Two isostructural Ni(Ⅱ)/Co(Ⅱ)-based metal-organic frameworks for selective dye adsorption and catalytic cycloaddition of CO2 with epoxides

Two isostructu ral Ni(Ⅱ)/Co(Ⅱ)-based metal-organic frameworks(MOFs),namely {[M₃(L)₂(bpb)₃(H₂ O)₄]·2 DMF·2 H₂O}_n [M=Ni(HL-5,HL is short for Hui-Ling Liu);M=Co(HL-6);H₃ L=2',6'-dimethyl-[1,1'-biphenyl]-3,4',5-tricarboxylic acid;bpb=1,4-bis(pyrid-4-yl)benzene],have been hydrothermally synthesized and structu rally characterized.Both HL-5 and HL-6,which have the same three-interpenetrated3 D pillared-layer framework with sqc306 type topology,present good selective methyl orange(MO)adsorption over rhodamine B(RhB).Moreover,the catalytic CO₂ cycloaddition properties with epoxides of the two MOFs have also been studied at ambient pressure and temperature.     

Carboxylate-induced Various Structures of Ni(II) Complexes with Fluorescence Sensing and Bifunctional Electrochemical Properties

We synthesized three new Ni(II) coordination polymers [Ni(LXHLPXH2O)2]- H2O(CP1),[Ni(LXNIP)]-2H2O(CP2) and [Ni(LXNDCXH20)2](CP3)[L=N,N′-bis(pyridme-3-yl)thiophene-2,5-dicarboxamide, H2HIP=5-hydroxyisophthalic acid, H2NIP=5-nitroisophthalic acid, H2NDC=2,6-naphthalenedicarboxylie acid] by hydrothermal method, which were characterized by means of infrared spectra(IR), TG analyses, PXRD and single-crystal X-ray diffraction. The CPI is a ID tubular structure based on [Ni-HIP]2 loops and pairs of L ligands. CP2 is a 2D 3,5-connected architecture, which consists of Ni-L linear chains and (Ni-NIP)2 double chains. CP3 is a 2D network, which features 4-connected topology. Solid-state luminescent behaviours of CP-P3 were investigated. The CPI can detect Fe^3+ ions through luminescence quenching. The electrochemical properties of CPI buk-modified carbon paste electrode(CP1-CPE) has also been investigated, which has bifunctional electrocatalytic activity for oxidation of ascorbic acid and reduction of NO2^-.     

Two Zinc(Ⅱ) Complexes Based on 7rany-(1R,2R)-cyclohexanediamine: Molecular Structure Analyses and Preparation of Composite Membrane

Two novel complexes Zn2(chda)2(TPA)Cl2(1) and [Zn(chda)2(H2O)2](TPAXH2O)2(2)[chda is a chiral ligand of trans-(1R,2R)-cyclohexanediamine, H2TPA is terephthalic acid] were synthesized at room temperature. The molecular structures of complexes 1 and 2 were identified by single-crystal X-ray diffraction measurement. The results showed that complex 1 had a binuclear structure, each Zn(Ⅱ) ion was four coordinated by two N atoms of chda, one O atom of TPA and one Cl atom, to construct a distorted tetrahedral geometry. For complex 2, the Zn(Ⅱ) ion was six coordinated by two chda molecules and two water molecules to form a ZnN4O2 octahedral geometry. Complexes 1 and 2 further extended into three-dimensional supramolecular frameworks by hydrogen-bonding interactions. Hirshfeld surface analysis and fingerprint plots were used to further analyze the contribution of diflerent intermolecular interactions. Further, a composite membrane [Zn(chda)2(H2O)2](TPA)(H2O)2/CA was prepared by adding 10%(mass fraction) of complex 2 into cellulose acetate using acetone/chloroform( V:V-1:1) as solvent.     

Noncentrosymmetric K2Mn3(SO4)3F2·4H2O and Rb2Mn3(SO4)3F2·2H2O with pseudo-KTP structures

Two fluoride sulfates,K₂Mn₃(SO₄)₃F₂·4H₂O(Ⅰ) and Rb₂Mn₃(SO₄)₃F₂·2H₂O (Ⅱ) are obtained by water solution method.Single-crystal X-ray diffraction analysis indicated that they crystallize in space groups of Cmc2_1.Their structures feature a pseudo-KTP structure consisting of interconnecting[Mn₃(SO₄)3F₂(H₂O)2]_∞ layers,which are further packing along the a axis with alkali metal cations balancing the charges.The structure relationships between the two compounds are discussed.Secondharmonic generation measurements manifest that Ⅰ and Ⅱ have similar second-harmonic generation responses of about 0.2 and 0.25 times that of KH₂PO₄.     

Two New Alkaline Metal Borates with Supramolecular Framework Constructed from 1D {B5}/{B6} Helical Chains

Two new alkaline metal borates containing 1D{B5}/{B6}oxoboron helical chains,namely Na0.5[B5O8(OH)2]0.5[B5O6(OH)2]0.5·0.5H3O(1)and NaKCs[B6O9(OH)3](2)were synthesized under solvothermal conditions.Compound 1 contains the interesting alternative left-and right-handed helical{[B5O8(OH)2][B5O6(OH)2]}2-({B5}-1 and{B5}-2)1D chains and compound 2 possesses the similar[B6O11(OH)3]7-({B6})chains.Their 1D chains are further assembled into 2D layers and 3D supramolecular frameworks through O-H…O hydrogen bonds.In addition,the UV cutoff edge of compounds 1 and 2 is both below 190 nm.     

Multi-functional Photoelectric Sensor Based on a Three-fold Interpenetrated Cd(II) Coordination Polymer for Sensitively Detecting Different Ions

Athree-fold interpenetrated cadmium coordination polymer[Cd₃(BTC)₂(H₂O)₉]·2H₂O(CP 1)(H₃BTC=1,3,5-benzenetricar-boxylic acid) was selected and synthesized to investigate its photoelectric properties. CP 1 showed excellent sensitivity for Cr₂O₇^2- and Fe³⁺, low limit of detection(LOD:0.39 µmol/L for Cr₂O₇^2- and 1.72 µmol/L for Fe³⁺) and stability as electrochemical sensor. More importantly, fluorescence sensing studies indicated that CP 1 exhibits sensing activity for Fe³⁺, Fe²⁺, and MnO₄^- with good cyclic stability and selectivity. Low LOD and high-sensitivity capability of CP 1 make it a potential multifunctional photoelectric sensor.     

Two New Borates Built by Different Types of {B9} Cluster Units

Two new belt-like borates Na₄[B₉O₁₄(OH)₃]·0.5H₂O(1) and Na₅[B₉O₁₄(OH)₄](2) have been synthesized under solvothermal conditions. Both compounds contain unprecedented B₉O₁₆(OH)_n^(n+5)-[n=3(1), 4(2)] clusters, which are constructed from four B₃O₃ rings via three BO₄ tetrahedra. Compound 1 exhibits a rare 1D belt with two types of 8-membered ring(MR) windows based on B₉O₁₆(OH)₃^8- clusters. Compound 2 features two different 1D belts built by different B₉O₁₆(OH)₄^9- units, which is first discovered in borate family. UV-Vis diffuse reflectance spectra reveal that compounds 1 and 2 have the cut-off edges below 190 nm, indicating that they may have potential application in deep UV(DUV) region.     

A New Tubular Borate Built by[B14O24(OH) 6]12- Cluster Units

Anew mixed alkali and alkaline-earth metal borate Na₄Ca₂[B₁₄O₂₂(OH)₆]·2H₂O(1) has been made under a mild solvothermal condition and characterized by single-crystal X-ray diffraction, infrared(IR) spectroscopy, UV-Vis diffuse reflectance spectroscopy, powder X-ray diffraction and thermogravimetric analysis, respectively. Compound 1 features a 1D tube based on[B₁₄O₂₄(OH)₆]^12-({B₁₄}-1) oxo-boron clusters. Such a tube built by {B₁₄}-1 units has been discovered for the first time in borate system. These tubes are arranged orderly to generate 2D layers and a further 3D supramolecular network through hydrogen bond interactions. UV-Vis diffuse reflectance spectrum reveals that compound 1 is a wide band-gap semiconductor and has potential application in UV region.     

Hydrothermal synthesis, crystal structure and characterization of [Zn(H2O)4]2 [H2As6V15O42(H2O)]·2H2O

The compound [Zn(H₂O)₄]₂[H₂As₆V₁₅O₄₂(H₂O)]·2H₂O (1) has been synthesized and characterized by elemental analysis, IR, ESR, magnetic measurement, third-order nonlinear property study and single crystal X-ray diffraction analysis. The compound 1 crystallizes in trigonal space group R3, a=b=12.0601(17) Å, c=33.970(7) Å, γ=120°, V=4278.8(12) Å³, Z=3 and R1(wR2)=0.0512 (0.1171). The crystal structure is constructed from [H₂As₆V₁₅O₄₂(H₂O)]⁴⁻ anions and [Zn(H₂O)₄]²⁺ cations linked through hydrogen bonds into a network. The [H₂As₆V₁₅O₄₂(H₂O)]⁶⁻ cluster consists of 15 VO₅ square pyramids linked by three As₂O₅ handle-like units.     

Assembly of Three Scandium-containing Heteropolytungstates Based on a Building-block Synthetic Strategy

Three novel scandium-containing heteropolytungstates[Sc₃(H₂O)₃NO₃(PW₉O₃₄)₂]^10-(1a),[Sc₈(H₂O)₂(GeW₉O₃₄)₂(GeW₆O₂₆)₂]^12-(2a) and[Sc₁₁(W₆O₁₀)₂(OH)₂(H₂O)₁₆(BiW₉O₃₃)₆]^27-(3a) were synthesized by reactions of Sc^III ions with trilacunary Keggin precursors,[A-α-XW₉O₃₄]^n-(X=P, Ge, n=9, 10) or[B-α-BiW₉O₃₃]^9-, in NaOAc/HOAc buffer solution under conventional synthetic condition, respectively. All the three compounds were characterized by means of single-crystal X-ray diffraction(XRD), Fourier transform-infrared(FTIR) spectroscopy ultraviolet-visible(UV-Vis) spectroscopy, elemental analysis, and thermogravimetric analysis. The aqueous solution stability of the sandwich polyanion[Sc₃(H₂O)₃NO₃(PW₉O₃₄)₂]^10- was also verified by electrospray ionization mass spectrometry(ESI-MS) due to its good solubility in water.     

Large heteropolymetalate complexes formed from lanthanide (Y, Ce, Pr, Nd, Sm, Eu, Gd), nickel cations and cryptate [As4W40O140]: synthesis and structure characterization

A new family of heteropolytungstate complexes (NH₄)₂₁[Ln(H₂O)₅{Ni(H₂O)}₂As₄W₄₀O₁₄₀]·xH₂O(Ln=Y, Ce, Pr, Nd, Sm, Eu, Gd) were prepared by the reaction of Na₂₇[NaAs₄W₄₀O₁₄₀]·60H₂O with NiCl₂·6H₂O and Ln(NO₃)₃·xH₂O at pH≈4.5. The crystal structures of (NH₄)₂₁[Gd(H₂O)₅{Ni(H₂O)}₂As₄W₄₀O₁₄₀]·51H₂O was determined by X-ray diffraction analysis and element analysis. The compound crystallizes in the monoclinic space group P2₁/n with a=19.754(3), b=24.298(4), c=39.350(6) Å, β=100.612(3)°, V=18564(5) ų, Z=2, R1(wR₂)=0.0544(0.0691). The central site S1 and two opposite sites S2 of the big cyclic ligand [As₄W₄₀O₁₄₀]²⁸⁻ are occupied by one Ln³⁺and two Ni²⁺, respectively, each site supply four O_d coordinating to metal ion, another one water molecule and other five water molecules coordinate, respectively, to Ni²⁺and Ln³⁺. Polyanion [Ln(H₂O)₅{Ni(H₂O)}₂As₄W₄₀O₁₄₀]²¹⁻ has C_2v symmetry. IR and UV–vis spectra of [NaAs₄W₄₀O₁₄₀]²⁷⁻ of the title compounds are discussed.     

Coordination Polymers with Bipyridyl Diene and Triene Ligands: Synthesis,Structures and Luminescent Properties

Solvothermal reactions of cadmium salts with bipyridyl diene and triene ligands[1,3-bis((E)-2-(pyridin-4-yl)vinyl)benzene-(1,3-bpeb) and 1,6-bis(4-pyridyl)-1,3,5-hexatriene(bphte)] and one bipyridyl triene ligand[1,6-bis(4-pyridyl)-1,3,5-hexatriene-(bphte)] in the presence of auxiliary carboxylic acids including 2,6-dichlorobenzoic acid(2,6-HDCBA) and 2-naphthal-enecarboxylic acid(2-HNCA) gave rise to four coordination polymers[Cd(bphte)(2,6-DCBA)₂]_n(1), {[Cd(bphte)(2-NCA)₂]·5.8H₂O}_n(2),[Cd₂(1,3-bpeb)₂(2,6-DCBA)₄]_n(3) and {[Cd₄(1,3-bpeb)₄(2-NCA)₇(HCOO)]·     

A new extended structural compound based on saturated Wells-Dawson polyoxoanions

A new 3D extended structural compound,(dpdo)_2H_2{[Cu(2,2'-bipy)_2]_2(P_2W_(18)O_(62))}·5H_2O 1(dpdo = 4,4'-bipyridine-N,N'-dioxide; 2,2'-bipy = 2,2'-bipyridine),has been hydrothermally synthesized and characterized by elemental analyses,IR,TG analyses,cyclic voltammetry,and single-crystal X-ray diffraction.Compound 1 is built up of[P_2W_(18)O_(62)]~(6-) cluster as the structural motif covalently linked by[Cu(2,2'-bipy)_2]~(2+) coordination complexes to yield the 1D chains,which are further in close cont...     

新型磷-钒-氧层状化合物[H2en]2[H3O]6[Co(H2O)2(VO)8(OH)4(PO4)8]的水热合成与晶体结构

金属磷酸盐材料在吸附、离子交换、离子传导和催化剂方面有潜在的应用前景[1～5]. 近年来, 通过水热反应合成了一些A-V-P-O化合物. 在这些化合物中, A一般为碱金属或有机阳离子, 如层状结构的[H2N(C4H8)2NH2][(VO)4(OH)4(PO4)2][6] 和[H2N(C2H4)3NH2][(VO)8(HPO4)3(PO4)4*(OH)2]*2H2O[6], 一维链状结构的 [H2NCH2CH2NH3(VO)(PO4)][7], 手性双螺旋结构的 [(CH3)2NH2]K4[(VO)10(H2O)2(OH)4(PO4)7]*H2O[8]以及具有三维骨架结构的化合物 [H3N(CH2)3NH3K(VO)3(PO4)3][9], [H3N(CH2)3NH3]2[V(H2O)2(VO)6(OH)2(HPO4)3(PO4)5]*3H2O[10]和[H3N(CH2)2NH3][(VO)3(H2O)2(PO4)2(HPO4)4][11].     

Formation of infinite 2D water layers in a crystal host

A self-assembled,(H_2O)_(38) cluster stabilized by a mono-nuclear copper(Ⅱ) complex 1 namely {[Cu(phen)_2(CO_3)]·7H_2O} is characterized by X-ray diffraction studies.The adjacent(H_2O)_(38) clusters connect together resulting in an infinite 2D water layer structure.The water morphology is stable at room temperature,but upon thermal decomposition,the water loss is irreversible.     

A Multifunctional {P2Mo5}-based Hybrid Applying to Catalysis,Electrocatalysis and Dye Adsorption

As a common environmental pollutant, thioether can cause serious environmental pollution, so selective oxidation of thioether has become one of the current research hotspots. In this paper, an inorganic-organic hybrid based on a Standberg-type polyoxometalate,[Hbiz]₅[HP₂Mo₅O₂₃]·5H₂O(1)(biz=benzimidazole), was obtained by adjusting pH under hydrothermal conditions. The structure was characterized by infrared spectroscopy, thermogravimetric analysis, and single-crystal X-ray diffraction. Compound 1 can be used as an excellent catalyst for the oxidation of thioanisole. The experimental results showed that thioanisole could be catalytically oxidized to methyl phenyl sulfoxide by compound 1 as a catalyst within 40 min. The conversion rate and selectivity reached 99%. Compound 1 had good cycling stability as a heterogeneous catalyst. In addition, the electrocatalytic reduction of H₂O₂ and Cr₂O₇^2‒ for hybrid 1 was preliminarily investigated. In addition, the adsorption performance of hybrid 1 on cationic dye crystal violet and methylene blue was tested, and the adsorption efficiencies can reach 98.5% and 86.3%, respectively.     

系列Sm3+配合物的合成、结构及光物理性能

采用水热方法合成了4种Sm³⁺配合物, 即{[SmZn(2,5-pdc)₂(tp)_0.5(H₂O)]·2H₂O}_n(1), [Sm₂Zn₂(C₆H₅COO)₁₀(Imh)₂(H₂O)₂](2), {[Sm₂(NO₂C₆H₄COO)₆(H₂O)₄]·H₂O}_n(3)和{[SmN(CH₂COO)₃(H₂O)₂]·H₂O}_n(4)[2,5-pdc=2,5-吡啶二羧酸根, tp=对苯二甲酸根, C₆H₅COO=苯甲酸根, Imh=咪唑, NO₂C₆H₄COO=对硝基苯甲酸根, N(CH₂COO)₃=氨三乙酸根]. 通过单晶X射线衍射确定了其晶体结构. 在室温下测定了其红外光谱、 紫外-可见-近红外光谱以及在近红外区和可见区的发射光谱. 结果表明, 4种配合物在近红外区或可见区均出现Sm³⁺离子的特征发射. 这是形成配合物后, Zn-配体部分和配体对Sm³⁺离子发光的敏化作用所致. 此外, 讨论了不同有机配体或d过渡金属离子对Sm³⁺离子发光的影响, 并分析了配合物中Sm³⁺离子的近红外发射带位移、 劈裂和加宽的原因.     

Hydrothermal synthesis, structural characterisation and magnetic behaviour of hybrid complexes of N-(phosphonomethyl)iminodiacetate

Two new compounds containing multidentate chelating organic residues of N-(phophonomethyl)iminodiacetic acid (H₄pmida), [M(pyr)(H₂O)₄][M₂(Hpmida)₂(pyr)(H₂O)₂]·2(H₂O) (where pyr=pyrazine and M=Co²⁺ or Ni²⁺ for I and II, respectively) have been synthesised and structurally characterised by single-crystal and powder X-ray diffraction, elemental analysis, infrared spectroscopy, thermal analysis and solid-state ³¹P MAS NMR. The compounds contain discrete binuclear anionic [M₂(Hpmida)₂(pyr)(H₂O)₂]²⁻ units in which one pyrazine ligand bridges two M²⁺ cations which are completely trapped inside three five-membered chelate rings formed by the Hpmida³⁻ ligands. These moieties close pack in the ac plane via a series of strong and highly directional O–HO hydrogen bonds leading to the formation of anionic layers. One-dimensional cationic coordination polymers are placed in-between and strongly hydrogen-bonded to these layers. The magnetic properties of these two materials are also reported.     

Dinuclear transition metal compounds of a decadentate pyrazole-containing chelating ligand. X-ray crystal structure of Co2(tthd)(ClO4)4(H2O)2(MeOH)1.75

A potentially decadentate ligand, 1,1,4,7,10,10-hexakis(3,5-dimethyl-1-pyrazolylmethyl)-1,4,7,10-tetraazadecane (tthd), has been synthesized from the reaction of tri-ethylenetetramine with six equivalents of N-hydroxymethyl-3,5-dimethylpyrazole. The tthd ligand forms coordination compounds, M₂(tthd)(ClO₄)₄(H₂O)_x, when M is Co, Ni, Cu, Zn and Cd and x = 4–8; and M₂(tthd)(A)₂(ClO₄)₂(H₂O)_x when M is Co and Ni, A is NCS or Cl, and x = 4–8. The cobalt compound, Co₂(tthd)(ClO₄)₂(H₂O)₂(MeOH)_1.75, crystallizes in the triclinic space group P1, a = 1.959(2), b = 1.5657(3), c = 2.1244(3) nm, = 105.5(1), β = 96.9(1), γ = 112.1(1). Due to severe disorder of the anions the structure could only be refined to an R_w, value of 0.099. The ligand acts as a decadentate, dinucleating ligand. The cobalt ions are distorted octahedrally surrounded by five N-atoms of the tthd ligand and an O-atom of water occupying the sixth coordination place. The other perchlorate compounds have very similar structures, as can be concluded from spectroscopic data.

In the thiocyanate and chloride compounds the anions have replaced the coordinated water molecules, resulting in octahedral Ni compounds. With Co thiocyanate, however, tthd acts as an octadentate ligand, resulting only in five-coordinated compounds.     

Controlling structural topology of metal-organic frameworks with a desymmetric 4-connected ligand through the design of metal-containing nodes

Two new metal-organic frameworks(MOFs),[Cu2(H_2O)_2(BCPIA)](BUT-20)and(Me_2NH_2)[In(BCPIA)](BUT-21)were designed and synthesized through the solvothermal reaction between a newly created desymmetric 4-connected ligand,5-(2,6-bis(4-carboxyphenyl)pyridin-4-yl)isophthalic acid(H_4BCPIA)and Cu(NO_3)2 2.5H_2O or In(NO_3)_3·5H_2O,respectively,and characterized by single-crystal and powder Xray diffraction,thermogravimetric analysis,infrared spectroscopy,and elemental analysis.The two MOFs have three-dimensional structures,in which both the BCPIA 4 ligand and metal-containing entities,Cu_2(COO)_4(H_2O)_2 and In(COO)_4 act as 4-connected nodes.However,different linkage configurations of the two metal-containing nodes,quadrilateral Cu_2_TD_2(COO)_4(H_2O)_2and tetrahedral In(COO)_4,lead to distinct structural networks of BUT-20 and 21,with Nbo and Unc topologies,respectively.