Mn(Ⅱ) Based Coordination Polymer Involving 1,2,4,5-Benzenetetraboxylic Acid and 4,4-Bis(imidazol-1-ylmethyl)biphenyl: Synthetic,Structure and Magnetic Property

A novel Mn(Ⅱ)coordination polymer(CP),[Mn(BBA)_(0.5)(BIYB)]_n(1),was gained by the 1,2,4,5-benzenetetracarboxylic acid(H_4BBA),4,4-bis(imidazol-1-ylmethyl)biphenyl(BIYB),and Mn(CH_3COO)_2·4H_2O under hydrothermal reaction.CP 1 was characterized and structurally determined by elemental analyses,PXRD,IR spectra,thermal behaviors,and X-ray single-crystal diffraction.The framework structure of 1 shows a novel(2,5,6)-connected 3Dnetwork with a Schlafli symbol of(4~3.6~6.8)~2(4~6.6~9)(6)~2.It crystallizes in triclinic system,space group ■,with a=7.5898(5),b=9.8201(6),c=14.1307(9)?,α=97.5850(10),β=99.6810(10),γ=111.6580(10)o,V=943.01(10)?~3,Z=2,C_(23)H_(15)MnN _4O_4,M_r=466.33,D_c=1.462 g/cm~3,F(000)=476,S=1.082,R=0.0361 and wR=0.1008.The magnetic property of CP 1 was investigated.The weak antiferromagnetic interactions are observed between the Mn(Ⅱ)ions.     

Crystal Structure,Thermal Behavior and Luminescence of a New Dimeric Manganese(Ⅱ) Complex Constructed with 3-Carboxy-1-carboxymethyl-2-oxidopyridinium

A new dimeric Mn(Ⅱ) complex,namely,[Mn(L)(PIP)]_2·H_2O(1),was synthesized under hydrothermal condition(H_2L = 3-carboxy-1-carboxymethyl-2-oxidopyridinium and PIP = 2-(pyridin-3-yl)-1H-imidazo[4,5-f][1,10]phenanthroline).It crystallizes in triclinic,space group P1 with a = 9.2037(13),b = 9.6794(13),c = 14.649(3) ?,α = 94.858(3),β = 94.928(3),γ = 114.468(2)o,V = 1172.9(3) ?~3,Z = 1,C_(52)H_(34)Mn_2N_(12)O_(11),Mr = 1112.79,Dc = 1.575 g/cm~3,F(000) = 568,μ(Mo Ka) = 0.618 mm~(-1),R = 0.0432 and w R = 0.1151.In 1,two L anions bridge two Mn(Ⅱ) atoms to give a dimeric [Mn(L)(PIP)] unit with the Mn···Mn distance of 3.009(2) ?.The two PIP ligands are located on both sides of the dimer,which provides suitable π-π stacking interactions between PIP ligands.By these π-π stacking interactions,adjacent dimers are extended into a two-dimensional supramolecular layer.Further,the strong N–H···O hydrogen bond stabilizes the supramolecular layer structure of 1.Moreover,the thermal behavior and luminescent property of 1 have been studied.     

Synthesis,Electrochemical and Fluorescent Properties of a New Zinc(Ⅱ) Complex through Self-assembly Reaction of 2,2'-Bipyridine-3,3'-dicarboxylic Acid

A new Zn(Ⅱ) complex [Zn(Phen)_2(C_(12)H_6O_4N_2)(H_2O)]·3H_2O with 2,2?-bipyridine-3,3?-dicarboxylic acid and 1,10-phenanthroline(Phen) as ligands was synthesized, and the crystal data are as follows: monoclinic, space group P2_(1/n), a=12.5581(11), b=17.3382(17), c=15.6687(14) ?, β=110.579(2)o, M_r=731.02, V=3193.9(5) ?~3, Dc=1.520 g/cm~3, Z=4, μ(Mo Kα)=0.833 mm~(-1), F(000)=1508, the final R=0.0431 and w R=0.0936. In the title complex, the central Zn(Ⅱ) ion is located in a distorted octahedral coordination environment. The electrochemical and fluorescent properties were studied. The title complex possesses irreversible electron transfer in the electrode reaction, and it has a strong emission peak in the range of 470~505 nm, with the excitation wavelength being 488 nm.     

In Situ Synthesis,Structural Characterization and Catalytic Properties of a 2D Cu(Ⅰ)-cyanide Coordination Polymer

A new Cu(Ⅰ) coordination polymer(CP) formulated as [Cu_2(L)(CN)_2]_n(1, L =1,1?-bis(5,6-dimethylbenzimidazole)methane) was synthesized, in which the cyanide anions were generated in situ by the cleavage of C–C bond of acetonitrile under hydrothermal conditions. CP 1 was characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. It crystallizes in the orthorhombic system, Pccn space group, with a = 10.314(3), b = 20.966(7), c =9.432(3) ?, V = 2039.5(11) ?~3, Z = 4, C_(21) H_(20) Cu_2 N_6, M_r = 483.51, D_c = 1.575 g×cm~(-3), μ = 2.105 mm~(-1) and F(000) = 984, the final R = 0.0608 and wR = 0.1942 for 1226 observed reflections with Ⅰ 2s(Ⅰ)for the CP 1. The CP 1 possesses a 2D {63} layer structure which is composed of Cu(Ⅰ) centers bridged by L and CN– ligands. The thermal stability and luminescence properties of CP 1 are discussed in detail. The complex also displays a remarkable activity for the degradation of methyl orange by hydrogen peroxide in a Fenton-like process.     

A New Manganese(Ⅱ) Coordination Compound Constructed by 1,10-Phenanthroline Derivative and Chlorine Anions: Synthesis,Crystal Structure and Theoretical Calculation

The new manganese(Ⅱ) coordination compound, [Mn(Cl)_2(L)_2](1, L = 11-fluorodipyrido[3,2-a:2?,3?-c]phenazine), has been achieved under hydrothermal conditions. The structure of compound 1 was determined by single-crystal X-ray diffraction. 1 crystallizes in monoclinic system, space group C2/c with a = 8.419(2), b = 12.286(2), c = 28.451(6) ?, β = 95.889(3)°, V =2927.5(10) ?~3, Z = 4, C_(36) H_(16) MnF_2 Cl_2 N_8, M_r = 724.41, D_c = 1.644 g/cm~3, F(000) = 1460, μ(Mo Ka)= 0.691 mm~(-1), R = 0.0445 and wR = 0.0982. Adjacent compounds are stacked by one type of π-πinteraction among L ligands to generate a 1D supramolecular chain. Further, the 1D supramolecular chains are stacked by another type of π-π interaction among L ligands to give a 2D supramolecular layer. Moreover, the C-F···π interactions between the carbon atom of the L ligand and the pyrazine ring of the adjacent L ligand further stabilize the supramolecular layer of 1. In addition, natural bond orbital(NBO) analysis has been calculated by the B3LYP/LANL2DZ method, which shows obvious covalent interaction between the coordinated atoms and Mn(Ⅱ) ion.     

Synthesis,Crystal Structure and Antifungal Activity of a New Ho(Ⅲ) Complex Based on 4,4?-Dicarboxybiphenyl Sulfone

A new lanthanide coordination polymer, [Ho(sba)(H_2O)_2(DMF)_2]×H_2O×DMF×Cl(1) based on the versatile ligand H2sba(H2sba = 4,4?-dicarboxybiphenyl sulfone), was prepared and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy and thermogravimetric analysis. Single-crystal X-ray diffraction indicates that complex 1 belongs to the triclinic system, space group P1 with a = 10.6942(6), b = 11.8452(7), c = 13.1814(8) ?, α = 94.854(2), b = 96.649(2), γ = 91.663(2)o, V = 1651.30(17) ?3, Z = 2, Dc = 1.565 g·cm~(-3), μ = 2.597 mm~(-1), Mr = 777.98, F(000) = 780, the final R = 0.0446 and w R = 0.1116 with I 2s(I). In the title complex, the Ho(III) ions exhibit 1D ∞-like double chains. The DMF molecules not only make the structure more stable, but also act as hydrogen bond acceptors making the 1D double chains into a three-dimensional(3D) supramolecular framework. In addition, the antifungal effects of the ligand, metal salt and Ho(III) complex have also been studied by the disc diffusion method against Colletotrichum gloeosporioides Penz. It was found that the antifungal activity of complex 1 was better than the corresponding ligand and the metal salt. Complex 1 has potential applications in the antifungal activity.     

Synthesis,Crystal Structure and Photoluminescent Property of a New Zn(Ⅱ) Complex Based on 3,4-Bis(2-pyridyl)-5-(4-pyridyl)-1,2,4-triazole

The coordination polymer[Zn_(1.5)(2,2?,4??-tpt)(tpa)_2]_n(2,2?,4??-tpt=3,4-bis(2-pyridyl)-5-(4-pyridyl)-1,2,4-triazole,H_2tpa=terephthalic acid)has been obtained by solution evaporation method and characterized by elemental analysis,IR,TG and single-crystal X-ray diffraction.The title compound crystallizes in the triclinic system,space group P1,with a=10.331(3),b=10.596(1),c=14.966(3)?,β=99.029(0)o,V=1448.86(6)?~3,Z=2,D_c=1.668g/cm~3,μ=1.320 mm~(-1),F(000)=740,R=0.0359 and w R=0.0841 with I2σ(I)).In this polymer,the asymmetric unit contains two crystallographically independent Zn(II)ions in different coordination environments.Zn(1)ion is five-coordinated,forming a distorted tetragonal pyramidal geometry,while the Zn(2)ion is six-coordinated to get a distorted octahedral geometry.Each Zn(II)ion is linked by 2,2?,4??-tpt and H_2tpa ligands,forming an infinite 2D structure.The existence of O(8)–H(8)···O(2)hydrogen bonding interactions leads the 2D chains to generate a 3D structure.In addition,1 shows strong photoluminescent emissions in the solid state at room temperature,so it can be used as potential optical materials.     

Hydrothermal Synthesis,Crystal Structure and Proton Conductivity of a Pr–Ca Heterometal-organic Framework Generated by 1,2,4,5-Benzenetetracarboxylic Acid

A heterometal-organic framework {[Pr_2Ca(betc)_2(H_2O)_7]·H_2O}_n(1) was prepared by the hydrothermal reaction of 1,2,4,5-benzenetetracarboxylic acid(H4betc) with Pr(NO_3)_3 and CaCO_3, and further characterized by single-crystal X-ray structural analysis, elemental analysis, IR, thermal gravimetric, and X-ray powder diffraction. Complex 1 crystallizes in triclinic, space group P1 with a = 7.3668(12), b = 10.1726(14), c = 11.2264(15) ?, a = 100.404(2), b = 106.113(3), g = 109.158(3)o, V = 728.48(19) ?~3, Mr = 966.26, Z = 1, F(000) = 470, Dc = 2.203 g/cm~3, m(Mo Kα) = 3.585 mm~(-1), the final R = 0.0195 and w R = 0.0470(I 2s(I)). Complex 1 is a 3D network with pcu topology with 1D porosity and rich hydrogen-bonding interactions. The proton conductivity of complex 1 was also studied under ~97% relative humidity and the different temperature conditions.     

Hydrothermal Synthesis,Crystal structure,DFT and Application of a Dinuclear Cadmium(Ⅱ) Complex Based on NPHSNPAB

A new dinuclear cadmium(Ⅱ) complex,[Cd(NPHSNPAB)(H_2O)_2(CH_3CH_2OH)]_2(1),was synthesized by the hydrothermal reaction of N-phenyl-2-[2-hydroxyl-3-sulfo-5-nitrophenylazo]butadiene-1,3(NPHSNPAB) and Cd(NO_3)_2·4H_2O,and characterized by elemental analysis,infrared,UV-visible,fluorescence,thermal behavior and single-crystal X-ray diffraction. For this complex: C_(36)H_(42)Cd_2N_8O_(22)S_2,Mr = 1227.74,triclinic system,space group P1,a = 7.555(9),b = 12.006(14),c = 13.943(16) ?,α = 67.955(2),β = 88.573(2),γ = 77.550(2)o,V = 1142.5(2) ?~3,Z = 2,Dc = 1.784 g/cm~3,λ = 0.71073 ?,F(000) = 620,S = 1.125,R = 0.0460 and w R = 0.1159 for 3949 observed reflections with I 2(I). X-ray diffraction analysis reveals that the central Cd(Ⅱ) ion is bound by six oxygen atoms,forming a slightly distorted octahedral geometry. Density functional theory of complex 1 was studied. Noticeably,the application of 1 on metallic yarn got good effect.     

Syntheses,Crystal Structures,and Magnetic Properties of Two Manganese(Ⅱ) Coordination Polymers Based on Bifunctional Pyridine-benzene Carboxylic Acids

Two manganese(II) coordination polymers, namely, {[Mn(PIP)(BIBP)]·(BIBP)0.5}n(1) and {[Mn(PTA)(BIMBP)(H_2O)]·H_2O_(0.69)}_n(2)(H_2PIP = 5-(4-pyridyl)-isophthalic acid, H_2 PTA =6-(4-pyridyl)-terephthalic acid, BIBP = 4,4?-bis(imidazol-1-yl)biphenyl, and BIMBP =4,4?-bis(imidazol-1-ylmethyl)biphenyl), have been synthesized by using the bifunctional pyrinde-benzene carboxylic acids and bis(imidazole) linkers as mixed ligands to react with Mn SO4,and further characterized by elemental analysis, IR, and PXRD. Compound 1 is in the triclicnic system, space group P1 with a = 10.1089(8), b = 13.1927(12), c = 14.0638(12) ?, α = 69.437(2), β= 73.2890(10), γ = 78.5320(10)o, V = 1671.9(2) ?~3, Z = 2, Dc = 1.449 g/cm3, F(000) = 705,μ(MoK α) = 0.453 mm-1, S = 1.053, R = 0.0491 and wR = 0.1367 for 5837 unique reflections(Rint =0.0208) with I 2σ(I). Compound 2 belongs to the monoclicnic system, space group C2/c with a =15.199(3), b = 19.731(3), c = 21.537(5) ?, β = 105.228(3)o, V = 6232(2) ?3, Z = 8, Dc = 1.363g/cm3, F(000) = 2648, μ(MoK α) = 0.475 mm-1, S = 1.048, R = 0.0489 and wR = 0.1151 for 7414 unique reflections(Rint = 0.0425) with I 2σ(I). Structural analyses reveal that complex 1 is a4-connected(44.62)-sql bilayer structure with binuclear [Mn_2(COO)_2] SBU, while complex 2 is a normally(3,5)-connected(42.67.8)(42.6)-3,5L2 monolayer. And the sheets interacted with the adjacent sheets through weak interactions, finally giving a stable three-dimensional(3D)supramolecule. Besides, the variable-temperature magnetic susceptibility measurement of complex1 was investigated.     

Synthesis,Crystal Structure and Gas Adsorption of a Two-fold Interpenetrated Three-dimensional Framework {[Cd(2-NO_2-BDC)(4,4?-DPA)]·(DMF)}_n

The reaction of Cd(NO_3)_2·4H_2O with 4,4?-dipyridylacetylene(4,4?-DPA) and 2-nitroterephthalic acid(2-NO_2-H_2BDC) in DMF/H_2O mixed solvent has afforded a compound {[Cd(2-NO_2-BDC)(4,4?-DPA)]·(DMF)}_n(1). Compound 1 has been characterized by single-crystal X-ray diffraction, powder X-ray diffraction, thermogravimetry analysis, and IR spectrum. Compound 1 crystallizes in the monoclinic system, space group P21/n, with a = 12.1488(3), b = 14.6689(3), c = 13.1615(3) ?, β = 111.809(3)o, V = 2177.63(9) ?~3, Z = 4, C_(23)H_(18)N_4O_7 Cd, M_r = 574.81, D_c = 1.753 g/cm~3, μ = 8.523 mm~(-1), F(000) = 1152, the final R = 0.0411 and wR = 0.1064 for 3589 observed reflections with I 2s(I). In compound 1, the Cd(Ⅱ) ions are linked by the carboxylate groups of 2-NO_2-BDC ligands to give a two-dimensional layered structure based on the centrosymmetric dinuclear Cd_2(COO)_2 units, which are further connected by the 4,4?-DPA ligands to produce a three-dimensional framework with pcu topology. Careful examination revealed that compound 1 is a 2-fold interpenetrating framework. Furthermore, the gas adsorption properties of 1 for N_2 and CO_2 have also been investigated.     

A New 3d-4f Heterobimetallic Complex Based on 4,4?-Dicarboxybiphenyl Sulfone: Synthesis,Crystal Structure and Antifungal Activity

A new 3 d-4 f heterobimetallic complex [PrCu(sba)_2(Hsba)(H_2 O)_3]·H_2 O(1) based on a versatile ligand H_2 sba(H_2 sba = 4,4?-dicarboxybiphenyl sulfone) was prepared and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy and thermogravimetric analysis. Single-crystal X-ray diffraction indicates that complex 1 belongs to the monoclinic system, space group P2_1/n with a = 12.4642(11), b = 16.0586(16), c = 21.9678(19) ?, β = 92.888(1)o, V = 4391.4(7) ?~3, Z = 4, D_c = 1.800 g·cm~(-3), μ = 1.812 mm-1, M_r = 1190.31, F(000) = 2388, the final R = 0.0663 and wR = 0.1539 for 7737 observed reflections with I 2s(I). Complex 1 exhibits 2D network skeletons which are linked by hydrogen-bonding interactions to give a 3D supramolecular architecture. In addition, the antifungal effects of H_2 sba, metal salts and the title complex have also been studied by disc diffusion method against Colletotrichum gloeosporioides Penz. Complex 1 has better antifungal activity than H_2 sba and the corresponding metal salts. Complex 1 has potential applications in the antifungal activity.     

Synthesis,Structure and Norbornene Polymerization Catalyzed by Bis{(2-benzhydryl-4,6-dimethyl-phenyl)-(3,5-di-tert-butyl-2-methyl-benzylidene)-amine-N,O}nickel(Ⅱ)

The title complex bis{(2-benzhydryl-4,6-dimethyl-phenyl)-(3,5-di-tert-butyl-2-methyl-benzylidene)-amine-N,O}nickel has been synthesized by the reaction of(2-benzhydryl-4,6-dimethyl-phenyl)-(3,5-di-tert-butyl-2-methyl-benzylidene)-amine with Ni(CH_3COO)_2·4H_2O, and characterized by IR spectrum and single-crystal X-ray diffraction analysis. The crystal belongs to the monoclinic system, space group P2_1/c with a = 12.373(4), b = 18.434(7), c = 27.814(10) ?, β = 92.291(6)o, V = 6339(4) ?~3, C7 2H8 0N2 Ni O_2, M_r = 1064.09, Z = 4, D_c = 1.115 g/cm~3, μ = 0.350 mm~(-1), F(000) = 2280, the final R = 0.0846 and wR = 0.2926(I 2s(I)). This title compound was used as homogeneous catalysis of polymerization of norbornene, and the complex exhibited good catalytic activity to catalyze norbornene polymerization using MAO as a cocatalyst.     

Synthesis,Structure and Luminescent Property of a Zn(Ⅱ) Complex with Mixed Multi-N Donor and 2,5-Dihydroxy-terephthalic Acid Ligands

A new complex, [Zn_2(HL)_2(2,5-OH-pbda)]n(1, L = 1-(1 H-imidazol-4-yl)-4-(4 Htetrazol-5-yl)benzene(H_2L) and 2,5-OH-H_2 pbda = 2,5-dihydroxy-terephthalic acid), has been hydrothermally prepared and characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis and PXRD. Complex 1 crystallizes in monoclinic, space group P2_1/n with a = 8.8101(10), b = 17.105(2), c = 9.4014(11) ?, β = 105.704(2)o, V = 1363.9(3) ?`3, Z = 4, C_(14)H_9N_6O_3Zn, M_r = 374.64, D_c = 1.824 g/cm~3, μ = 1.831 mm~(-1), S = 1.042, F(000) = 756, the final R = 0.0309 and w R = 0.1003 for 3130 observed reflections(I 2σ(I)). The H_2L ligand was deprotonated to be an HL-anion, and coordinated with Zn~(2+) to form two-dimensional(2D) Zn_2(HL~-)_2~(2+) sheets, which were pillared by the 2,5-OH-pbda2-ligands to form a three-dimensional(3D) dmc net with Point(Schl?fli) symbol of(4·82)(4·85). The large vacancy of the dmc net is filled via mutual interpenetration of another independent framework, leading to the formation of a 2-fold interpenetrating architecture. Solid state luminescent property of 1 has been investigated.     

Synthesis,Crystal Structure and Luminescence Study of a New Two-dimensional Mn(Ⅱ) Coordination Polymer

The coordination polymer [Mn_2(cipt)_2(aic)_2]_n(cipt = 2-(3-chlorophenyl)-1Himidazo[4,5-f][1,10]phenanthroline, aic = 5-amino-isophthalic acid) has been obtained from hydrothermal reaction and characterized by elemental analysis, IR, TG and single-crystal X-ray diffraction. The title compound crystallizes in the triclinic system, space group P1, with a = 11.523(3), b = 12.162(3), c = 18.706(5) ?, β = 81.789(5)o, V = 2455.2(1) ?3, C_(54)H_(32)Cl_2Mn_2N_(10)O_8, Mr = 1129.68, Z = 2, Dc = 1.528 g/cm3, μ = 0.692 mm-1, F(000) = 1148, R = 0.064 and wR = 0.145 for 9571 observed reflections(I 2σ(I)). In this polymer, the Mn(Ⅱ) atoms adopt different coordination modes. The Mn(1) atom is five-coordinated, forming a distorted tetragonal pyramidal geometry. Mn(2) atom is six-coordinated to get a distorted octahedral geometry, which is different from the Mn(1) atom. Each Mn(Ⅱ) atom is linked by aic ligands with neighboring Mn(Ⅱ) atoms, forming an infinite one-dimensional(1D) double-chain structure. The existence of N–H···O hydrogen bonding interactions leads the 1D chains to generate a 2D structure. Luminescent properties for the ligand cipt and compound 1 have also been discussed in detail.     

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 New Cd(Ⅱ) Coordination Compound Based on 4-(1,2,4-Triazol-4-yl)phenylacetic Acid:Synthesis,Structure and Photoluminescence Property

A new complex [Cd_2(L)_2(Cl)_2(H_2O)]_n(1) was synthesized by reacting CdCl_2·2.5 H_2O with 4-(1,2,4-triazol-4-yl)phenylacetic acid(HL) ligand.The structure of the complex was characterized by single-crystal X-ray diffraction,IR spectroscopy,elemental analysis and PXRD.Complex 1 crystallizes in triclinic,space group P21/c with a = 11.4303(8),b = 14.1792(10),c = 14.6857(10) ?,β = 96.3780(10)o,V = 2365.4(3) ?~3,Z = 4,C_(20)H_(16)Cl_2N_6O_5Cd_2,M_r = 716.09,D_c = 2.011 g/cm3,μ = 2.069 mm~(-1),S = 1.051,F(000) = 1392,the final R = 0.0458 and wR = 0.0949 for 5402 observed reflections(I 2σ(I)).Complex 1 is a two-dimensional(2D) layer structure and non-covalent bonding interactions such as C–H···π and π···π extend the 2D to form a three-dimensional supramolecular polymer.     

Synthesis,Crystal Structure,Theoretical Calculations,and Photoluminescent Property of a Mn(Ⅱ) Complex Assembled by 5-Aminoisophthalic Acid and Phen Ligands

A coordination polymer[Mn_2(ctpt)_2(aic)_2]_n(1,ctpt=2-(4-chloro-phenyl)-1H-1,3,7,8-tetraaza-cyclopenta[l]phenanthrene,H_2aic=5-amino-isophthalic acid)was hydrothermally designed and synthesized.The complex was characterized by elemental analysis,IR spectroscopy,single-crystal X-ray diffraction,and thermogravimetric analysis(TGA).Each Mn(II)atom is linked by the aic ligands with neighbor Mn(II)atoms,forming an infinite one-dimensional(1D)double-chain structure.Complex 1 crystallizes in monoclinic,space group C2/c,with a=18.23(1),b=17.27(1),c=16.69(1)?,V=4814.0(7)?~3,C_(27)H_(16)Cl Mn N_5O_4,M_r=564.84,D_c=1.559 g/cm~3,μ(Mo Kα)=0.706 mm~(-1),F(000)=2296,Z=8,the final R=0.0487 and w R=0.1269(I2σ(I)).The 1D chain structure of complex 1 is stable below 458℃.In addition,to elucidate the essential electronic characters of this complex,theoretical calculation analysis of 1 was performed by the PBE0/LANL2DZ method in Gaussian 03 Program.     

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,Structure and Characterization of a 3D Chiral Barium Carboxylate Metal-organic Framework Based on TADDOL Ligand

A novel alkaline earth-based chiral metal-organic framework 1 {[Ba_(1.5)L(μ-OH_2)_2(DMF)_2(H_2O)]·DMF·1.5 H_2O}_n was synthesized from C2-symmetric TADDOL-based ligand H_4L and structurally characterized by single-crystal and powder X-ray diffraction, Fourier-transform infrared spectra(FTIR), solid-state circular dichroism(CD) and thermal gravimetric analysis(TGA). 1 crystallizes in monoclinic space group C2 with a = 43.5105(12), b = 9.4781(3), c = 15.5620(4) ?, β = 99.7770(10)o, V = 6324.5(3) ?~3, Z = 2, M_r = 1434.18 g/mol, D_c = 1.506 g/cm~3, F(000) = 2904, GOOF = 1.026, the final R = 0.0358 and w R = 0.0952 for 21747 observed reflections with I 2σ(I). Each Ba3 cluster in 1 is linked by eight ligands and each ligand with one coordination-free carboxyl oxygen, O(5), is coordinated to four Ba_3 clusters to generate a 3D network. In addition, the photoluminescence of 1 and H_4L was also investigated.