Synthesis,Crystal Structure and Antitumor Activity of a Ca(Ⅱ) Coordination Polymer Based on 4-Acetylphenoxyacetate Ligands

A novel Ca(Ⅱ) coordination polymer,[Ca L₂(H₂O)₂]_n (1,HL=4-acetylphenoxyacetic acid) has been synthesized with 4-acetylphenoxyacetic acid,Ca(ClO_4)₂·4H₂O and Na OH as raw materials.Complex 1 was characterized by elemental analysis and single-crystal X-ray diffraction analysis.The results show that the Ca(Ⅱ)ion is eight-coordinated in a distorted triangular dodecahedral geometric configuration with six carboxylate Oatoms of four L ligands and two O atoms of two coordinated water molecules.Complex 1 forms a one-dimensional chained structure by the bridging effect of carboxylate O atoms.The antitumor activity of HLligand and complex 1 has also been investigated.     

Synthesis,Crystal Structure and Antitumor Activity of a New Zn(Ⅱ) Complex Based on N-Acetyl-L-phenylalanine and 1,10-Phenanthroline

A new Zn(Ⅱ) complex, [Zn(L)_2(phen)(H_2O)](1, HL = N-acetyl-L-phenylalanine, phen = 1,10-phenanthroline) has been synthesized and characterized by elemental analysis, IR and X-ray single-crystal diffraction analysis. The Zn(Ⅱ) complex belongs to monoclinic, space group P21 with a = 12.6749(13), b = 5.5965(6), c = 22.985(2) ?, β = 104.296(2)°, V = 1580.0(3) ?~3, Z = 2, M_r = 676.02, D_c = 1.421 μg·m~(-3), μ = 0.833 mm~(-1), F(000) = 704, and the final R = 0.0460, wR = 0.0899 for 4422 observed reflections with I 2σ(I). The molecules form a 1D chained structure by hydrogen bonds. The antitumor activities of Zn(Ⅱ) complex against human hepatoma SMMC-7721 cells, human lung adenocarcinoma A549 cells and human colon carcinoma WiDr cells have also been investigated.     

Synthesis, Crystal Structure and Fluorescent Property of a New One-dimensional Cadmium(Ⅱ) Coordination Polymer Based on 3,4-Thiophenedicarboxylic Acid and 1,10-Phenanthroline

A new cadmium(Ⅱ) polymer [Cd(tdc)(Phen)]n 1 (H2tdc = thiophene-3,4-dicar-boxylic acid, Phen = 1,10-phenanthroline) was synthesized under hydrothermal conditions. The compound crystallizes in the triclinic system, space group P , with a = 7.3150(10), b = 10.3598(14), c = 10.8784(15) , α = 82.2740(10), β = 72.9730(10), γ = 80.236(2)°, V = 773.68(18) 3, Z = 2, Mr = 462.74, Dc = 1.986 Mg/m3, μ = 1.58 mm-1, F(000) = 456, the final R = 0.0218 and wR = 0.0465 for 3361 observed reflections with Ⅰ > 2σ(Ⅰ). The compound presents a one-dimensional (1-D) double-stranded structure and exhibits fluorescent emission at room temperature. Furthermore, infrared spectroscopy, elemental analyses, thermogravimetric analysis and powder X-ray diffraction properties of the compound are also investigated.     

A Fe(Ⅱ) Coordination Polymer Based on 1,10-Phenanthroline Derivative and Oxalic Acid:Synthesis,Structure,and Properties

A Fe-based coordination polymer,[Fe(C₂O_4)_0.5(4-NCP)]_n·2nH₂O (1,4-HNCP=2-(4-carboxyphenyl)-1H-imidazo(4,5-f)-(1,10)phenanthroline,H₂C₂O₄=oxalic acid),was hydrothermally synthesized and characterized by infrared spectrum,elemental analysis,single-crystal X-ray diffraction,power X-ray diffraction,and UV-vis absorption spectrum.Structural analyses reveal that polymer 1 possesses a (4,4)-connected 2D network.In addition,1 shows photocatalytic activity toward the degradation of rhodamine B (RhB) in the presence of H₂O₂ under visible light illumination.     

Synthesis,Crystal Structure and Catalytic Properties of a 2D Cobalt(Ⅱ) Coordination Polymer Based on Mixed Ligands

A new Co(II) metal-organic coordination polymer based on flexible bis(imidazole) and aromatic dicarboxylate co-ligands, namely [Co(bix)(nph)]n(H2nph = 3-nitrophthalic acid, bix = 1,4-bis(imidazole-1-ylmethyl)benzene), has been hydrothermally synthesized and characterized by elemental analyses, TG, IR spectroscopy and single-crystal X-ray diffraction. It crystallizes in the triclinic space group P1 with a = 9.3767(14), b = 10.1451(15), c = 12.1488(17), α = 102.6450(10), β = 108.856(2), γ = 98.807(2)°, V = 1035.3(3)3, Z = 2, C22H17 Co N5O6, Mr = 506.34, Dc = 1.624 g/cm3, μ = 0.882 mm-1 and F(000) = 518. In the complex, the nph2- ligands connect neighbouring cobalt atoms to form binuclear [Co(nph)]2 subunits, which are linked by pairs of bix ligands to form a 2D honeycomb-like(6,3) network. In addition, the compound is further extended into a 3D supramolecular architecture by π···π stacking interactions. Moreover, the luminescence and catalytic properties of the complex are investigated.     

Synthesis, Structure and Characterization of Manganese(Ⅱ) Coordination Polymer with Camphoric Acid and 1,10-Phenanthroline

A novel coordination polymer, Mn(H2O)(CA)(Phen)·H2O(CA=camphoric acid, Phen=1,10-phenanthroline), was synthesized and its crystal structure was determined by single crystal X-ray diffraction. Six-coordinated Mn(Ⅱ) atoms are linked with carboxyl groups from camphoric acid ligands to form infinite one-dimensional chains. These chains are packed by means of hydrogen bonding and π-π stacking, forming a three-dimensional structure. IR, thermogravimetric analysis and magnetic susceptibility data for Mn(H2O)(CA)(Phen)·H2O are given.     

Synthesis, Structure and Photoluminescence of a New Cd(Ⅱ)Coordination Polymer Based on 4-(Carboxymethoxy)-benzoic Acid and 1,10-Phenanthroline Derivative

A new 1D coordination polymer, [Cd2(L1)2(L2)2]·H2O (1, H2L1 = 4-(carboxy-methoxy)benzoic acid and L2 = 2-(4-fluorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline), has been hydrothermally synthesized and characterized by elemental analysis and single-crystal X-ray diffraction. It crystallizes in triclinic, space group Pī with a = 9.985(5), b = 10.768(5), c = 12.512(5), α = 68.959(5), β = 80.354(5), γ = 79.663(5)°, V = 1227.4(10) 3, Z = 1, C56H36Cd2F2N8O11, Mr = 1259.73, Dc = 1.704 g/cm3, F(000) = 630, μ(MoKa) = 0.949 mm-1, R = 0.0261 and wR = 0.0655. The L1 anions link the neighboring Cd(II) atoms to form a 1D double chain structure. The L2 ligands are alternately located on both sides of the double chains. More interestingly, the lateral L2 ligands from adjacent double chains are paired to furnish strong π-π interactions, yielding a 2D supramolecular layer. N-H···O, O-H···N and O-H···O hydrogen bonds further stabilize the structure of 1. The luminescent property of 1 was studied in solid state at room temperature.     

Synthesis,Crystal Structure and Photoluminescence of a Copper(Ⅰ)-iodide Coordination Polymer Based on Polyimidazolate Ligand

A copper(Ⅰ)-iodide coordination polymer, namely {[Cu3 I3(Tipa)2]·3(DMF)}n(1), was synthesized from tetrahedral Cu4 I4(py)4 precursor and tris(4-(~1H-imidazol-1-yl)phenyl) amine)(Tipa) ligand in N,N-dimethylformamide(DMF) and methanol, and characterized by single-crystal X-ray diffraction. Its crystal crystallizes in monoclinic system, space group P2/c with a = 12.849(4), b = 12.034(3), c = 24.619(7) ?, β = 104.681(4)°, Mr = 1604.52, V = 3682.4(18) ?3, Z = 2, Dc = 1.447 g/cm3, μ = 2.163 mm-1, S = 0.975, F(000) = 1580, the final R = 0.0835 and wR = 0.2354 for 6471 observed reflections(I 2σ(I)). In compound 1, the Cu4 I4(py)4 was in-situ changed into another neutral CuI unit. Interestingly, two CuI units and two imidazole rings of the tipa ligands form a macrocyclic loop, which are further linked by another CuI unit and the third imidazole ring of the tipa ligands to produce a 1 D loop-containing chain. Solvent molecules were filled in the pore of the loop, which prevents the interpenetration of each other. The packing of these 1 D chains generates a 1 D channel along the a-axis, which is filled by disordered DMF molecules. In addition, compound 1 exhibits high thermal stability and strong photoluminescence at room temperature.     

Synthesis,Crystal Structure and Theoretical Calculations of a New Co(Ⅱ) Coordination Polymer Based on 5-Nitroisophthalic Acid and Bis(imidazol) Ligands

A new complex[Co(NIPH)(mbix)]_n(1,H_2NIPH = 5-nitroisophthalic acid,mbix =l,3-bis(imidazol-l-ylmethyl)benzene) has been hydrothermally synthesized and structurally characterized by elemental analysis,IR spectrum,UV spectrum,TG and single-crystal X-ray diffraction.Pink crystals crystallize in the triclinic system,space group P1 with a = 8.3797(8),b= 10.2522(10),c= 13.4244(13) A,α=94.820(2),β=108.105(2),γ=104.816(2)°,V=1042.84(17) A~3,C_(22)H_(17)CoN_5O_6,M_r = 506.34,D_c = 1.613 g/cm~3,F(000) = 518,Z = 2,μ(MoKα) =0.876 mm~(-1),the final R = 0.0505 and wR = 0.1254 for 3267 observed reflections(I2σ(I)).The structure of 1 exhibits a two-dimensional network structure and is extended into a three-dimensional supramolecule through hydrogen bonds and n-n interactions.In addition,Natural Bond Orbital(NBO) analysis was performed by using the PBE0/LANL2 DZ method built in Gaussian 09 Program.The calculation results showed obvious covalent interactions between the coordinated atoms and Co(Ⅱ) ion.     

Synthesis,Crystal Structure and Theoretical Calculations of a New Two-dimensional Co(Ⅱ) Coordination Polymer Based on Oxalic Acid and Bis(imidazol) Ligands

A new Co(Ⅱ) coordination polymer has been successfully synthesized under hydrothermal conditions [Co(C2O4)(mbix)]n(1, H2C2O4 = oxalic acid, mbix = 1,3-bis(imidazol-1-ylmethyl)benzene). Its structure has been determined by elemental analyses, IR, UV spectroscopy and single-crystal X-ray diffraction analysis. Pink crystals crystallize in the triclinic system, space group P1 with a = 8.8666(7), b = 9.5859(8), c = 10.8537(9) , α = 67.6810(10), β = 66.1260(10), γ = 77.1300(10)°, V = 777.77(11), C16H14CoN4O4, Mr = 385.24, Dc = 1.645 g/cm3, F(000) = 394, Z = 2, μ(Mo Kα) = 1.134 mm-1, the final R = 0.0482 and w R = 0.1231 for 2968 observed reflections(Ⅰ 2σ(Ⅰ)). It shows a two-dimensional(2D) network structure. The intermolecular C–H···O hydrogen bonding and π-π stacking interactions extend complex 1 into a 3D supramolecular architecture andplay an important role in stabilizing 1. In addition, Natural Bond Orbital(NBO) analysis was performed by using the PBE0/LANL2 DZ method built in Gaussian 09 Program. The calculation results showed obvious covalent interaction between the coordinated atoms and Co(Ⅱ) ion.     

Synthesis, Crystal Structure and Thermal Stability of a Saturated Dimeric Ce(Ⅲ)-chelated Complex Based on Benzoate and 1,10-Phenanthroline Ligands

The title complex, [Ce(BA)3phen]2 (BA = benzoate, phen = 1,10-phenanthroline),was prepared by the reaction of Ce(NO3)3·6H2O, benzoic acid and 1,10-phenanthroline. The complex was characterized by single-crystal X-ray diffraction, elemental analysis, IR spectra and TG-DTG techniques. The results show that the crystal is of triclinic, space group P(1) with a =10.912(2), b = 11.962(3), c = 12.474(3)(A), a = 104.889(3), β = 93.523(3), γ = 113.332(3)°,C66H46Ce2N4O12, Mr = 1366.90, V= 1420.2(6) (A)3, Z = 1, Dc = 1.598 g/cm3,μ = 1.652 mm-1, S =1.024 and F(000) = 682. The final R = 0.0391 and wR = 0.0947 for 4878 observed reflections with I ＞ 2σ(1). The structure of the title complex consists of two Ce(C6H5COO)3(C12H8N2) units,forming a binuclear molecule. Each Ce(Ⅲ) is coordinated by two O atoms of one bidentate chelating carboxylate group, five O atoms of two bidentate bridging and two tridentate chelating-bridging carboxylate groups, and two N atoms of one 1,10-phenanthroline molecule to complete a distorted monocapped square antiprism geometry. Its thermogravimetric analysis was determined by TG-DTG techniques.     

Synthesis, Crystal Structure and Thermal Stability of a Saturated Dimeric Ce(III)-chelated Complex Based on Benzoate and 1,10-Phenanthroline Ligands

The title complex, [Ce(BA)3phen]2 (BA = benzoate, phen = 1,10-phenanthroline), was prepared by the reaction of Ce(NO3)3·6H2O, benzoic acid and 1,10-phenanthroline. The complex was characterized by single-crystal X-ray diffraction, elemental analysis, IR spectra and TG-DTG techniques. The results show that the crystal is of triclinic, space group P1 with a = 10.912(2), b = 11.962(3), c = 12.474(3) , α = 104.889(3), β = 93.523(3), γ = 113.332(3)o, C66H46Ce2N4O12, Mr = 1366.90, V = 1420.2(6) 3, Z = 1, Dc = 1.598 g/cm3, μ = 1.652 mm-1, S = 1.024 and F(000) = 682. The final R = 0.0391 and wR = 0.0947 for 4878 observed reflections with I > 2σ(I). The structure of the title complex consists of two Ce(C6H5COO)3(C12H8N2) units, forming a binuclear molecule. Each Ce(III) is coordinated by two O atoms of one bidentate chelating carboxylate group, five O atoms of two bidentate bridging and two tridentate chelating-bridging carboxylate groups, and two N atoms of one 1,10-phenanthroline molecule to complete a distorted monocapped square antiprism geometry. Its thermogravimetric analysis was determined by TG-DTG techniques.     

Synthesis,Structure and Luminescent Properties of a Two-dimensional Cobalt(Ⅱ) Coordination Polymer Based on 2-Thiobarbituric Acid

A two-dimensional coordination polymer [Co(H_2tba)_2(DMF)_2]_n 1(H_2tba = 2-thiobarbituric acid anion, DMF = N,N-dimethylformamide) has been synthesized by Co Cl2·6H2O with the 2-thiobarbituric acid ligands under solvothermal conditions. Compound 1 was further characterized by FTIR, elemental analysis, TGA and powder XRD techniques. Single-crystal X-ray diffraction studies revealed that the title compound crystallizes in the monoclinic space group Pbca with a = 12.5948(12), b = 11.4269(11), c = 14.8939(15) ?, V = 2143.5(4) ?~3, Z = 4, Dc = 1.523 g·cm-3, F(000) = 1012, μ = 1.038 mm~(-1), R = 0.0358 and w R2 = 0.0888(I 2σ(I)). Single-crystal X-ray diffraction analysis reveals that 1 is the first two-dimensional noninterpenetrating(4, 4) net coordination polymer based on the 2-thiobarbituric acid. Coordination polymer 1 exhibits two luminescent emission spectra at 477 and 489 nm with the excitation peak at 273 nm.     

Solvothermal Synthesis,Crystal Structure and Photoluminescence Property of a 3D Lead(Ⅱ) Coordination Polymer Based on Terephthalic Acid

Solvothermal reaction of Pb(NO_3)_2·6H_2O with rigid linear ligand terephthalic acid(H_2pta) in N,N-dimethylformamide(DMF) produced a new three-dimensional(3D) lead(Ⅱ)coordination polymer[Pb_2(pta)_(1.5)(μ4-OH)(DMF)]_n 1,and its structure was characterized by single-crystal X-ray diffraction analyses.In polymer 1,the μ_4-OH bridges the nearby lead(Ⅱ) ions into an infinite one-dimensional(1D) chain,and then the organic ligand pta~(2-) joins the neighbored chains into a 3D structure by two similar connection modes in different configurations.The solid-state photoluminescent studies revealed that 1 exhibits a strong greenish emission mainly originating from ligand-to-metal charge transfer between the delocalized π bonds of the aromatic carboxylate ligand pta~(2-) and the p orbitals of the Pb~(2+) centers.     

Synthesis,Crystal Structure and Luminescent Mechanochromism of a Square-planar Pt(Ⅱ) Complex Based on 1,10-Phenanthroline Derivative

A new square-planar platinum(Ⅱ) complex, [Pt(Me3SiC≡Cphen)(C≡CC6H4Cl-3)2](1), was synthesized by using 3-trimethylsilylethynyl-1,10-phenanthroline(Me3SiC≡Cphen) and 3-chlorophenylacetylene ligands, and its structure was characterized by single-crystal X-ray crystallography. 1 crystallizes in triclinic, space group P1 with a = 6.9524(5), b = 12.7796(11), c = 17.5846(10) ?, α = 78.484(5), β = 88.700(5), γ = 75.600(6)°, V = 1482.23(19) ?3, Z = 2, C33H24Cl2N2 PtSi, Mr = 742.62, Dc = 1.664 g/cm3, F(000) = 724, μ(Mo Ka) = 4.979 mm-1, R = 0.0369 and wR = 0.0786. In 1, adjacent molecules along the a axis are stacked in a columnar structure through π···π interactions, and such neighboring columnar structures are connected with each other by C–H···π hydrogen bonds to form a 2D supramolecular network. 1 exhibits reversible luminescence mechanochromic property with the luminescence red shift in a range of ca. 146~182 nm. Extremely large red-shifts of luminescence spectra suggest that luminescent mechanochromic property of 1 is due to the formation of aggregate via Pt–Pt interaction during the mechanical grinding. Based on this property, a simple device was developed and used for rewritable data storage.     

Syntheses,Crystal Structure and Luminescent Properties of a Novel Mn(Ⅱ) Coordination Polymer Based on 1,3,5-Benzenetricarboxylic Acid

Coordination polymers are a novel class of crystalline materials, which have attracted a huge amount of interest in recent decades. We selected an organic ligand 1,3,5-benzenetricarboxylic acid(H_3 BTC) to assemble with Mn(Ⅱ) ions to construct a novel Mn(Ⅱ) coordination polymer crystal material(namely complex 1). The resultant sample was successfully synthesized under the solvothermal reaction. Complex 1 possesses a three-dimensional(3D) framework based on two different Mn(Ⅱ) clusters: [Mn_4(COO)_8] and [Mn_2(COO_4)]. Furthermore, the resultant sample can be characterized in detail by powder X-ray diffraction(PXRD), Fourier-transform infrared spectra(FT-IR), thermal gravimetric analyses(TGA), elemental analysis(C, H and N) and luminescence.     

Synthesis,Crystal Structure and I_2 Capture of a Cd(Ⅱ) Coordination Polymer Based on a Linear Bipyridyl Benzene Ligand

A new complex with formula [Cd(3-pbpmb)_2 I_2]_n 1(3-pbpmb = 1,4-bis(pyridine-3-ylmethoxy)benzene), has been solvothermally synthesized and characterized. The crystal belongs to monoclinic system, space group P21/n with a = 8.2905(17), b = 16.078(3), c = 13.213(3) ?, β = 99.44(3)°, Mr = 950.86, V = 1737.3(6) ?~3, Z = 2, Dc = 1.818 g/cm~3, F(000) = 924, m = 2.450 mm~(-1), the final R = 0.0198 and w R = 0.0467 for 3053 observed reflections(I 2σ(I)). The Cd(Ⅱ) ion is coordinated by four N atoms of four 3-pbpmb ligands and two iodine ions to furnish a distorted octahedral coordination geometry. The Cd(Ⅱ) ion and its own symmetry-related ions are bridged by N atoms from two 3-pbpmb ligands to generate a zigzag 1-D chain coordination polymer. These 1D chains are further connected into a three-dimensional(3D) framework by C–H×××pinteractions and intermolecular C–H×××I hydrogen bond. Interestingly, 1 displays efficient sorption of molecular iodine gas(up to 111 wt%), but invalid sorption of molecular water gas.     

Synthesis, Crystal Structure and Thermal Stability of a Saturated Dimeric Ce（III）-chelated Complex Based on Benzoate and 1,10-Phenanthroline Ligands

The title complex, [Ce（BA）3phen]2 （BA = benzoate, phen = 1,10-phenanthroline）, was prepared by the reaction of Ce（NO3）3.6H2O, benzoic acid and 1,10-phenanthroline. The complex was characterized by single-crystal X-ray diffraction, elemental analysis, IR spectra and TG-DTG techniques. The results show that the crystal is of triclinic, space group P1 with a = 10.912（2）, b = 11.962（3）, c = 12.474（3） A, α = 104.889（3）, β = 93.523（3）, γ = 113.332（3）^o, C66H46Ce2N4O12, Mr = 1366.90, V= 1420.2（6） ,A^3, Z = 1, Dc = 1.598 g/cm^3, μ = 1.652 mm^-1, S = 1.024 and F（000） = 682. The final R = 0.0391 and wR = 0.0947 for 4878 observed reflections with I 〉 2σ（I）. The structure of the title complex consists of two Ce（C6HsCOO）3（C12H8N2） units, forming a binuclear molecule. Each Ce（Ⅲ） is coordinated by two O atoms of one bidentate chelating carboxylate group, five O atoms of two bidentate bridging and two tridentate chelating-bridging carboxylate groups, and two N atoms of one 1,10-phenanthroline molecule to complete a distorted monocapped square antiprism geometry. Its thermogravimetric analysis was determined by TG-DTG techniques.