Two cobalt complexes derived from 1H-1,2,3-triazole-4,5-dicarboxylic acid: Syntheses,structures and magnetic properties

Two cobalt(II) homometallic complexes, [Co₂(HTDA)₂(H₂O)₆·2H₂O] (1) and {[Co₃(TDA)₂(H₂O)₈]·H₂O}_n (2) (H₃TDA = 1H-1,2,3-triazole-4,5-dicarboxylic acid) have been synthesized and structurally characterized in detail. Single-crystal X-ray crystallographic study reveals that they crystallize in trigonal space group R-3 and orthorhombic space group Pna2₁, respectively. In 1, two Co^2 + cations are bonded by two HTDA^2 − ligands to generate a binuclear Co^II unit, which can further be extended to a 3D supermolecular structure via the hydrogen bonds. At variance with 1, the nearest Co^2 + cations of 2 are connected via TDA^3 − ligands to form a 1D coordination polymer and can be further linked to each other to result in a 3D supermolecular framework through the hydrogen bonding interactions as well. The magnetic properties of them were studied in detail.     

A new 3D pillared-layer porous framework with intersecting open channels in the Co/triazolate/carboxylate system: Synthesis,structure and magnetism

A new Co(II) coordination polymer, namely [Co₆(btc)₄(dtb)₂(H₂O)₃]_n (1) (H₃btc = 1,3,5-benzenetricarboxylic acid, dtb = 1,3-di-(1,2,4-triazole-4-yl)benzene), has been synthesized by combining the mixed ligands of H₃btc and dtb with Co(Ac)₂·4H₂O under solvothermal conditions. Single-crystal X-ray diffraction analysis reveals that 1 feature a 3D open framework with intersecting channels based on Co-btc^3 − layers and btc^3 − and dtb pillars. The magnetic property of the complex has also been investigated at room temperature.     

Hydrothermal synthesis,characterization and magnetic properties of a new 2D arsenic–vanadate layers supported cobalt coordination complex: [Co(en)2(H2O)]{[Co(en)2]2As8V14O42(SO4)} · 3H2O

The title compound [Co(en)₂(H₂O)]{[Co(en)₂]₂As₈V₁₄O₄₂(SO₄)} · 3H₂O (1) (en = ethylenediamine) has been hydrothermally synthesized and characterized by single crystal X-ray diffraction, IR spectrum and thermogravimetric analysis. The single crystal diffraction analysis shows that compound 1 exhibits {[Co(en)₂]₂As₈V₁₄O₄₂(SO₄)}n²ⁿ⁻ layers act as ligand of coordination cations [Co(en)₂]²⁺, and water molecules are inserted in the layers. The magnetic measurement indicates a weak antiferromagnetic exchange coupling within the molecular unit, which is deemed to attribute to the contribution of V^iv and Co²⁺.     

Three cobalt (II) complexes with triethylenetetraaminehexaacetic acid: From binuclear complex to 3d-4f coordination polymers

The cobalt(II)–lanthanide(III) heteronuclear complexes [Ln(H₂O)₄Co₂(TTHA)(SCN)₂]·H₃O⁺ (H₆TTHA = triethylenetetraaminehexaacetic acid, Ln = La(2), Ce(3)) have been synthesized based on a binuclear building block of [Co₂(H₂TTHA)(H₂O)₂] in [Co₂(H₂TTHA)(H₂O)₂]·4H₂O (1). Single-crystal structures show that complex 1 is a binuclear complex, containing the [Co₂(H₂TTHA)(H₂O)₂] unit as a useful building block. Adding the La^3 + and Ce^3 + ions to this synthesis system, two new 3d-4f mixed complexes 2 and 3 were obtained. Complexes 2 and 3 show 3D framework, comprising an infinite 1D (one-dimensional) chain based on heterometallic Ln₂Co₂ (Ln = La(2), Ce(3)). Further investigations such as IR spectra, UV–vis spectra, TGA, XRD and magnetic properties were studied.     

A novel three-dimensional coordination polymer containing tetranuclear [Co4(μ3-OH)2] building blocks: Synthesis,crystal structure and magnetic behavior of {[Co2(btc)(μ3-OH)(H2O)2] · H2O}n

A cobalt coordination polymer {[Co₂(btc)(μ₃-OH)(H₂O)₂] · H₂O}_n 1 (btc = 1,2,4-benzenetricarboxylate) was synthesized hydrothermally and structurally characterized by single-crystal X-ray diffraction method. In 1, the six-coordinated Co(II) ions are held together by two bridging hydroxides to form a tetranuclear [Co₄(μ₃-OH)₂] unit, which are connected further through btc³⁻ ligands in a new μ₇-bridging mode to give a porous three dimensional framework. The study of magnetic properties indicated dominant antiferromagnetic coupling interactions between the adjacent Co(II) sites.     

Synthesis,structural characterization and properties of a novel 1D helical chain arsenomolybdate {[Cu(en)2][Cu(en)(H2O)][(Cu(en)2(H2O)] [AsIIIAsVMo9O34)]} · 2H2O

An organic–inorganic hybrid 1D helical chain arsenomolybdate {[Cu(en)₂][Cu(en)(H₂O)][(Cu(en)₂(H₂O)] [As^IIIAs^VMo₉O₃₄)]} · 2H₂O (1) (en = ethylenediamine) has been hydrothermally synthesized and characterized by elemental analyses, IR, UV and CD spectrum, powder X-ray diffraction, TG-DTA and single-crystal X-ray diffraction. The asymmetric unit of 1 consists of a monocapped trivacant Keggin [As^IIIAs^VMo₉O₃₄]^6 − subunit, a pendant [Cu(en)₂(H₂O)]^2 + cation, a pendant [Cu(en)(H₂O)]^2 + cation, one bridging [Cu(en)₂]^2 + cation and two lattice water molecules. It should be noted that 1 illustrates a one-dimensional (1D) helical chain assembled by {[Cu(en)(H₂O)][(Cu(en)₂(H₂O)][As^IIIAs^VMo₉O₃₄)]}^2 − clusters and [Cu(en)₂]^2 + linkers.     

Hydrothermal syntheses and characterization of a series of mixed-ligand luminescent CdII frameworks with novel 2-(3-(pyridin-2-yl)-1H-pyrazol-1-yl) acetate ligand and benzenedicarboxylate isomers

Under similar hydrothermal synthetic conditions using a novel flexible ligand 2-(3-(pyridin-2-yl)-1H-pyrazol-1-yl)acetonitrile (PPAN), benzenedicarboxylate isomers (H₂pa = phthalate, H₂ip = isophthalate, and H₂tp = terephthalate) and Cadmium(II) acetate, three novel mixed-ligand Cd(II) coordination polymers {[Cd₂(PPAA)₂(μ-pa)(H₂O)]·2H₂O}_n (1), {[Cd₄(PPAA)₄ (μ₄-ip)₂]·2H₂O}_n (2) and {[Cd₂(PPAA)₂(μ-tp)]·2H₂O}_n (3) (PPAA⁻ = 2-(3-(pyridin-2-yl)-1H-pyrazol-1-yl) acetate) have been isolated, in 1–3 PPAN, and are also hydrolyzed into a novel PPAA⁻ ligand. Complex 1 is a 1D coordination polymer in which the tetra-nuclear [Cd₄(PPAA)₄]^4 + structural units are extended by tri-dentate μ-pa^2 − ligands. Complex 2 contains binuclear [Cd₂(PPAA)₂]^4 + structural units, which are extended by four tetra-dentate μ₄-ip^2 − ligands to link eight neighboring binuclear [Cd₂(PPAA)₂]^4 + units ultimately forming a 2D layered framework, while complex 3 contains 1D double chain containing [Cd(PPAA)]_n cation structural units, which are further extended by tetradentate μ-tp^2 − ligands to form a new 2D layered framework. All the complexes have been investigated by elemental analysis, FT-IR, thermal analysis and fluorescence characterization. The flexible coordination modes of PPAA⁻ are also briefly analyzed. The flexible coordination modes of PPAA⁻ and benzenedicarboxylate isomers also reveal great potential in the construction of these novel mixed-ligand luminescent frameworks with diverse structural motifs and unique functional properties.     

Six isostructural lanthanide-containing MOFs built on a semi-rigid tripodal organic ligand

By using a semi-rigid tripodal ligand 1,1′,1′′-(2,4,6-trimethylbenzene-1,3,5-triyl)tris(methylene)tripyridinium-4-olate) (L), six isomorphous lanthanum metal-organic frameworks (MOFs), namely, [Pr(L)₂(Cl)₂]·(Cl)(DMF)_0.5·(H₂O)·(1), [Nd(L)₂(Cl)₂]·(Cl)(2), [Tb(L)₂(Cl)₂]·(Cl)·(DMF)·(H₂O)(3), [Eu(L)₂(Cl)₂]·(Cl)(DMF)·(H₂O)(4), [La(L)₂(Cl)₂]·(Cl)(5), [Sm(L)₂(Cl)₂]·(Cl) (DMF)·(H₂O) (6), were obtained and characterized by single crystal X-ray diffraction, IR and elemental analysis. Six compounds are isostructural with Ln^3 + (Ln = Pr, Nd, Tb, Eu, La, Sm) and in which the Ln^3 + is considered as a 6-connecting node and the L ligand is a 3-connecting node to afford a (3,6)-connected 2D layer with kgd topology, which further stacks into 3D supramolecular networks through C-H^…O weak interactions. Luminescent properties of these lanthanide MOFs have also been assessed at ambient temperature, in which the Pr^3 +-1 and the La^3 +-5 are slightly blue-shifted with respect to the ligand. Series of sharp peaks characteristic of the Eu^3 +-4, the Tb^3 +-3 and Sm^3 + − 6 metal-centered luminescence appear. The Nd^3 +-2 has no emission.     

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.     

Syntheses,structural characterization and electrochemical properties of two rare-earth–isonicotinic-acid containing silicomolybdates

Two rare-earth–isonicotinic-acid containing silicomolybdates [NH₄]₆[RE(INA)₂(HINA)(H₂O)₃]₂[α-SiMo₁₂O₄₀]₂·6H₂O [RE = Nd^III (1), Er^III (2); HINA = isonicotinic acid] have been synthesized in the conventional aqueous solution and characterized by elemental analyses, IR spectra, UV spectra and single-crystal X-ray diffraction. Both 1 and 2 crystallize in the triclinic P–1 space group and consist of two typical Keggin [α-SiMo₁₂O₄₀]^4 − polyanions, one isolated rare-earth-isonicotinic-acid [RE(INA)₂(HINA)(H₂O)₃]₂^2 + dimeric complex cation, six NH₄⁺ ions and six lattice water molecules. Interestingly, two rare-earth ions are linked by four INA⁻ ligands in the [Ln(INA)₂(HINA)(H₂O)₃]₂^2 + complex cation, which is very rare in polyoxometalate chemistry. The UV spectral measurements of 1 indicate that 1 is stable in aqueous solution in the pH range of 4.49–9.39. Furthermore, the electrochemical and electrocatalytic properties of 1 have been measured by cyclic voltammetry in 0.5 mol·L^− 1 Na₂SO₄ + H₂SO₄ aqueous solution at the scan rate of 100 mV·s^− 1.     

A new cadmium-organic framework fluorescent sensor for Al3 + and Ca2 + ions in aqueous medium

A new metal-organic framework (MOF), [Cd₂(bptc)(HCOO)]·NH₂(CH₃)₂·3H₂O (1), where H₄bptc = 3,3′,5,5′-biphenyltetracarboxylic acid, was obtained by solvothermal reaction. The topology of MOF 1 is a (5,8)-connected net with {4¹⁶ · 5⁸ · 6⁴}{4⁴ · 5⁶}₂ point symbol. MOF 1 shows high stability in aqueous solution. Luminescence study indicates that MOF 1 possesses selective turn-on luminescent sensing functions towards Al^3 + and Ca^2 + ions in aqueous solutions.     

Syntheses,structures and properties of a series of 3s–5d–4f mixed metal substituted sandwich-type arsenotungstates

A class of 3s–5d–4f mixed metal substituted sandwich-type arsenotungstates [H₂N(CH₃)₂]₈H₃[LnNa(H₂O)₄(OH)WO(H₂O) (B-α-AsW₉ O₃₃)₂]·8H₂O [Ln = La^III (1), Ce^III (2), Pr^III (3)] have been isolated from an aqueous solution reaction system (pH = 4) of Na₂WO₄·2H₂O, C₂H₇N·HCl, NaAsO₂ and Ln(NO₃)₃·6H₂O and structurally characterized by elemental analyses, IR spectra, UV spectra and single-crystal X-ray diffraction. It is the most prominent in 1–3 that the [LnNa(H₂O)₄(OH) WO(H₂O)(B-α-AsW₉O₃₃)₂]^11 − polyanion consists of two trivacant Keggin [B-α-AsW₉O₃₃]^9 − moieties linked by one [WO(H₂O)]^4 + group and a dimeric [LnNa(H₂O)₄(OH)]^3 + group resulting in the special 3s–5d–4f mixed metal substituted sandwich-type assembly. Interestingly, lanthanide and sodium ions simultaneously occupy the two positions located at the central belt of 1–3 with the site occupancy of 50% for each position. Moreover, the electrochemical and electrocatalytic properties of only 1 and 2 have been measured by cyclic voltammetry (CV) in 0.5 mol·L^− 1 Na₂SO₄ + H₂SO₄ aqueous solution. 1 and 2 illustrate electrocatalytic activities for the hydrogen peroxide reduction.     

Syntheses,crystal structures and luminescent investigations of cobalt(II) and zinc(II) complexes with 2-propyl-4,5-dicarboxylate-imidazole (H3PIDC)

Presented in this communication are four metal complexes based on 2-propyl-4,5-dicarboxylate-imidazole (H₃PIDC), including two Co(II) coordination compounds, [Co(H₂PIDC)₂(H₂O)₂] · 4H₂O (1) and 2[Co(H₂PIDC)₂(H₂O)₂] · 5H₂O (2), as well as two Zn(II) coordination compounds, [Zn(H₂PIDC)₂(H₂O)₂] · 4H₂O (3) and 2[Zn(H₂PIDC)₂(H₂O)₂] · 7H₂O (4). They contain the same coordinated unit of [M(H₂PIDC)₂(H₂O)₂] (M = Zn or Co). Interestingly, among these four complexes, 1 and 2, or 3 and 4 crystallized in different space group, which may be related with the number of the crystallized H₂O molecules.     

A unique 3D Co(II)-MOF based on [Co6(μ3-OH)4]8 +n chains: Synthesis,crystal structure,and magnetic property

A novel metal-organic framework, [Co₆(μ₃-OH)₄(ndc)₄(bip)₂(H₂O)₂]_n (1)[H₂ ndc = 1,4-naphthalenedicarboxylic acid, bip = 1,5-bis(imidazole-1-yl)pentane], constructed from unique [Co₆(μ₃-OH)₄]^8 +_n chains containing alternate [Co₄(OH)₂]^6 + and [Co₂(OH)₂]^2 + subunits, was reported, which has a new (3,3,8,12)-connected or 12-connented fcu/cubic network and shows weak antiferromagnetic interaction between the adjacent Co(II) ions mediated through the carboxylate and hydroxyl groups.     

Syntheses,structures and properties of two copper-2-picolinic-acid germanomolybdate hybrids with mixed organic components

Two inorganic–organic hybrids based on saturated α-Keggin-type germanomolybdates with mixed organic components [H₂DAP]₂[Cu(PA)₂][α-GeMo₁₂O₄₀]·8H₂O (1) and [NH₄]₂[H₈L] [Cu(PA)₂][α-GeMo₁₂O₄₀]·8H₂O (2) (DAP = 1.2-diaminopropane, HPA = 2-picolinic acid, H₆L = 1,3-bis[tris(hydroxymethyl)methylamino]propane) have been obtained via the conventional aqueous solution method and structurally characterized by elemental analysis, IR spectra, thermogravimetric (TG) analysis and single-crystal X-ray diffraction. 1 stands for an one-dimensional linear organic–inorganic hybrid germanomolybdate chain constructed from classical Keggin [α-GeMo₁₂O₄₀]^4 − units supported by [Cu(PA)₂] linkers, whereas 2 represents the first hybrid germanomolybdate containing the H₆L component and consists of a saturated α-Keggin polyanion [α-GeMo₁₂O₄₀]^4 −, a diprotonated [H₈L]^2 + cation, a copper coordination complex [Cu(PA)₂], two ammonium cations [NH₄]⁺ and eight lattice water molecules. Furthermore, the electrochemical and electrocatalytic properties of 1 and 2 have also been investigated in detail.     

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.     

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.     

A cyanide-bridged two-dimensional grid-like FeIII–CoII complex based on the pentacyanideferrite(III) building block

A cyanide-bridged Fe^III–Co^II heterometallic complex {[Fe(1-CH₃im)(CN)₅][Co(H₂O)₂]}n·3H₂O (1-CH₃im = 1-methylimadazole) (2) has been synthesized by the reaction of Co^II(ClO₄)₂·6H₂O with the pentacyanideferrite(III) building block (Ph₄P)₂[Fe^III(1-CH₃im)(CN)₅]·4.5H₂O (1). X-Ray single crystal diffraction analysis shows that complex 2 has a two-dimensional (2D) grid-like structure. Magnetic investigations show that complex 2 displays long-range antiferromagnetic ordering with T_N = 9.45 K. The typical metamagnetic behaviors were observed with the critical field of ca. 4000 Oe at 1.82 K.     

One novel 3D tetranuclear cadmium coordination polymer based on 2,3′,4,5′-biphenyltetracarboxylic acid: Synthesis,crystal structure and luminescence

One novel 3D cadmium coordination polymer, namely, {[Cd₂(bptc^4 −)(ox^2 −)_0.5(H₂O)₂] · 4.5H₂O}_n (1), has been hydrothermally synthesized through a reaction of 2,3′,4,5′-biphenyltetracarboxylic acid (H₄bptc) with divalent cadmium salt in the presence of a second ligand (ox = oxalic acid). X-ray single crystal structure analysis reveals that tetranuclear cadmium clusters are formed by linking two Cd1 and two Cd2 ions with carboxyl groups. Each ox^2 − ligand, with a bidentate chelating mode, connects two Cd2 ions from two adjacent tetranuclear clusters to afford 1D zigzag cadmium cluster chains. Furthermore, 1D chains are connected by bptc^4 − ligands to extend a 3D framework with one-dimensional channels along the [001] direction. From a topology view, complex 1 exhibits an unprecedented 2-nodal 4, 10-connected net with the Schläfli symbol of {4⁶}₂{4⁹. 5¹².6²².7²}. The luminescence analyses reveal that complex 1 shows an emission maximum at 437 nm, which may be attributed to the intra-ligand transition. A red shift of 31 nm compared with H₄bptc ligand was observed and the luminescent decay lifetime is 2.74 ns, which indicates that it might be a potential blue light-emitting candidate. In addition, it was also characterized by elemental, IR spectra, PXRD and TG analyses.     

A novel Dawson-like cerium(IV)-hybridizing selenotungstate Na13H7[Ce(SeW17O59)2]·31H2O

A novel cerium(IV)-hybridizing selenotungstate with Dawson-like structure Na₁₃H₇[Ce(SeW₁₇O₅₉)₂]·31H₂O (1) has been synthesized by reaction of Na₂WO₄·2H₂O, Na₂SeO₃ and (NH₄)₂Ce(NO₃)₆ in the aqueous solution and characterized by elemental analysis, IR spectrum, UV spectrum, thermogravimetric analysis (TGA) and single-crystal X-ray diffraction. To the best of our knowledge, 1 stands for 1:2-type Dawson-like selenotungstate constructed from two identical [SeW₁₇O₅₉]^12 − moieties combined via one Ce^4 + ion. The Ce^4 + cation displays a distorted square prismatic geometry defined by eight oxygen atoms from two [SeW₁₇O₅₉]^12 − moieties. In the [Ce(SeW₁₇O₅₉)₂]^20 − polyoxoanion, the {SeO₃} trigonal pyramid encapsulated into the [SeW₁₇O₅₉]^12 − fragment is situated on the side close to the Ce^4 + ion. The TGA curve of 1 reveals two steps of weight loss between 25 °C and 700 °C. Furthermore, the electrochemical and the electrocatalytic properties of 1 have been measured by cyclic voltammetry (CV) in 0.5 M Na₂SO₄ + H₂SO₄ aqueous solution.