M2（pbtcH）（phen）2（H2O）2 [M（II）= Co,Ni]：Mixed-ligated metal phosphonates based on 5-phosphonatophenyl-1,2,4-tricarboxylic acid showing double chain structures

Two new mixed-ligated metal phosphonates, M2（pbtcH）（phen）2（H2O）2 [M（Ⅱ）=Co （1）, Ni （2）] （pbtcH5 = 5-phosphonatophenyl-1,2,4-tricarboxylic acid, phen = 1,10-phenanthroline）, have been syn- thesized and characterized. Both show one-dimensional double chain structures, where the M（phen）（H2O） moieties are chelated and bridged by pbtcH4 through the carboxylate and phosphonate oxygen atoms. The chains are connected by hydrogen bonding interactions and π-π stacking, forming a three-dimensional supramolecular structure. The IR and magnetic properties of the two compounds are also investigated.     

Synthesis,Crystal Structure and Luminescence Property of [MnL2（bipy）（H2O）2]n

A new one-dimensional Mn（Ⅱ） complex, [MnL2（bipy）（H2O）2]n 1, has been obtained by the reaction of MnCl2·4H2O, 2,2＇-bipyridine （bipy） and 1-（4-phenoxyacetate）-5-thioacetatetetrazole （H2L）. The crystal crystallizes in the triclinic system, space group Pi with a = 7.6088（2）, b = 12.2795（2）, c = 13.6617（3）A, α = 75.416（2）, β =79.264（2）, γ = 74.271（2）°, V = 1179.48（4） A3, Z = 2, Mr = 555.43, F（000） = 570, Dc = 1.564 g/cm^3, μ = 0.704 mm^-1, the final R = 0.0454 and wR = 0.0849 for 3127 observed reflections （Ⅰ〉 2σ（Ⅰ））. The Mn（Ⅱ） is six-coordinated by two water molecules, two N atoms from bipy and two carboxylate O atoms from two L^2- to form a distorted octahedral geometry. Each L^2- ligand serves as a bridging ligand to link two Mn（Ⅱ） atoms, leading to a single-strand zigzag coordination polymer. Hydrogen-bonding interactions between adjacent chains as well as π-π stacking interactions extend the complex into a three-dimensional supramolecular architecture. Moreover, the title compound emits strong red fluorescent light （λem（max） = 610 nm） in EtOH solution.     

Synthesis and Structure of 1.5Zn（phen）3·L·3NO3 Supramolecule （phen = o-Phenanthroline,L = 4-Aminoacetophenone Thiosemicarbazone）

A supramolecular framework, 1.5Zn（phen）3·L·3NO3 （C63H48Zn1.5N16O9S）, has been synthesized. The ligand L was synthesized by the condensation of p-aminoacetophenone with thiosemicarbazide. The crystal belongs to the monoclinic system, space group C2/c, with a = 31.005（2）, b = 15.114（2）, c = 24.887（3） A, β = 94.260（2）° Z = 8, V = 11630（2）A^3 Dc = 1.489 g/cm^3, Mr = 1303.29,λ（MoKa） = 0.71069 A,μ= 0.735 mm^-1, F（000） = 5368, Rint = 0.0699, R= 0.0505 and wR= 0.0707. Two independent Zn atoms are both coordinated by six N atoms from three phen ligands. π-π and C-H…π interactions among the L ligands and Zn（phen）3 cations, π-π and C-H...π interactions among the Zn（phen）3 cations and N-H...O hydrogen bonds among the L ligands and nitrate anions connect the whole structure into a 3-D supramolecular framework.     

Synthesis and Crystal Structure of a Coordination Polymer [Zn（p-pdoa）（bbp）]n with a One-dimensional Helical Chain

The coordination polymer [Zn（p-pdoa）4（bbp）]n 1 （p-pdoa = p-phenylenedioxydiacetate dianion and bbp = 2,6-bis（benzimidazol-2-yl）pyridine） has been synthesized by hydrothermal method and characterized by elemental analysis, IR and X-ray single-crystal diffraction. The title complex crystallizes in the triclinic system, space group P1^- with a = 7.8383（2）, b = 12.6610（4）, c = 13.1792（5）A, a = 84.433（2）,β = 74.2980（1）, γ = 87.4290（1）°, V = 1252.93（7）A^3, Z = 2, Dc = 1.593 g/cm^3,/z = 1.038 mm^-1, F（000） = 616, the final R = 0.0361 and wR = 0.1139. The Zn（Ⅱ） atom assumes a distorted trigonal bipyramidal geometry, involving two carboxyl O atoms from two different p-pdoa ligands and three N atoms from the bbp ligand. The Zn（Ⅱ） atom is alternately interlinked by p-pdoa ligands in a bismonodentate mode into a helical chain with a long pitch of 12.661 A and the adjacent Zn…Zn distance of 11.056 and 12.245 A. There exists a 2D supramolecular framework linked by π-π stacking （3.312 A） between adjacent benzimidazoles of bbp ligands and intermolecular hydrogen-bonding interactions between the uncoordinated carboxylate oxygen atoms （O（2）, 0（5）） and the uncoordinated imidazolyl N atoms （N…O distances 2.706 and 2.786 A）. There also exist two interlayer π-π stacking interactions of 3.299 A between adjacent central pyridines of bbp ligand and 3.176 A between the phenyl groups of p-pdoa ligand. Such π-π stacking interactions extend the two-dimensional layers into a 3D supramolecular network.     

Synthesis of a New Two-dimensional Cd（Ⅱ） Coordination Compound by Benzotriazole-5-carboxylate Acid and 1,10-Phenanthroline and Its Crystal Structure and Characterization

A mixed-ligand metal-organic complex [Cd（C7H3N3O2）（C12H8N2）]n was synthesized by cadmium（Ⅱ） nitrate, 1,10-phenanthroline（phen） and benzotriazole-5-carboxylate acid（H2btca）. Single crystal X-ray analysis indicates that complex 1 has a two-dimensional layer structure and crystallizes in an orthorhombic space group（Pbca）, with cell parameters, a=1.7422（6） nm, b=0.9264（3） nm, c=2.0729（7） nm, α=90°, β=90°,γ=90°, V=3.346（2） nm^3, Z=8. Each central Cd（Ⅱ） is six-coordinated by four N atoms, two of which are from 1,10-phenanthroline, and the other two from two different triazole nitrogen atoms and two O atoms from benzotriazole-5-carboxylate, forming a distorted octahedral geometry. Adjacent Cd（Ⅱ） centers are bridged by benzotriazole-5-carboxylate molecules to form a one-dimensional chain, which is further connected by the nitrogen atoms of btca^2- to form an extended two-dimensional wave-like layer, with OFF（offset face-to-face） stacking interactions between phen ligands in adjacent layers, which are helpful to forming the three-dimensional supramolecular structure.     

Synthesis and Crystal Structure of a Manganese（Ⅱ） Complex with 2-（4′-Chlorine- benzoyl）-benzoic Acid and 1,10-Phenanthroline

A new metal-organic complex Mn2（cbba）4（phen）2 （Hcbba = 2-（4＇-chlorine-benzoyl）- benzoic acid, phen = 1,10-phenanthroline） 1 has been hydrotherrnally synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analyses and IR spectroscopy. The compound crystallizes in orthorhombic, space group Pbcn with α = 12.154（5）, b = 18.166（7）, c = 31.197（13） A, V = 6887（5） A^3, C80H48Cl4Mn2N4O12, Mr= 1508.90, Dc = 1.455 g/cm^3, μ（MoKα） = 0.591 mm^-1, F（000） = 3080, Z = 4, the final R = 0.0408 and wR = 0.0873 for 4033 observed reflections （I 〉 2σ（I））. In the crystal structure, the manganese atom is six-coordinated with four carboxylate oxygen atoms from three different cbba ligands and two nitrogen atoms from phen ligands, showing a distorted octahedral geometry. Furthermore, it exhibits a 3D supramolecular network through π-π interactions.     

Synthesis and Crystal Structure of a New Threedimensional Thiocyanate Supramolecular Compound [Cd（phen）（NCS）（SCN）]n

The compound [Cd（phen）（NCS）（SCN）]n（phen = 1,10-phenanthroline） was synthe- sized under hydrothermal conditions and characterized by IR and single-crystal X-ray diffraction. The complex is of monoclinic, space group C2/c with a = 14.607（3）, b = 10.505（2）, c = 10.631（2）A,β = 115.14（3）^o, V = 1476.8（5）A^3, C14H8CdN4S2, Mr = 408.76, Z = 4, F（000） = 800, μ = 1.757 mm^-1 and Dc = 1.839 g/cm^3. The final R = 0.0409 and wR = 0.0811 for 1367 observed reflections （I 〉 2σ（I））. In the title compound, each cadmium atom is six-coordinated and connected with two adjacent metal ions by two NCS bridges, creating a zigzag chain. The neighboring chains are linked to each other by the weak van der Waals＇ S…S interactions and π…π interactions to form a new three-dimensional supramolecular framework.     

Crystal Structure,Thermal Behavior and Luminescence of a One-dimensional Coordination Polymer [Zn（4-CPOA）（Phen）（H2O）]n

A novel coordination polymer of [Zn（4-CPOA）（Phen）（H2O）]n （C21H16N2O6Zn,1,4-CPOA = 4-carboxylato-phenoxyacetate dianion and Phen = 1,10-phenanthroline） has been synthesized and characterized by elemental analysis,IR,TG,PL and single-crystal X-ray diffraction. The crystal crystallizes in the triclinic system,space group of P1 with a = 9.622（3）,b = 9.631（3）,c = 11.526（4）A,α = 67.719（5）,β = 71.203（5）,γ = 83.552（6）o,V = 935.5（5） A^3,Z = 2,Dc = 1.625 g/cm^3,μ = 1.357 mm^-1 and F（000） = 468. The Zn（II） ion is surrounded by three carboxylate O atoms from two different 4-CPOA groups,two N atoms from the Phen ligand and one water molecule,forming a distorted octahedral coordination configuration. The Zn（II） ions were alternately interlinked by carboxylate groups of 4-CPOA with chelating bisbidentate and monodentate modes into a one-dimensional zigzag chain having an intrachain distance of ca. 9.631（1） . Under the direction of supramolecular recognition and attraction,the adjacent chains yield a double-stranded chain through π-π stacking between the phen ligands,which was further expanded into a 2-D framework via strong C–H–π interaction （ca. 2.95（1） ） between the 4-CPOA ligands and into a 3-D supramolecular network by strong hydrogen bond between terminal water molecule and carboxyl group. TG/DTG shows that its chain skeleton is thermally stable up to 419 oC and the blue fluorescent emission of the complex was determined at 471 nm in a solid state with its long decay lifetime of 1.83 ns.     

Synthesis and Crystal Structure of a Novel Tetranuclear Zinc（Ⅱ） Coordination Polymer [Zn4（o-bda）4（p-pbim）4]n

A novel tetranuclear zinc（H） coordination polymer [Zn4（o-bda）a（p-pbim）4]n 1 （p-pbim = 4-pyridylbenzimidazole, o-bda2 = o-phenylenediacetic acid dianion） has been synthesized by a hydrothermal method and characterized by elemental analysis, IR and X-ray singlecrystal diffraction. The title complex crystallizes in monoclinic, space group of P21/n with α = 14.231（1）, b = 16.257（1）, c = 16.794（1） ]k, β = 100.26（1）°, V = 3823.1（2）A3, Z = 8, Dc = 1.573 g/cm^3,β = 1.321 mm^-1, F（000） = 1856, R = 0.0420 and wR = 0.111. The Zn（1） atom assumes a distorted trigonal bipyramidal geometry, involving three carboxyl O atoms from two different o-bda ligands and two N atoms from two p-pbim ligands. The Zn（2） atom is coordinated by two oxygens from two distinct bda2- anions and two nitrogen atoms from two p-pbim ligands to form a distorted tetrahedral geometry. The Zn（Ⅱ） atoms are alternately interlinked by o-bda ligands in bis-monodentate or chelating-bidentate and monodentate modes into one-dimensional undulate chains along axis c with the adjacent Zn…Zn distances of 8.32 and 8.47 A. Such neighboring chains are further extended into a 1D bi-chain structure with two different subrings A and B, which are 32- and 14-membered rings through interchain p-pbim ligands. There exists a 2D supramolecular network linked by intermolecular hydrogen-bonding interactions between the uncoordinated carboxylate 0（4） atom or coordinated carboxylate 0（7） atom and the uncoordinated imidazolyl N（2） and N（5） atoms with the O...N distances to be 2.695 and 2.807A.     

Synthesis and Single-crystal Structure of a One-dimensional Zinc（Ⅱ） Phosphonate： [Zn3（PhPO3）2（PhPO3H）2（Phen）2]n

A new Zn（II） phosphonate complex, [Zn3（PhPO3）2（PhPO3H）2（Phen）2]n （Phen = 1,10-phenanthroline）, has been synthesized and structurally determined by X-ray single-crystal diffraction. The complex crystallizes in the monoclinic system, space group C2/c with a = 14.997（3）, b = 18.108（4）, c = 17.237（3） A, β = 96.61（3）°, V = 4649.9（16） A3, Z = 4, C48H38N4O12P4Zn3, Mr = 1182.87, Dc = 1.690 g/cm3^,μ = 1.743 mm^-1, F（000） = 2400, the final R = 0.0363 and wR = 0.0963. In the structure, the connectivity between two 5-coordinated Zn（II） atoms and four phosphonates as well as two Phen ligands form a Zn2（PhPO3H）2（PhPO3）2（Phen）2 unit, and such a neighboring unit is bridged by 4-coordinated Zn（II） to give rise to a 1D chain along the c axis. The π-π stacking interactions between Phen rings assemble adjacent chains packed together to form a 3D supermolecular architecture.     

之字链聚合物[Zn(o-bda)(phen)(H2O)]n·nH2O的结构

[Zn(o-bda)(phen)(H₂O)]_n·nH₂O (C22H20N2O6Zn) (1) [where o-bda is o-phenylenediacetic acid dianion and phen is 1,10-phenanthroline] crystallizes in triclinic system, space group P1 with a=0.826 5(4) nm, b=1.042 4(5) nm, c=1.238 1(6) nm, α=76.987(9)°, β=70.987(9)°, γ=78.281(8)°, V=0.9728(8) nm³, Z=2, D_c=1.617 g·cm^-3, μ=1.308 mm^-1 and F(000)=488. Zn(Ⅱ) ion has a distorted trigonal bipyramid coordination geometry formed by two carboxyl O atoms from two different o-bda groups, two N atoms from the phen ligand and one terminal water molecule. Adjacent Zn(Ⅱ) ions are interlinked by o-bda groups into a infinite zigzag chain structure with a Zn…Zn distance of 0.825 6(4) nm. The adjacent zigzag chains may also be paired under direction of supramolecular recognition and attraction through both π-π stacking and hydrogen bonding interactions into molecular zippers, which further interlinked into a three-dimensional supramolecular network by these noncovalent interactions. CCDC: 600935.     

一维链状锰配位聚合物的合成、晶体结构与性能研究

本文合成了1个新的一维链状锰的配位聚合物{[Mn(HL)(phen)(H2O)2].1.5H2O}n,(H3L=2-羟基-5-羧基苯磺酸),并且进行了元素分析、红外、热重、荧光、紫外、粉末XRD及单晶X射线衍射等表征及研究。标题化合物属于单斜晶系,C2/c空间群,a=0.840 57(17)nm,b=1.757 5(4)nm,c=2.873 4(6)nm,β=92.54(3)°,V=4.240 7(16)nm 3,Z=4,R=0.027 0。每个Mn(Ⅱ)离子与邻菲咯啉配体的2个N原子、磺酸配体中的1个磺酸基O原子和羧基O原子以及2个配位水分子配位,展示出扭曲的八面体几何构型。2个相邻的Mn(Ⅱ)八面体单元通过1个磺酸基氧原子和1个羧基氧原子连接形成一维链状结构,该一维链进一步通过氢键作用构筑成三维网状结构。     

Synthesis and Structure of 1.5Zn(phen)_3·L·3NO_3 Supramolecule(phen=o-Phenanthroline,L=4-Aminoacetophenone Thiosemicarbazone)

A supramolecular framework,1.5Zn(phen)3·L·3NO3(C63H48Zn1.5N16O9S),has been synthesized.The ligand L was synthesized by the condensation of p-aminoacetophenone with thiosemicarbazide.The crystal belongs to the monoclinic system,space group C2/c,with a = 31.005(2),b = 15.114(2),c = 24.887(3) ,β = 94.260(2)o,Z = 8,V = 11630(2) 3,Dc = 1.489 g/cm3,Mr = 1303.29,λ(MoKα) = 0.71069 ,μ = 0.735 mm-1,F(000) = 5368,Rint = 0.0699,R = 0.0505 and wR = 0.0707.Two independent Zn atoms are both coordinated by six N atoms from three phen ligands.π-π and C-H···π interactions among the L ligands and Zn(phen)3 cations,π-π and C-H···π interactions among the Zn(phen)3 cations and N-H···O hydrogen bonds among the L ligands and nitrate anions connect the whole structure into a 3-D supramolecular framework.     

配合物[Cu2(C4H2O6)(Phen)2(H2O)]·8H2O的合成、晶体结构和抗菌活性

在pH≈10的乙醇-水溶液中以硫酸铜、酒石酸和邻菲咯啉反应合成了分子式为[Cu₂(C₄H₂O₆)(Phen)₂(H₂O)]·8H₂O的配合物单晶。用X-射线单晶衍射测定了晶体结构，并研究了配合物对大肠杆菌、金黄色葡萄球菌、枯草杆菌的抗菌活性。晶体属单斜晶系，空间群P2₁。标题化合物为双核铜配合物，2个铜原子配位数不同。Cu(1)是五配位的，具有扭曲的四方锥结构，5个配位原子分别是酒石酸的去质子的羟基氧和羧基氧、邻菲咯啉的2个氮原子及1个水分子的氧原子。Cu(2)为四配位的，配位原子分别是酒石酸的去质子的羟基氧和羧基氧和邻菲咯啉的2个氮原子。分子中Cu(1)…Cu(2)间的距离为0.354 8 nm。存在分子内邻菲咯啉-邻菲咯啉的面—面π-π相互作用，面间距为0.381 3 nm。配合物对大肠杆菌、金黄色葡萄球菌、枯草杆菌具有较强的抗菌活性。     

[Ag(4，4′-bpy)]+及[Zn(phen)2(H2O)2]2+两种配合物的合成、结构与荧光性质

用水热法和溶液法分别合成了2个新的配合物{[Ag(4,4′-bpy)]·3-HSBA.H2O}n(1)和[Zn(phen)2(H2O)2]·(A-2,5-DSA)·3H2O(2)(3-HSBA=3-羧基苯磺酸根,A-2,5-DSA=苯氨-2,5-二磺酸根,4,4′-bpy=4,4′-联吡啶,phen=1,10-邻菲咯啉),用X-射线单晶衍射结构分析方法测定了其晶体结构。配合物1是一维链状结构。在1个不对称单元中包含1个[Ag(4,4′-bpy)]+阳离子,1个3-羧基苯磺酸根阴离子和1个晶格水分子。Ag髣离子与2个4,4′-联吡啶的2个氮原子配位。配合物2是单核结构。在1个不对称单元中包含1个[Zn(phen)2(H2O)2]2+阳离子,1个苯氨-2,5-二磺酸根阴离子和3个晶格水分子。Zn髤离子与2个1,10-邻菲咯啉的4个氮原子和2个水氧原子配位。配合物1和2中,配位阳离子、抗衡阴离子以及晶格水分子之间存在丰富的氢键,进而构筑成超分子网络结构。配合物的荧光均来自于配体的π-π*电子跃迁。     

Studies on cage-type tetranuclear metal clusters with ferrocenylphosphonate ligands

Reaction of FcCH(2)PO(3)H(2) [Fc=(eta(5)-C(5)H(5))Fe(eta(5)-C(5)H(4))] (H(2)FMPA) and 1,10-phenanthroline (phen) with Cd(OAc)(2).2 H(2)O or ZnSO(4).7 H(2)O in methanol in the presence of triethylamine resulted in the formation of two new ferrocenylphosphonate metal-cage complexes [M(4)(fmpa)(4)(phen)(4)] 7 CH(3)OH (M=Cd 1, M=Zn 2). Both structures contain two kinds of isomeric tetranuclear metal phosphonate cages, which are linked to one another by pi-pi interactions between the phen molecules. In 1, the Cd1, Cd3, and Cd4 atoms are all pentacoordinate, while the Cd2 atom is coordinated by four oxygen atoms from three phosphonate ligands and two nitrogen atoms from the chelating phen in a distorted octahedral geometry. Four Cd atoms from each unit are interconnected through bridging phosphonate ligands with different coordination modes, such as 5.221, 4.211, and 2.11 (Harris notation), yielding a {Cd(4)} cage. In 2, each Zn atom is coordinated by three oxygen atoms from three phosphonate ligands and two nitrogen atoms from phen, leading to a distorted square-pyramidal geometry. The four Zn atoms of each isomeric unit are also interconnected through four bridging phosphonate ligands to yield a {Zn(4)} cage. Fluorescent studies indicate that ligand-to-ligand charge-transfer photoluminescence is observed for 1, while the emission bands of 2 can be assigned to an admixture of ligand-to-ligand and metal-to-ligand charge transfer. Solution-state differential pulse voltammetry indicates that the half-wave potentials of the ferrocenyl moieties in 1 and 2 have different deviations relative to the relevant H(2)FMPA ligand. This may be because the highest occupied molecular orbital (HOMO) in 1 is located in the FMPA(2-) groups, while in 2 the HOMO is located in the phen and Zn(II) groups, so the Fe(II) centers in complex 1 are more easily oxidized to Fe(III) centers than those of 2. The third-order nonlinear optical (NLO) measurements show that both 1 and 2 exhibit strong third-order NLO self-focusing effects; hence, they are promising candidates for NLO materials. By calculating the component of the lowest unoccupied molecular orbitals of 1 and 2, we confirmed that the co-planar phen rings control their optical nonlinearity, while the H(2)FMPA ligands and metal ions have only a weak influence on their NLO properties.     

Synthesis and Crystal Structure of a Zinc(II) Complex with 2-(4′-Chlorine-benzoyl)-benzoic Acid and 1,10-Phenanthroline

A new metal-organic complex Zn2(cbba)4(phen)2 (Hcbba = 2-(4′-chlorine-ben-zoyl)benzoic acid, phen = 1,10-phenanthroline) 1 has been hydrothermally synthesized and structurally characterized by elemental analysis, IR, fluorescence spectrum and single-crystal X-ray diffraction. The compound crystallizes in orthorhombic, space group Pbcn with a = 12.0821(11), b = 18.3140(17), c = 30.961(3), V = 6850.7(11)3, C80H48Cl4N4O12Zn2, Mr = 1529.76, Dc = 1.483 g/cm3, μ(MoKα) = 0.925 mm?1, F(000) = 3120, Z = 4, the final R = 0.0559 and wR = 0.1146 for 3963 observed reflections (I > 2σ(I)). In the crystal structure, the zinc atom is five-coordinated with three carboxylate oxygen atoms from three different cbba ligands and two nitrogen atoms from the phen ligand, showing a distorted square-pyramidal geometry. Furthermore, it exhibits a 3D supramolecular network through π-π interactions and shows yellow photoluminescent property at room temperature.     

1，4-苯二硫乙酸配体构筑的锌(Ⅱ)及镉(Ⅱ)配合物的合成、晶体结构及荧光性质

基于1,4-苯二硫乙酸(H2L)及中性含氮配体,水热法合成了两个新的d10金属配合物[ZnClL0.5(bpp)](1)和[Cd2L(phen)4(H2O)2].L.2.78H2O(2)(bpp=1,3-di(4-pyridyl)propane,phen=1,10-phenanthroline),并通过单晶X-射线衍射、元素分析、红外光谱和热重对其结构进行了表征。结构分析表明,在配合物1中,Zn(Ⅱ)呈现四配位的扭曲四面体构型,进一步连接形成一维双链状结构。在配合物2中,Cd(Ⅱ)呈现六配位的扭曲八面体构型,并通过可能存在的氢键及π-π堆积作用,形成最终的三维超分子结构。同时,讨论了两种配合物的固体荧光性质。