and 2 were examined, indicating antiferromagnetic interactions between the cobalt(II) ions in the temperature range of 2–300 K.