Synthesis,Structure and Characterization of a Cd(Ⅱ) Polymer Based on 6-Hydroxynicotinic Acid

A new 2D layered Cd(II) coordination polymer,[Cd(HnicO)(phen)(NO3)]n 1(H2nicO = 6-hydroxynicotinic acid,phen = 1,10-phenanthroline),has been hydrothermally synthesized and characterized by elemental analysis,IR,and single-crystal X-ray diffraction.It crystallizes in the monoclinic system,space group P21/c with a = 11.1107(2),b = 13.7639(2),c = 12.1457(4) ,β = 108.695(1)°,V = 1759.40(7) 3,Z = 4,Mr = 492.72,F(000) = 976,Dc = 1.860 g/cm3,μ = 1.289 mm-1,the final R = 0.0205 and wR = 0.0550 for 3663 observed reflections(I > 2σ(I)).X-ray single-crystal structural analyses reveal that in complex 1,the H2nicO ligands and Cd(II) nodes define the structure to be(4,4) 2D nets which are further assembled into the final 3D architecture via supramolecular interactions such as hydrogen bonds and aromatic interactions.Moreover,the solid-state luminescent study shows the title polymer possesses intense luminescent property at room temperature.     

Urothermal Synthesis,Crystal Structure,and Luminescent Property of a New Zn(Ⅱ) Coordination Polymer Constructed from TerephthalicAcid and 5-Methyl-1H-tetrazole Ligands

A new luminescent Zn(II) compound, [Zn(pbdc)0.5(mtz)(DMPU)]n(1, H2pbdc = terephthalic acid, Hmtz = 5-methyl-1H-tetrazole, DMPU = N,N'-dimethylpropyleneurea), has been urothermally synthesized and characterized by elemental analysis, IR, X-ray powder diffraction(PXRD) and single-crystal X-ray diffraction. The title compound crystallizes in orthorhombic Pbca space group with a = 17.2649(5), b = 10.4680(3), c = 17.4457(7) ?, V = 3152.94(18) ?3, C12H17N6O3Zn, Mr = 358.71, Z = 8, Dc = 1.511 g/cm3, F(000) = 1480, μ = 1.579 mm-1, the final R = 0.0379 and wR = 0.0971 for 2785 observed reflections(I 2?(I)). Single-crystal X-ray structural analysis reveals that compound 1 features a 2D undulated layer with a 3-connected hcb topology. Moreover, the luminescent properties of 1 have also been investigated in the solid-state at room temperature.     

Synthesis,Crystal Structure and Electrochemical Properties of a Cobalt Compound Based on N-（4-pyridylmethyl）imidazole Ligand①

One compound with N-(4-pyridylmethyl)imidazole liand, [Co(pyim)2(N3)2]n 1(pyim = N-(4-pyridylmethyl)imidazole), was synthesized and structurally characterized. Compound 1 crystallizes in triclinic, space group P21/c with a = 8.090(3), b = 16.109(3), c = 8.590(3), B= 117.800(12)o, V = 990.3(5) A3, Z = 2, Mr = 461.37, Dc = 1.547 g/cm3, F(000) = 474, μ = 0.901 mm-1, the final R = 0.0381 and wR = 0.0950 for 1581 observed reflections with I 2A(I). In this compound, the unique Co(Ⅱ) resides at a crystallographic inversion center and exhibits an octahedral coordination geometry. The adjacent Co(Ⅱ) ions are connected by the pyim ligands to form a 2D layer structure. The layers are stacked in an ABAB mode and reinforced by the weak interlayer C–H···N hydrogen bonds and π-π stacking to give a 3D architecture. The thermal property and electrochemical property of compound 1 have also been studied.     

A Zn(Ⅱ) 5-Aminoisophthalate Coordination Polymer

The title compound, [Zn(AIP)(4,4-bipy)0.5(H2O)]n·0.75nH2O 1, was synthesized via the hydrothermal reaction of Zn(OAc)2 with 5-aminoisophthalic acid (H2AIP) and characterized by elemental analysis and infrared spectra. The complex crystallizes in monoclinic system, space group P21/c with a = 12.672(1), b = 7.6557(4), c = 16.181(1) (A),β = 109.187(2)o, V = 1482.6(2) (A)3, Z = 1, C52H52N8O23Zn4, Mr = 1418.58, Dc = 1.589 g/cm3, F(000) = 724 and μ(MoKα) = 1.685mm-1. The final R = 0.0702 and wR = 0.1524 for 1847 observed reflections with Ⅰ ＞ 2σ(I), and R = 0.0873 and wR = 0.1664 for all data. X-ray diffraction studies reveal that the title compound has an interesting 2D microporous architecture with guest water molecules inside the channel.     

Hydrothermal Synthesis,Crystal Structure and Luminescent Property of a New Cd(Ⅱ) Coordination Polymer with Four-fold Interpenetrated dia Topology

A new Cd(ΙΙ) coordination polymer with 2-nitroterephthalic acid(H2npa) and 1,4-bis(2-methyl-imidazol-1-yl) butane(bib) has been prepared by hydrothermal synthesis and characterized by single-crystal X-ray diffraction, IR and EA. Complex [Cd(npa)(bib)]n(1) is of orthorhombic system, space group Pcca with a = 16.1750(5), b = 9.8764(5), c = 15.5890(3) A, V =2490.4(2) A3, Z = 4, Mr = 539.82, Dc = 1.440 g/cm3, F(000) = 1088, μ = 0.918 mm-1, the final R =0.0320 and w R = 0.0775 for 2253 reflections with I 2σ(I). X-ray diffraction analysis reveals that complex 1 displays a four-fold interpenetrated dia topology. Furthermore, the luminescent property for complex 1 is also investigated in solid state at room temperature.     

Synthesis,Crystal Structure and Photoluminescent Property of a New Ca(Ⅱ) Compound Constructed from 5-Oxyacetateisophthalic Acid

A new coordination polymer, namely [Ca(HOABDC)]n(1, H3 OABDC = 5-oxyacetateisophthalic acid), has been synthesized through hydrothermal reactions of Ca(NO3)2 and H3 OABDC. The title compound crystallizes in monoclinic, space group P21/c with a = 4.3043(2), b = 21.4959(11), c = 10.7450(6) A, β = 91.411(5)o, V = 993.88(9)A3, C10H6O7 Ca, Mr = 278.23, Z = 4, Dc = 1.859 g/cm3, F(000) = 560, μ = 0.659 mm-1, the final R = 0.0328 and wR = 0.0670 for 1469 observed reflections(I 2A(I)). Single-crystal X-ray structural analysis reveals that compound 1 features 1D Ca(Ⅱ)-carboxylate chain-shaped subunits, which are further connected together via HOABDC2- ligands into a 3D(6,6)-connected nia-type hybrid framework. Moreover, the luminescent property and thermal stability of 1 were also investigated.     

Hydrothermal Synthesis,Crystal Structure and Properties of a Lanthanum(Ⅲ) Complex Based on a N,O-Donor Ligand

A novel metal-organic complex [La(o-NCP)3]n(o-HNCP = 2-(2-carboxyphenyl)imidazo(4,5- f)(1,10)-phenanthroline) has been hydrothermally synthesized and characterized by elemental analysis, infrared analysis and X-ray single-crystal diffraction. The complex crystallizes in triclinic, space group P1 with a = 9.898(2), b = 16.193(3), c = 16.909(3) , α = 67.68(3), β = 80.85(3), γ = 78.78(3)o, V = 2448.2(8) A3, Z = 2, Mr = 1156.9, Dc = 1.569 g/cm3, μ = 0.71073 A, F(000) = 1164, GOOF = 1.065, the final R = 0.051 and wR = 0.123 for 8539 observed reflections with I 2A(I). The complex exhibits a one-dimensional double chain structure. The adjacent chains are further connected by N–H...N hydrogen bonds which help to form a two-dimensional supramolecular architecture. Furthermore, the complex exhibits excellent thermal stability and luminescent property.     

A Luminescent Cd(Ⅱ) Coordination Polymer Constructed from Isophthalic Acid and 1,3-Bis-(4-pyridyl)propane

A new coordination complex [Cd2(ip)2(bpp)]n(1, H2 ip = isophthalic acid, bpp = 1,3-bis-(4-pyridyl) propane) has been synthesized and structurally characterized. Crystal data for the title complex are as follows: triclinic system, space group P1 with a = 9.6724(6), b = 10.2243(6), c = 14.8205(9) ?, α = 88.927(5), β = 71.664(6), γ = 75.767(5)°, V = 1345.79(14) ?3, Mr = 751.29, Z = 2, F(000) = 740, Dc = 1.854 g/cm3, μ(Mo Kα) = 1.636 mm-1, R = 0.0259 and w R = 0.0623 for 4754 observed reflections with I 2σ(I). X-ray structure analysis reveals that complex 1 holds a 3D architecture based on α-Po primitive cubic units with the [Cd4(COO)8] units treated as 6-connected nodes. Solid-state properties for 1, such as infrared spectroscopy, elemental analyses, thermal stability and luminescent property, have also been investigated.     

Synthesis,Crystal Structure,Theoretical Calculation,and Photophysical Property of a New Cd(Ⅱ) Complex Based on N-heterocyclic Ligand and Isophthalic Acid

A new metal-organic coordination complex[Cd(imp)(m-bdc)]_n (1,ipm=5-(1H-imidazo[4,5-f][1,10]phenanthrolin-2-yl)-2-methoxyphenol,m-bdc=isophthalic acid) has been synthesized by hydrothermal reaction and characterized by elemental analysis,thermogravimetric (TG) analysis,infrared spectrum (IR) and single-crystal X-ray diffraction.Complex 1 crystallizes in monoclinic,space group C2/c with a=15.373(5),b=16.719(5),c=19.406(6)A,β=106.995(5)°,V=4770(2)A³,C₂₈H₁₈Cd N₄O₆,M_r=618.86,D_c=1.724 g/cm³,μ(Mo Kα)=0.971 mm^–1,F(000)=2480,Z=8,the final R=0.0391 and w R=0.1044 for 4701 observed reflections (I>2σ(I)).Single-crystal X-ray diffraction reveals that 1 exhibits a one-dimensional (1D) double-chain architecture,and the H-bond intersections link the 1D double-chain architecture into a 2D layer structure.TG analysis shows clear courses of weight loss,which corresponds to the decomposition of different ligands.We also study the luminescent properties of complex 1.In addition,to elucidate the essential electronic characters of this complex,theoretical calculation analysis was performed by the PBE0/LANL2DZ method in Gaussian 03 Program.     

Hydrothermal Synthesis,Crystal Structure,Thermal Stability and Photophysical Property of a Novel Zinc Complex with Mixed Ligands

A novel metal-organic coordination complex [Zn(CHIP)(AIC)]n(1, CHIP = 2-(4-chlorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline, AIC = 5-amino-isophthalic acid) has been synthesized by hydrothermal reactions and characterized by elemental analysis, thermogravimetric(TG) analysis, infrared spectrum(IR) and single-crystal X-ray diffraction. Complex 1 crystallizes in monoclinic, space group C2/c with a = 18.259(5), b = 17.191(4), c = 16.371(4) A, V = 4717(2) A3,C27H-116 ClN 5O4Zn, Mr = 575.29, Dc = 1.620 g/cm3, μ(Mo Kα) = 1.202 mm, F(000) = 2335, Z = 8, the final R = 0.032 and w R = 0.074 for 4723 observed reflections(I 2σ(I)). Single-crystal X-ray diffraction reveals that 1 exhibits one-dimensional(1D) double chains, which are linked by H-bond intersections into a 2D structure. TG analysis shows clear weight loss due to the decomposition of different ligands. The luminescent properties for the ligand and complex 1 were also studied.     

A Zn(II) 5-Aminoisophthalate Coordination Polymer

The title compound, [Zn(AIP)(4,4-bipy)0.5(H2O)]n·0.75nH2O 1, was synthesized via the hydrothermal reaction of Zn(OAc)2 with 5-aminoisophthalic acid (H2AIP) and characterized by elemental analysis and infrared spectra. The complex crystallizes in monoclinic system, space group P21/c with a = 12.672(1), b = 7.6557(4), c = 16.181(1) , β = 109.187(2)o, V = 1482.6(2) 3, Z = 1, C52H52N8O23Zn4, Mr = 1418.58, Dc = 1.589 g/cm3, F(000) = 724 and μ(MoKα) = 1.685mm-1. The final R = 0.0702 and wR = 0.1524 for 1847 observed reflections with I > 2σ(I), and R = 0.0873 and wR = 0.1664 for all data. X-ray diffraction studies reveal that the title compound has an interesting 2D microporous architecture with guest water molecules inside the channel.     

Synthesis and Crystal Structure of a New Pr(Ⅲ)–K(Ⅰ) Heterometallic Oxalate Coordination Polymer

A new 3D heterometallic coordination polymer, namely [K2Pr2(C2O4)4·H2O]n(1), has been successfully synthesized under hydrothermal conditions. X-ray single-crystal diffraction determination reveals that 1 crystallizes in monoclinic system, space group P21/n with a = 12.060(4), b = 8.493(3), c = 15.776(5)(A), β = 93.235(3)°, V = 1613.4(9) 3, Z = 4, Mr = 730.12, Dc = 3.006 Mg/m3, μ = 6.581 mm-1, F(000) = 1368, the final R = 0.0283 and w R = 0.0866 for 2939 observed reflections with I 2σ(I). Complex 1 features an unusual 3D heterometallic coordination framework, in which oxalates exhibit three different coordination behaviours. Moreover, powder X-ray diffraction and thermal properties for 1 have also been investigated.     

Synthesis,Structure and Luminescent Property of a New bnn-type Zn(Ⅱ) Coordination Polymer

A new Zn(Ⅱ) coordination polymer, namely [Zn(Htci)(bib)0.5(H2O)]n·nH2O(1, H3 tci = tri(2-carboxyethyl)isocyanurate, bib = 1,4-bis(imidazol-1-ylmethyl)-butane) has been synthesized by combining H3 tci and bib ligands with Zn(Ⅱ) salts under solvothermal conditions. The title compound crystallizes in monoclinic, space group P21/c with a = 13.3424(7), b = 7.9051(5), c = 20.4650(12) , β = 101.935(5)o, V = 2111.8(2) 3, C17H24N5O11 Zn, Mr = 539.8, Z = 4, Dc = 1.698 g/cm3, F(000) = 1116, μ = 1.236 mm-1, the final R = 0.0398 and wR = 0.00879 for 3722 observed reflections(I 2■(I)). X-ray structural analysis reveals that compound 1 exhibits a three-dimensional(3D) pillar-layered framework, and can be simplified into a 5-connected bnn topological network. Moreover, the luminescent properties for compound 1 were also studied at room temperature.     

Synthesis and Supramolecular Structure of a Novel :r-Extended TTF Derivative

A novel x-extended TTF derivative (C24H20N6S8, Mr=649.02) has been synthesized and characterized by IR,1H NMR and MS. The crystal structure was prepared by crystallization from CH2Cl2-MeOH. The crystal belongs to the monoclinic system, space group P21/c with a=5.465(5), b=26.835(5), c=10.180(5) A, β=101.929(5)°, V=1460.7(15) A3, Z=2, Dc=1.476 g/cm3,F(000)=668,μ=0.638 mm-1, the final R=0.0390 and wR=0.0586 for 1694 observed reflections with I > 2σ(I). The structure reveals planarity of the two dithiole tings, different from the boat-shaped structure usually found in neutral derivatives of TTF. The central ring of the benzene also adopts a planar conformation, while it is twisted from planarity of the two dithiole rings and forms a dihedral angle of 61.8°. The molecule exhibits a three-dimensional supramolecular architecture constructed through hydrogen bonds. In the molecular structure a noticeable feature can be found that there exist S…S interactions which further reinforce the 3D supramolecular framework.     

Synthesis and Characterization of a Homochrial Manganese（Ⅱ）Complex Constructed from （1R,2R）-（-）-Diaminocyclohexane-N,N biscarboxyl-salicylidene）

A homochrial manganese(Ⅱ) complex derived from chiral salen ligand (1R,2R)-(-)diaminocyclohexane-N,N-biscarboxyl-salicylidene) (1) has been synthesized through solvothermal procedure and characterized by IR,elemental analysis,TGA,circular dichroism (CD),powder and single-crystal X-ray crystallography.It crystallizes in monoclinic,space group C2 with a=32.987(7),b=7.4662(15),c=17.931(4),β=97.82(3)°,V=4375.0(15) 3,Z=8,D c=1.544 g/cm 3,F(000)=2096,M r=508.36,μ=0.658 mm-1,the final GOOF=0.975,R=0.0676 and wR=0.2068 for 6357 observed reflections with I > 2σ(Ⅰ).The coordination polymer 1 possesses a 1D infinite zigzag chain architecture constructed by the dicarboxyl-functionalized metallosalen ligand (MnSalen),and the polymeric chains are further assembled into a 2D supramolecular network structure via strong intermolecular hydrogen bonding interactions between the adjacent zigzag chains.     

Syntheses,Structures and Properties for Zn~Ⅱ Coordination Polymers Based on a Functional 4'-(3-Pyridyl)-3,2':6',3'-terpyridine Ligand

Two new Zn~Ⅱ coordination polymers,namely,[Zn L(o-bdc)]n(1) and [Zn L(mbdc)]_n·n H_2O(2)(L = 4?-(3-pyridyl)-3,2?:6?,3??-terpyridine,H_2(o-bdc) = benzene-1,2-dicarboxylic acid,H_2(m-bdc) = benzene-1,3-dicarboxylic acid),were synthesized by hydrothermal methods. The crystal structures have been determined by single-crystal X-ray diffraction. Compound 1 crystallizes in monoclinic C2/c space group,with a = 28.016(2),b = 11.3815(11),c = 19.8071(17) ?,β = 133.961(2)°,V = 4546.2(7) ?3,Z = 8,Mr = 539.83,Dc = 1.577 Mg/m~3,μ = 1.127 mm-1,F(000) = 2208,the final R = 0.0426 and w R = 0.0986 for 2875 observed reflections with I 2σ(I) and displays a 1D coordination chain. While compound 2 crystallizes in monoclinic C2/c space group,with a = 15.6003(14),b = 11.9152(11),c = 26.633(3) ?,β = 94.320(2)°,V = 4936.5(8) ?~3,Z = 4,M_r = 1115.67,Dc = 1.496 Mg/m~3,μ = 1.043 mm~(-1),F(000) = 2272,the final R = 0.0499 and w R = 0.1342 for 2659 observed reflections with I 2σ(I) and shows a classical 3D cds topological network with point symbol of {65.8}. Furthermore,thermal stability and luminescent properties of 1 and 2 have also been investigated.     

Synthesis,Crystal Structure and Theoretical Calculations of a Manganese(Ⅱ) Coordination Polymer Assembled by 2,5-Thiophenedicarboxylic Acid and 3-(2-Pyridyl)pyrazole Ligands

A new Mn(Ⅱ) complex, [Mn_(0.5)(tdc)_(0.5)(L)]_(2n)(1, H2 tdc = 2,5-thiophenedicarboxylic acid, L = 3-(2-pyridyl)pyrazole), has been successfully synthesized under hydrothermal conditions. Its structure has been determined by single-crystal X-ray diffraction analysis, elemental analyses, IR, TG and UV spectrum. Single-crystal X-ray diffraction analysis reveals that complex 1 belongs to the orthorhombic system, space group Pnna with a = 11.5184(6), b = 16.8399(8), c = 11.7249(5) ?, V = 2274.26(19) ?3, Z = 4, D3c = 1.505 g/cm, μ = 0.715 mm-1, Mr = 515.41, F(000) = 1052, the final R = 0.0336 and w R = 0.0802 with I 2σ(I). It exhibits a one-dimensional zigzag-chain structure, which was stabilized through intermolecular C–H···O and intramolecular N–H···O hydrogen bonding interactions. Moreover, we analyzed Natural Bond Orbital(NBO) by using the PBE0/LANL2 DZ method built in Gaussian 09 Program. The calculation results showed obvious covalent interaction between the coordinated atoms and Mn(Ⅱ) ion.     

Synthesis and Characterization of a New Metal-organic Framework with Nou Topology

A new compound, [H2N(CH3)2]2[Zn(btec)].H2O(1, H4 btec = 1,2,4,5-benzenetetracarboxylic acid) has been solvothermally synthesized and structurally characterized by singlecrystal X-ray diffraction. The crystal structure is of monoclinic, space group P21/c with a = 9.5741(3), b = 14.5044(4), c = 13.7329(5) , β = 100.582(4)°, V = 1874.61(10) 3, C14H20N2O9 Zn, Mr = 425.7, Z = 4, Dc = 1.387 g/cm3, μ = 1.349 mm-1, F(000) = 776, R = 0.0560 and w R = 0.1684 for 2834 observed reflections(I 2σ(I)). Compound 1 based on μ4-btec and tetrahedral building unit features a three-dimensional(3D) anionic framework with mixed connected nou topology. The luminescent property and thermogravimetric analysis of compound 1 are investigated.     

Syntheses,Crystal Structures,DFT Calculation and Optical Properties of a Schiff Base and Its Dinuclear Mercury(Ⅱ) Complex

A pyridine-contained Schiff base ligand L(L =(pyridine-2-vinyl)hydrazine) has been synthesized and fully characterized. By self-assembly of the ligand with HgI_2, a binuclear complex Hg_2I_4L(C) was obtained. The structures of L and C were analyzed through single-crystal X-ray diffraction. L crystallizes in monoclinic, space group P21/n with a=11.286(5), b=3.981(5), c=23.865(5) ?, β=100.043(5)°, V=1056(1) ?~3, Z=4, Dc=1.323 g/m~3, F(000)=440, Μr=210.24, μ=0.084 mm~(-1), the final R=0.0928 and w R=0.2867 for 6955 observed reflections with I 2(I). The complex is of monoclinic system, space group P21/n with a=8.706(5), b=17.468(5), c=14.675(5) ?, β=93.922(5)°, V=2227(2) ?~3, Z=4, Dc=3.338 g/m~3, F(000)=1928, Μr=1119.02, μ=19.321 mm~(-1), the final R=0.0366 and w R=0.1276 for 3920 observed reflections with I 2(I). The structural analysis revealed that the molecule of L possesses a well planar structure. However, in the complex, the coordinated ligand distorts greatly. The absorption spectra of L and the complex in ethanol were experimentally and theoretically studied. The result indicates that the complex exhibits different absorption spectrum compared with the free ligand.     

A Metal-organic Framework Constructed from a Rare Rod-shaped Secondary Building Unit and Its Highly Efficient Photocatalytic Activity

A new Cu(Ⅱ) coordination polymer,{[Cu_3(oba)_2(μ~3-OH)_2(H_2O)_2].6H_2O}_n(H_2 oba=4,4'-oxydibenzoic acid),was synthesized by the solvothermal route and characterized by IR,TGA and XRD.The complex crystallizes in the monoclinic system,space group P2_1/c with a=5.957(6),b=29.746(3),c=9.351(7) A,β=125.709(4)°,V=1345.4(2) A~3,Z=2,C_(28)H_(36)Cu_3O_(20),M_r=883.09,D_c=1.913 g/cm~3,F(000)=782,μ=2.427 mm~(-1),R=0.0780 and wR=0.1688 for 3120 observed reflections with I 2σ(I).The complex forms a 3D framework based on rare infinite rod-shaped secondary building units(SBUs),and C-H…π interactions play an important role in stabilizing the 3D supramolecular architecture.It shows excellent catalytic activities for the degradation of safranin O(SO) and methylene blue(MB) dyes in aqueous solution under UV light irradiation.Furthermore,the apparent rate constants have also been investigated.