Structural Diversity and Photoluminescent Properties of Two Mn(Ⅱ) Sulfoterephthalate Complexes from Multi-pyridine N-containing Ligands

Solvothermal reaction of manganese(II) salt with monosodium 2-sulfoterephthalate(2-NaH_2stp) and two multi-pyridine N-containing auxiliary ligands results in the formation of two new complexes formulated with [Mn_2(Hstp)_2(bpp)_2(H_2O)_4](1) and [Mn_3(stp)_2(tpy)_3(H_2O)](H_2O)_5(2)(bpp = benz-2,3-pyrimidine-[2,3-f]-1,10-phenanthroline, tpy = 2,2?:6?,2??-terpyridine). X-ray diffraction structural analyses of two complexes reveal their structural diversity(0D and 1D) due to the difference of auxiliary ligands. 1 is a discrete structure, in which the Mn(Ⅱ) ion is hexa-coordinated with one stp, one bpp ligand and two water molecules. Complex 2 is a one-dimensional(1D) chain-like structure with three crystallographically independent Mn(Ⅱ) ions. The photoluminescent properties could be assigned to the π-π* transition of 2-sulfoterephthalate ligands.     

Impact of the flexibility of pillar linkers on the structure and CO_2 adsorption property of ‘‘pillar-layered' MOFs

A new metal–organic framework {[Zn_2(bpta)(bpy-ee)(H_2O)_2]·x solve}_n(1)(H_4bpta = biphenyl-2,20,6,60-tetracarboxylic acid and bpy-ee = 1,2-bis(4-pyridyl)ethylene) has been obtained under hydrothermal condition, and structurally characterized by single-crystal X-ray diffraction. Complex 1 reveals a threedimensional(3D) ‘‘pillar-layered' framework with non-flexible linker, in which some different structure characters can be found compared to that of some related other ‘‘pillar-layered' MOFs based on flexible pillar linkers. It demonstrates the impact of the flexibility of pillar linker on the final structure in this system. In addition, the selective CO_2 adsorption performance of 1 was also investigated.     

Synthesis,structure, and magnetism of three manganese-organic framework with PtS topology

Three 3D manganese-organic frameworks, Mn2(BPTC)(DMF)2(H2O)·DMF·3H2O(1), Mn2(BPTC)(bipy)(DMF)·DMF·H2O(2), and Mn2(BPTC)(phen)(DMF)·EtOH(3), have been solvothermally synthesized using 3,3′,5,5′-biphenyltetracarboxylic acid(H4BPTC). All complexes are characterized by PXRD, EA, IR and TG. The results show that they all bear the PtS topology with(42.84)(42.84) for the vertex symbols of the planar and tetrahedral nodes, in which the BPTC ligand is considered as a square-planar 4-connected linker, and every binuclear SBU connected to the four BPTC ligands is simplified into tetrahedral 4-connected nodes. Because the three coordination sites of one metal center of SBU are occupied by the coordinated solvent molecules, complex 1 exhibits low stability. After substituting 2,2′-bipy or 1,10-phen for two coordinated solvent molecules, complexes 2 and 3 display evidently higher structure stability. The magnetism property of complex 2 is also discussed in detail.     

Four Complexes of Mn(Ⅱ), Co(Ⅱ), Ni(Ⅱ) and Cu(Ⅱ) Based on 2-Morpholine-4-yl-4,6-di-pyrazol-1-yl-1,3,5-triazine

Three azide bridged complexes, namely, [Mn_2L_2(N_3)_4(H_2O)_2](1), [Co_2L_2(N_3)_4]·(H_2O)_3(2) and [Ni_2L_2(N_3)_3(H_2O)]N_3·(H_2O)_4(3)(L = 2-morpholine-4-yl-4,6-di-pyrazol-1-yl-1,3,5-triazine), were synthesized by the reaction of L ligand, sodium azide with Mn(Ⅱ), Co(Ⅱ) and Ni(Ⅱ) chlorides. The copper(Ⅱ) chloride combined with thiocyanate and L ligand to form a mononuclear complex [CuL(CH_3OH)(SCN)(NCS)](4). Complexes 1~4 were characterized by IR, elemental analysis and X-ray crystallographic analysis. It was worth noting that two Mn(Ⅱ) atoms were connected by the end-to-end mode in 1, while Co(Ⅱ) and Ni(Ⅱ) atoms were connected by the end-on mode in 2 and 3. In complex 4, the central copper atom was coordinated with a sulfur atom and a nitrogen atom of the two thiocyanate ligands, respectively. Hydrogen bonds, π-π stacking interactions, thermogravimetric analysis and fluorescence properties of 1~4 were studied.     

Combination of Lindqvist-type Tungstovanadates and Transition Metal Clusters under Hydrothermal Conditions

<正>Two novel organic-inorganic heteropolyoxometalate compounds [{Cu(1,10- phen)OH}_2]_2[V_2W_4O_19]·6H_2O (1) and [Co(1,10-phen)_3]_2[V_2W_4O_(19)]·5H_2O (2) (1,10-phen = 1,10- phenanthroline) were hydrothermally synthesized and characterized by elemental analysis, IR spectra and single-crystal X-ray diffraction. Compound 1 contains a di-V substituted classical Lindqvist-type polyanion [V_2W_4O_(19)]~(4-), two dinuclear copper cations [{Cu(1,10-phen)OH}_2]~(2+) and six water molecules of crystallization. Two dinuclear copper cations [{Cu(1,10-phen)OH}_2]~(2+) consist of four transition metal coordination cations {Cu(1,10-phen)}~(2+), bridged by four hydroxyl groups. Meanwhile, both two dinuclear cations are grafted on the Lindqvist polyanion [V_2W_4O_(19)]~(4-) through two terminal oxygen (O(9)) and two μ_2-oxygen (O(6)) atoms. Such an unusual linking fashion is unique in the polyoxometalate chemistry. The basic framework of 2 is similar to that of 1 and contains one Lindqvist-type polyanion [V_2W_4O_(19)]~(4-), two six-coordinated cobalt cations [Co(1,10-phen)_3]~(2+) and five free water molecules.     

Syntheses and Anti-lung Cancer Activities of Zn(Ⅱ) and Cu(Ⅱ) Complexes Based on Triazole and Tetrazole,respectively

The reactions of 4H-1,2,4-triazole(Htrz) with ZnCl_2, 1H-tetrazole(Htez) and Cu(NO_3)2·6H_2O afford two novel coordination polymers respectively, {[Zn_2(trz)_2(ox)](H_2O)_3}n(1) and {[Cu_3(tez)_3(OH)_2(H_2O)_2](NO_3)(DMF)_4}_n(2)(H_2ox =(COOH_)2, DMF = N,N-dimethylformamide). 1 shows 1D channels along the a axis filled with water molecules and 2 features a 2D bi-layered framework based on trinuclear Cu(II) units bridged by two μ3-OH groups. In addition, in vitro antitumor activities of compounds 1 and 2 on four human lung cancer cells(16HBE, NCI-H1299, NCI-H460 and NCI-H292) were further determined.     

One Novel Mn(Ⅱ) Complex with 1-Substituted-1H-1,2,3-triazole-4-carboxylic Acid:Crystal Structure,Fluorescence and Hirshfeld Surface Analysis

The crystal structure of one novel Mn(II) complex, [Mn(pmta)_3]_2[Mn(H_2O)_6]·4H_2O(1), is reported(Hpmta = 5-methyl-1-phenyl-1H-1,2,3-triazole-4-carboxylic acid). In the title compound, the asymmetric unit consists of a [Mn(pmta_)3]ˉ anion, half [Mn(H_2O)_6]~(2+) counter cation and two lattice H_2O molecules, and the intra- and intermolecular hydrogen bonds connect the complex into a supramolecular structure. The liquid-state fluorescence spectra of complex 1 have been determined. Hirshfeld surface analysis was also studied. The main intermolecular interactions in the complex are O···H and H···H contacts.     

Synthesis,Structure,and Spectroscopic Studies of a Chiral Supramolecular Complex with Excellent Semiconductor Property

A novel chiral copper(Ⅱ) complex with racemic 1,2-diaminocyclohexane and iodide,[Cu(Ⅱ)(1,2-diaminocyclohexane)_3](I)_2·3H_2O(1) has been synthesized and structurally characterized by X-ray single-crystal diffraction,elemental analysis,infrared spectroscopy,Raman spectroscopy and thermogravimetric analysis. In complex 1,the CuⅡ ion was coordinated by six nitrogen atoms of three 1,2-diaminocyclohexane molecules. The structure of complex 1 can be described as a supramolecular 3D-like structure which was formed by intermolecular hydrogen-bonding interactions between mononuclear molecules,uncoordinated water molecules and two iodide anions. UV-vis absorption spectrum and surface photovoltage properties of complex 1 have also been studied.     

A 3D Nickel(Ⅱ) Complex Constructed by Bis(2-dimethylaminoethyl) Ether: Solvothermal Synthesis,Crystal Structure and Catalytic Properties

Treatment of bis(2-dimethylaminoethyl) ether(BDMAE) with nickel acetate afforded a novel 3D nickel(Ⅱ) complex [Ni(BDMAE)(H_2O)_3·(CH_3COO)_2·(H_2O)_2] under solvothermal conditions. Its crystal structure was characterized by elemental analysis, IR spectrum, PXRD and single-crystal X-ray diffraction analysis. The complex belongs to the orthorhombic system, space group C2221 with a=8.823(2), b=13.932(3), c=17.563(4) ?, V=2158.9(8) ?~3, Z=4, C_(12)H_(36)N_2NiO_(10), Mr=427.14, Dc=1.314 g/cm~3, F(000)=920 and μ=0.944 mm~(-1). Single-crystal X-ray diffraction reveals that the mononuclear nickel(Ⅱ) ion is six-coordinated to one oxygen, two nitrogen atoms of the BDMAE ligand and three oxygen atoms of coordinated water molecules. The complex exhibits a 3D supramolecular structure through a variety of intermolecular and intramolecular hydrogen bonding interactions. In addition, the complex has been investigated for catalytic properties towards the Henry reaction of nitromethane with p-nitrobenzaldehyde, and the results indicated that the 1-p-nitrophenyl-2-nitroethanol product was obtained in excellent yield under optimum conditions with the complex as the catalyst.     

Synthesis,Crystal Structure and Properties of a Novel Coordination Polymer Based on a Trinuclear Mn（II） Cluster： [Mna（bpta）2（bip）2]n

The coordination polymer, [Mn3（bpta）2（bip）2], （H3bpta = biphenyl-3,3＇,5-tricar- boxylic acid, bip = 2,6-bis（imidazole-1-yl）pyridine）, has been synthesized under hydrothermal con- ditions and characterized by elemental analysis, FT-IR, XRD, TGA and single-crystal X-ray diffraction. It crystallizes in monoclinic, space group P21/c with a = 14.919（3）, b = 9.780（2）, c = 20.352（7） A, V = 2344.4（10） A3, Z= 2, C52H32Mn3N10012, Mr = 1153.70, Dc = 1.634 g/cm3, p（MoKa） = 0.876 mm-1, F（000） = 1170, the finalR = 0.0605 and wR = 0.1177. The complex forms a 2D layer with trinuclear Mn（II） units and further assembles into a 3D supramolecular network structure through C-H..＇O hydrogen bonding and C-H...π interactions. Moreover, the negative J value indicates the presence of antiferromagnetic coupling between the Mn（II） ions within a trinuclear unit.     

Syntheses,Crystal Structures and Fluorescence Properties of Two Complexes Based on a New Chiral Ligand

A new homochiral ligand,(R)-2-(4-pyridyl)-4,5-dihydrothiazole-4-carboxylic acid(HL~R), has been synthesized. Two complexes, [ZnL_2~R(H_2O)_2]?H_2O(1) and [MnL_2~R(H_2O)_2]?H_2O(2) have been prepared by the reactions of Zn(Ⅱ) and Mn(Ⅱ) ions with the ligand HLR, and characterized by single-crystal X-ray diffraction analysis and fluorescence. Complexes 1 and 2 are isomorphs, and both of the Zn(Ⅱ) and Mn(Ⅱ) centers in 1 and 2 are six-coordinated by the two NO units of two ligands and two water oxygen atoms, showing distorted octahedral coordination geometry. Complexes 1 and 2 show fluorescent properties in the solid state at room temperature.     

NMR STUDIES ON THE HYDRATION OF IONS IN MICROEMULSION——THE NAPHTHENIC ACID SOAP-ALCOHOL-KEROSINE-WATER MICROEMULSION SYSTEM

The difference △δ between the proton shift of water of hydrauon of metar ions δ(H_2O(M~4))and that of pure liquid water δ_(H_2O(1)) so far observed is very small, only about ± 0.1 ppm,because the ratio of metal ions to H_2O molecules M~ /H_2O cannot exceed 0.36 even in veryconcentrated aqueous solutions. In the present investigation, we study the hydration of metalions in microemulsions and propose a novel method to vary M~ /H_2O ratio from 100:1 to1:100. Under such conditions, we have obtained the limits of δ(H_2O(M~ )) for various cations asfollows: 7.54 ppm (NH_4~ ), 7.08(Li~ ), 6.22(Na~ ), 6.00(K~ ), while δ(H_2O(1)) = 4.80 ppm, sothat the largest △δ observed amounts to 2.74 ppm, thus rendering NMR method an effectivemeans to study the hydration of metal ions.     

Metal-ion Interactions with Sugars: Crystal Structure of Bis(4-dehydro-L-arabinose) Calcium Methanol Bishydrate

The crystal structure of the metal-organic frame Ca(C5H9O5)2·CH3OH·2H2O(1) has been synthesized and characterized.Complex 1 belongs to a tetragonal P43212 space group.In complex 1,the sugar moiety shows a beta-L configuration of pyranose form.The calcium(Ⅱ) is eight-coordinated,binding to four such sugar moieties,via O(1),O(2) of two molecules and O(3),O(4) of the other two,with the 4-hydroxy group being deprotonated.The water and methanol molecules are not coordinated to the calcium ion.     

Synthesis,Crystal Structure,and Luminescence of a 1D Chain Cd(Ⅱ) Polymerwith 3,3?,5,5?-Benzene-1,3-biyl-tetrabenzoic Acid

A new Cd(Ⅱ) coordination polymer, [Cd(H_2btb)(bpy)]_n(1, H_4btb = 3,3?,5,5?-benzene-1,3-biyl-tetrabenzoic acid, bpy = 2,2?-bipyridine), has been synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric(TG) analyses and single-crystal X-ray diffraction techniques. Complex 1 belongs to monoclinic system, C2/c space group. In 1, two carboxylate groups of the H_4btb ligand adopt bidentate chelating and μ_2-η~1:η~1 coordination modes, respectively, bridging the Cd(Ⅱ) atoms to generate a 1D polymeric ribbon. In addition, the photoluminescence property of complex 1 has also been studied.     

Three New Isostructural Metal-organic Coordination Polymers from Triangular Pyridinedicarboxylate Ligand:Syntheses,Structures and Properties

Three new isostructural coordination polymers, namely, [Mg(cpna)(H_2O)_2]_n(1), [Mn(cpna)(H_2O)_2]_n(2) and [Co(cpna)(H_2O)_2]_n(3)(H_2 cpna = 5-(3-carboxylphenyl)nicotic acid) are reported. They were synthesized by hydrothermal reactions of transition metal or alkaline earth metal chloride with 5-(3-carboxylphenyl)nicotic acid,respectively. Complexes 1～3 exhibit 2D layers with a 3,3-connected topology with Schl?fli symbol {4.82}. Such layers including hexagonal rings and a quadrangular ring are further extended into an ordered 3D framework by hydrogen bonds between the cpna~(2-) ligands and water molecules. The rare complex 1 has excellent luminescence and can be used as luminescent materials, while 2 and 3 possess prominent magnetism with potential applications in magnetic materials.     

Mixed-solvothermal Synthesis,Crystal Structure and Luminescence of a New Dinuclear Yttrium(Ⅲ) Coordination Polymer with 1-D Wave-like Infinite Chains

A new dinuclear Y~(3+) coordination polymer{[Y_2(H_2O)_2(C_(14)H_8O_4)_3(C_(12)H_8N_2)_2]·3 H_2O}_n (1, C_(14)H_8 O_4 = 2,2?-biphenyldicarboxylate, phen = 1,10-phenanthroline), has been obtained by means of a mixed-solvothermal method using ethylene glycol and water as solvent. The compound was characterized by elemental analysis, energy-dispersive X-ray spectroscopy(EDS), IR spectrum and single-crystal X-ray diffraction. The results reveal that 1 belongs to monoclinic system, space group C2/c with a = 24.249(3), b = 12.069(48), c = 22.7304(08) ?, β = 113.480(7)°, Z = 4, V = 6102(2) ?~3, Dc = 1.462 g·cm~(-3), F(000) = 2728, μ = 1.968 mm~(-1), the final R = 0.0673, w R = 0.1508 and S = 1.085. Its structure can be regarded as a 1-D coordination polymer constructed by Y~(3+) cations, 2,2?-biphenyldicarboxylate, 1,10-phenanthroline and water molecules. The compound not only contains two kinds of organic ligands, but also exhibits interesting wave-like infinite chains and 18-MR windows with the diameter of 4.070(7)? × 5.326(9)?. The structure is further stabilized by means of O–H···O hydrogen bonds and π-π stacking interactions. Furthermore, the luminescent properties(including emission spectrum, CIE chromaticity coordinate and decay curve) of 1 were also investigated in the solid-state at room temperature.     

Synthesis,Crystal Structure and Antitumor Activity of a Novel Zn(Ⅱ) Complex with 2-(Nicotinoyloxy)acetic Acid Ligand

A novel Zn(Ⅱ) complex, [ZnL_2(H_2O)_4]·H_2O(1, HL = 2-(nicotinoyloxy)acetic acid), was synthesized using Zn(OAc)_2·2H_2O and 2-(nicotinoyloxy)acetic acid as raw materials. Its structure has been elucidated by elemental analysis, IR and single-crystal X-ray diffraction. The structural analysis revealed that complex 1 crystallizes in triclinic, space group P1 and the Zn(Ⅱ) atom is six-coordinated with two N atoms from two different 2-(nicotinoyloxy)acetate anion ligands and four O atoms from coordinated water molecules. Complex 1 forms a 3D network structure by O–H···O hydrogen bonds. The antitumor activities of 2-(nicotinoyloxy)acetic acid ligand and its Zn(Ⅱ) complex were evaluated against human lung adenocarcinoma A549 cells, human hepatoma SMMC-7721 cells and human colon carcinoma Wi Dr cells.     

Synthesis,Crystal Structure,Fluorescence, Thermal Stability and Magnetic Properties of the Dinuclear Manganese(Ⅱ) Complex [Mn_2(L)_2(2,2'-bipy)_2(H_2O)_5]_2·3H_2O

A new dinuclear manganese complex [Mn2(L)2(2,2'-bipy)2(H2O)5]2·3H2O has been synthesized with Mn SO4·H2O, 2,2'-bibenzoic acid(H2L) and 2,2'-bipyridine(2,2'-bipy) in the mixed solvent ethanol and water. It crystallizes in monoclinic, space group P1 with a = 9.9944(10), b = 21.939(2), c = 25.628(3) ?, α = 108.429(3), β = 100.613(4), γ = 102.821(3)o, V = 4997.9(9) ?3, Dc = 1.355 g/cm3, Z = 2, F(000) = 2108, GOOF = 1.074, the R = 0.0626 and w R = 0.1531. The structure of the complex contains two [Mn2(L)2(2,2'-bipy)2] units, ten coordinated H2 O molecules and three uncoordinated H2 O molecules. The fluorescence, thermal stability and magnetic properties of the complex were investigated.     

A Novel 3D Pillar-layered Co(Ⅱ)-MOF with(4,8)-Connected Topology: Synthesis,Structure and Magnetic Properties

By using "pillaring" strategy, a new Co(Ⅱ)-MOF, [Co_2(abtc)(bimb)_2]·2H_2O(1, H_4abtc = 3,3?,5,5?-azobenzenetetracarboxylic acid, bimb = 4,4?-bis(imidazole-1-ylmethyl)biphenyl), has been solvothermally synthesized and structurally characterized. The structural determination revealed that 1 features a 3D pillar-layered framework with(4,8)-connected {4~4.6~2}{4~8.6~(20)} topology based on dinuclear Co(Ⅱ)-SBUs. The magnetic investigation shows that the dominant antiferromagnetic coupling is observed in compound 1.     

Syntheses,Crystal Structures and Catalytic Activities of Two Novel Mn_2Dy_2O_2 Complexes

Two novel heteronuclear manganese-dysprosium complexes have been synthesized and characterized, both of which contain a [Mn_2Dy_2O_2] core ligated by eight But CO_2-anions and four neutral ligands. In complex 1, [Mn_2Dy_2O_2(Bu~tCO_2)_8(Bu~tCO_2H)_4], all the four neutral ligands coordinated to Dy~(3+) are pivalic acids; Instead, two of these four pivalic acids have been replaced by ethanol in complex 2 [Mn2 Dy2 O2(Bu~tCO_2)_8(Bu~tCO_2H)_2(CH_3CH_2OH)_2]. The crystal of complex 1(C_(60)H_(112)Dy_2Mn_2O_(26), Mr = 1684.36) belongs to the orthorhombic system, space group Pbca with a =19.853(3), b = 18.565(3), c = 20.952(3) ?, V = 7723(2) ?3, Z = 4, Dc = 1.449 g/cm~3, S = 1.210, μ =2.302 mm~(-1), F(000) = 3448, the final R = 0.0802 and w R = 0.1570 for 8736 independent reflections.The crystal of complex 2(C_(54)H_(104)Dy_2Mn_2O_(24), Mr = 1572.25) belongs to the monoclinic system,space group C2/c with a = 27.814(6), b = 13.194(3), c = 22.912(5) ?, β = 124.89(3)o, V = 6897(3) ?3,Z = 4, Dc = 1.514 g/cm~3, S = 1.086, μ = 2.570 mm~(-1), F(000) = 3208, the final R = 0.0256 and wR =0.0592 for 7763 independent reflections. The cyclic voltammogram and catalytic activity measurements of complex 1 suggest that this type of complex can serve as a catalyst for oxygen-evolving reaction.