三维配位聚合物[Zn(HCO2)2(4,4''-bipy)]∞的合成、晶体结构及性质研究

以ZnO,HCO2H及4,4-bipy(摩尔比131.25)溶于H2O和DMF(体积比131),并在60℃反应,合成了标题化合物[Zn(HCO2)2(4,4'-bipy)∞,对其进行了元素分析、红外光谱等表征,并测定了晶体结构.该化合物晶体属四方晶系,P43212空间群,a=b=0.79675(5)nm,c=1.7627(2)nm,V=1.1190(3)nm3,Z=4,Dc=1.850 g/cm3,Mr=311.60,F(000)=632,μ=22.07 cm-1,最终偏离因子R1=0.0183和wR2=0.0483.该化合物中Zn原子和两个4,4'-bipy的N原子和四个甲酸根的O原子配位,形成的ZnN2O4八面体通过4,4'-bipy和甲酸根桥联,组成一种新颖的3D网络结构.同时,研究了该化合物的热性质和荧光性质.     

一维链状配位聚合物[Zn（acac）2（4,4＇-bipy）]n的合成、表征及量子化学研究

以Zn（ClO4）2·6H2O,4,4＇-联吡啶及乙酰丙酮（物质的量比1∶1∶2）在甲醇中通过溶剂热法合成得到了标题聚合物[Zn（acac）2（4,4＇-bipy）]n.经元素分析、红外光谱、核磁共振氢谱、热重及X射线单晶衍射等表征,其晶体属单斜晶系,P2（1）/c空间群,晶胞参数：a=1.1366（10）nm,b=1.4914（14）nm,c=1.5534（10）nm,β=132.00（4）°,V=1.957（3）nm^3,Z=4.标题聚合物分子由Zn（acac）2与4,4＇-bipy是以分子比1∶1形成一维无限的链状结构.热重分析结果表明,聚合物在197℃以下稳定性良好.运用Gaussian03W对聚合物结构单元进行了量化计算分析,原子电荷分布及前沿占据轨道组成很好地佐证了晶体结构的配位环境.     

Syntheses and Structures of Two New Cobalt Supramolecular Complexes, [Co（4,4＇-bipy）2（H2O）4]·[Co2（4,4＇-bipy）3（H2O）8]·2TST·2（4,4＇-bipy）·4H2O and [Co（4,4＇-bipy）2（H2O）4]DSNT·4,4＇-bipy

Two new cobalt（II） supramolecular complexes [Co（4,4＇-bipy）2（H2O）4]·[Co2（4,4＇-bipy）3（H2O）8]·2TST·2（4,4＇-bipy）·4H2O 1 and [Co（4,4＇-bipy）2（H2O）4]DSNT·4,4＇-bipy 2 based upon the assembly of Co（II）, 4,4＇-bipyridine （4,4＇-bipy） and two new multifunctional organic ligands, 2,4,6-tris（4-sulfophenyl- amino）-1,3,5-triazine （H3TST） and 2,4-bis（p-sulfanilato）-6-diethylamino-1,3,5-triazine （H2DSNT）, have been prepared by hydrothermal method and characterized by elemental analysis, IR spectrum, and single-crystal X-ray diffraction. The crystal structure of 1 is of monoclinic, space group P21/n with a = 13.599（4）, b = 18.988（6）, c = 22.995（7） A, β = 90.273（6）°, V = 5938（3）A^3, Z = 4, C56H59Co1.5N13O17S3, Mr = 1370.74, Dc = 1.533 g/cm^3, μ = 0.613 mm^-1, F（000） = 2842, GOOF = 1.018, the final R = 0.0796 and wR = 0.1498 for 9019 observed reflections with I 〉 2σ（I）. The crystal structure of 2 belongs to the monoclinic system, space group C2/c with a = 18.864（6）, b = 14.283（5）, c = 20.246（7）A, β = 107.799（6）°, V = 5194（3）A^3, Z = 4, C49H52CoN12O10S2, Mr = 1092.08, Dc = 1.397 g/cm^3, μ = 0.480 mm^-1, F（000） = 2276, GOOF = 1.059, the final R = 0.0665 and wR = 0.1900 for 4887 observed reflections with I 〉 2σ（I）. The results of X-ray crystal structure analysis revealed that complexes 1 and 2 exhibit layered supramolecular frameworks stabilized by electrostatic interactions, π-π interactions and hydrogen bonds.     

新颖的（4,4′-bipy）{[Ag（4,4′-bipy）]3·[PMo12^ⅥO40]}·H2O三维超分子多金属氧酸盐的合成和晶体结构

利用H3PMo12O40.4H2O,4,4′-bipy和AgNO3反应,在中温水热条件下合成了一种新颖的三维超分子多金属氧酸盐（4,4′-bipy）{[Ag（4,4′-bipy）]3[PMo12^ⅥO40]}.H2O（1）,并通过元素分析、红外光谱、热重分析和X射线单晶衍射对其结构进行了表征.结果表明,该化合物属三斜晶系,P^-1空间群,晶胞参数a=1.1275（2）nm,b=1.1910（2）nm,c=1.2898（3）nm,α=112.63（3）°,β=94.63（3）°,γ=99.53（3）°,V=1.5567（5）nm^3,Z=1.该化合物具有三维超分子结构及荧光性质.     

有机-无机复合物[Cu（en）（H_2O）（2,2-′bipy）]_2H_3[BW_（12）O_（40）]·2.5H_2O的水热合成、结构及性质

利用水热合成方法制备了组成为[Cu（en）（H2O）（2,2′-bipy）]2H3BW12O4.02.5H2O的多金属氧簇有机-无机复合物,并用元素分析、IR和UV光谱、XPS、TG、荧光光谱、X射线单晶衍射对化合物进行了表征和性质研究.该化合物属于单斜晶系,P2（1）/c空间群,a=1.951 1（2）nm,b=1.229 76（12）nm,c=2.505 9（3）nm,β=91.266（2）°,V=6.011 1（11）nm3,Z=4.化合物阴离子[BW12O40]5-与配位阳离子[Cu（en）（H2O）（2,2′-bipy）]＋通过静电作用相结合.XPS表明化合物中Cu、W氧化态分别为＋1和＋6价.     

Synthesis, Crystal Structure and Electrochemical Properties of One-dimensional Chain Coordination Polymer [Co（Ⅱ）（C6H5CH=CHCOOH）2（4,4＇-bipy）（H2O）5]n

A one-dimensional chain coordination polymer [Co（Ⅱ）（C6H5CH--CHCOOH）2（4,4＇- bipy）（H20）5]n has been synthesized with cinnamylic acid, 4,4＇-bipy and cobaltous chloride as raw materials. Crystal data for this complex： monoclinic, space group P21/c, a = 1.1481（3）, b = 1.1230（2）, c = 1.1759（3） nm, β = 97.054（4）^o, V= 1.5046（6） nm^3, Mr= 617.50, Dc = 1.363 g/cm^3, Z = 2, ,u（MoKa） = 0.627 mm^-1, F（000） = 646, S = 1.062, R 0.0443 and wR = 0.1178. The crystal structure shows that two neighboring cobalt（ID ions are linked together by one 4,4＇-bipy, and the whole complex molecule adopts a one-dimensional chain structure. Each cobalt（H） ion is coordinated with two nitrogen atoms from two 4,4＇-bipy molecules and four oxygen atoms from four water molecules, giving a distorted octahedral coordination geometry. The electrochemical properties were analyzed by combining with the crystal structure.     

[Zn2（C7H8O6）2（bipy）2（H2O）2]·4H2O手性配位聚合物的合成与晶体结构

采用溶剂热技术合成了一种新型手性配位聚合物[Zn2（C7H8O6）2（bipy）2（H2O）2]·4H2O（C7H8O6=2,3-氧-异丙叉基-L-酒石酸根,bipy=4,4′-联吡啶）,并通过单晶X射线衍射结构分析、元素分析、热重分析以及红外光谱进行了表征.结构分析数据表明,该化合物属单斜晶系,C2空间群,晶胞参数a=2.02334（14）nm,b=1.13896（4）nm,c=1.01094（6）nm,β=117.366（3）°,V=2.0689（2）nm^3.两个晶体学独立的Zn原子均为八面体构型,其中Zn1原子赤道配位点被2个酒石酸根中的4个羧酸根氧螯合配位,2个酒石酸根中剩下的4个羧酸根氧中的2个分别与2个Zn2原子连接形成无限一维链,Zn2原子的另外2个反式赤道配位点被2个水分子氧占据,同时这两种Zn原子的轴向配位点均被4,4′-联吡啶的氮原子占据,形成具有矩形格子[0.51165（3）nm×1.13896（5）nm]的二维层状结构,游离的2个水分子通过氢键作用形成二聚体,并与酒石酸根中未与Zn配位的羧酸氧连接,把二维层状结构连接成三维网状的超分子结构.     

Syntheses and Crystal Structures of Two New Metal Phosphonates： [Mn（H2O）2（C12H8N2） （HO3PCH2CH2CO2） ] and [Co（H2O）4（C10H8N2）]-（HOaPCH2CH2CO2）

By the reactions of manganese（if） acetate, 2-sulfoethylphosphonic acid, 1,10-phen （1,10-phen = 1, 10-phenanthroline） or cobalt（Ⅱ） acetate, 4,4＇-bipy and 2-carboxyethylphosphonic acid, two novel compounds of [Mn（H2O）2（C12H8N2） （HO3PCH2CH2CO2） ] （1） and[Co（H2O）4（C10H8N2）]-（HOaPCH2CH2CO2） （2） have been synthesized and characterized by IR spectroscopy, elemental analyses and single-crystal X-ray diffraction. Compound 1 has a 0D structure. Two Mn（ii） ions are linked by two 2-carboxyethylphosphonic acid ligands, forming a centrosymmetric dimer. These dimers are further interlinked into a 2D layer structure by π-π stacking interactions and hydrogen bonds. Compound 2 has a 1D chain structure. The 2-carboxyethylphosphonic acid remains uncoordinated and acts as the organic template. By the bridge of 4,4＇-bipy, the [Co（4,4＇-bipy）]^2＋ chains are formed.     

三维多孔配位聚合物{[Zn2(mal)2(4,4''-bipy)(H2O)2]·2(H2O)0.25}∞(mal=丙二酸根)的合成、结构及性质研究

ZnO,丙二酸及4,4'-bipy按物质的量之比1∶3∶0.3溶于H2O和DMF混合溶剂中(体积比4∶1),形成的无色溶液在50℃反应3d,得到了标题化合物{[Zn2(mal)2(4,4'-bipy)(H2O)2]?2(H2O)0.25}∞(mal=丙二酸根),对其进行了元素分析、红外光谱和X射线衍射表征,测定了晶体结构.该聚合物属单斜晶系,P21/n空间群,a=0.71215(16)nm,b=1.8685(4)nm,c=0.73890(17)nm,β=91.486(5)°,V=0.9829(4)nm3,Z=4,Dc=1.811g/cm3,Mr=268.03,F(000)=542,μ=25.02cm-1.最终偏离因子R1=0.0499,wR2=0.1374.该化合物中Zn原子和三个丙二酸根中的4个O原子、一个水分子和4,4'-bipy的一个N原子配位,形成的ZnNO5八面体通过4,4'-bipy和丙二酸根桥联,组成一种新颖的三维多孔结构,其孔道中充填游离水分子.此外还研究了该聚合物的热性质.     

配位聚合物[Mn（4，4＇-bpy）1．5（H2O）3]（ClO4）·（4，4＇-bpy）（L）·H2O的水热合成和晶体结构

The title compound, [Mn（4,4＇-bpy）1.5（H2O）3]（ClO4）＇（4,4＇-bpy）（L）·H2O（1）, where L=2,4,6-trimethylbenzoic acid, was synthesized and its crystal structure was determined by X-ray diffraction analysis. The crystal is of triclinic, space group P1 with a=2.929 9（6） nm, b=1.0364（2） nm, c=8.2220（1） nm, α=105.300（2）°,β=97.495（2）°,）,=91.118（2）°, V=1.884 0（4） nm^3, Z=2, Mr=780.10, Dc=1.375 g·cm^-3,μ=0.483 mm-1, F（000）=812, R=0.055 4, wR= 0.135 2. The Mn atoms are octahedrally coordinated by three N atoms of three 4,4＇-bipyridine ligands and three O atoms of water. The complex shows a one-dimensional chain structure bridged by water and 4,4＇-bipyridine molecules. CCDC： 615707.     

Synthesis,Structure, Electrochemistry and Fluorescence Properties of a One-dimensional Coordination Polymer {[ CdLu-（4,4＇-dps） ]2（H2O）2]＇（4＇abs ）2（H2O）2

A new cadmium（N） compound, {[ CdLu-（4,4＇-dps） ]2（H2O）2]＇（4＇abs ）2（H2O）2n 1 （4,4＇-dps = 4,4＇-dipyridylsulfide, 4-abs = deprotonated 4-amino benzenesulfonic acid）, has been synthesized and structurally characterized. It belongs to the orthorhombic system, space group Pbcn with a = 19.950（3）, b = 10.6381（13）, c = 18.055（2）A, V= 3831.8（8） A3, Z = 4, C32H36CdN6010S4, Mr = 905.31, F（000） = 1848, μ= 0.850 mm^-1, Dc = 1.569 Mg/m^3, the final R = 0.0238 and wR = 0.0589 for 3080 observed reflections with I 〉 2σ（I）. Complex I is a one-dimensional linear chain coordination polymer and the repeat unit is comprised of doubly charged cadmium complex cation, uncoordinated 4-aminobenzene sulfonate anions and water molecules. The cadmium（H） ion adopts a six-coordinate distorted octahedral geometry. Complex 1 is stabilized and linked into a three-dimensional layered structure through intermolecular O-H…O and N-H…O hydrogen bonds together with electrostatic force. The cyclic voltammograms and fluorescence spectrum of 1 were also measured. It shows one irreversible redox process and emits a very strong and sharp fluorescent band at about 341 nm.     

新颖的(4,4′-bipy){[Ag(4,4′-bipy)]_3·[PMo_(12)~ⅥO_(40)]}·H_2O三维超分子多金属氧酸盐的合成和晶体结构

利用H3PMo12O40.4H2O,4,4′-bipy和AgNO3反应,在中温水热条件下合成了一种新颖的三维超分子多金属氧酸盐(4,4′-bipy){[Ag(4,4′-bipy)]3[PMo12ⅥO40]}.H2O(1),并通过元素分析、红外光谱、热重分析和X射线单晶衍射对其结构进行了表征.结果表明,该化合物属三斜晶系,P1空间群,晶胞参数a=1.1275(2)nm,b=1.1910(2)nm,c=1.2898(3)nm,α=112.63(3)°,β=94.63(3)°,γ=99.53(3)°,V=1.5567(5)nm3,Z=1.该化合物具有三维超分子结构及荧光性质.     

三维配位聚合物[Zn(HCO2)2(4,4''''-bipy)]∞的合成、晶体结构及性质研究

以ZnO,HCO_2H及4,4'-bipy(摩尔比1∶3∶1.25)溶于H_2O和DMF(体积比13∶1),并在60℃反应,合成了标题化合物[Zn(HCO_2)_2(4,4'-bipy)]_∞,对其进行了元素分析、红外光谱等表征,并测定了晶体结构.该化合物晶体属四方晶系,P4_32_12空间群,a=b=0.79675(5)nm,c=1.7627(2)nm,V=1.1190(3)nm~3,Z=4,Dc=1.850g/cm3,M_r=311.60,F(000)=632,μ=22.07cm-1,最终偏离因子R1=0.0183和wR_2=0.0483.该化合物中Zn原子和两个4,4'-bipy的N原子和四个甲酸根的O原子配位,形成的ZnN_2O_4八面体通过4,4'-bipy和甲酸根桥联,组成一种新颖的3D网络结构.同时,研究了该化合物的热性质和荧光性质.     

新颖的(4,4’-bipy){[Ag(4,4’-bipy)]3[PMo12ⅥO40]}·H2O三维超分子多金属氧酸盐的合成和晶体结构

利用H3PMo12O40·4H2O, 4,4’-bipy和AgNO3反应, 在中温水热条件下合成了一种新颖的三维超分子多金属氧酸盐 (4,4’-bipy){[Ag(4,4’-bipy)]3[PMo12ⅥO40]}·H2O(1), 并通过元素分析、红外光谱、热重分析和X射线单晶衍射对其结构进行了表征. 结果表明, 该化合物属三斜晶系, P1空间群, 晶胞参数a=1.1275(2) nm, b=1.1910(2) nm, c =1.2898(3) nm, α = 112.63(3)°, β=94.63(3)°, γ=99.53(3)°, V=1.5567(5) nm3, Z=1. 该化合物具有三维超分子结构及荧光性质.     

Hydrothermal Synthesis and Crystal Structure of a New One-dimensional Cobalt（Ⅱ） Complex with 2-Pyridinecarboxyic Acid and 4,4＇-Bipyridine Ligands

A new metal-organic coordination polymer [Co（2-pya）2（4,4＇-bipy）]2n-[（4,4＇- bipy）0.5· H2O]2n （2-pya = 2-pyridinecarboxylic acid, 4,4＇-bipy = 4,4＇-bipyridine） 1 has been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, TG and single-crystal X-ray diffraction. The complex crystallizes in tetragonal, space group I41/a with a = b = 22.719（2）, c = 10.710（2）/k, V = 5527.8（14） A3, C54H46N10Co2O10, Mr= 1112.87, Dc = 1.337 g/cm3,μ（MoKa） = 0.665 mm-1, F（000） = 2296, Z = 4, the final R = 0.0633 and wR = 0.1096 for 1261 observed reflections （I 〉 2σ（I））. It exhibits a one-dimensional chain-like structure constructed by mixed ligands of 2-pyridinedicarboxylic acid and 4,4＇-bipyridine.     

Syntheses and Crystal Structures of Three Novel Zn~Ⅱ-sulfonyldibenzoilate Coordination Polymers

Three coordination polymers based on the V-shaped 4,4＇-dicarboxybiphenyl sulfone （H2sdba） ligands, [Zn3（μ-OH）2（sdba）2]n·2nH2O 1, [Zn2（sdba）2（4,4＇-bipy）]n·2nH2O 2 and [Zn3（sdba）3（py）2]n·n（py）·nH2O 3 （4,4＇-bipy = 4,4＇-bipydine）, were hydrothermally synthesized and structurally characterized. Complex 1 features the 2D planes constructed by the sdba ligands linking infinite Zn-O-C SBUs. The 4,4＇-bipy ligands in 2 bridge the Zn^II-sdba chains into interpenetrated 2D planes. The 3D network of α-Po topology in 3 is built from tri-nuclear Zn3 units with a [Zn3（OOC）6] structure. The intense blue and yellow luminescence was observed in complexes 1～3 which may result from ligand-to-metal charge transfer （LMCT）.     

Synthesis,Crystal Structure and Luminescent Property of [Zn（C12H9O3）2（C10H8N2）]n·nH2O

Under hydrothermal condition, the reaction of 2-naphthoxyacetic acid with ZnCl2 and 4,4′-bipyridine （4,4′-bipy） has afforded a new Zn（Ⅱ） compound, [Zn（C12H9O3）2（C10H8N2）]n·nH2O1, which was structurally characterized by single-crystal X-ray diffraction analysis. The crystal is of monoclinic, space group P21/c with a = 7.7335（2）, b = 19.3834（4）, c = 20.1707（4） A, β = 104.9830（10）°, V = 2920.82（11） A^3, C34H28ZnN2O7, Mr = 641.95, Z = 4, Dc = 1.460 g/cm^3,μ = 0.895 mm^-1, F（000） = 1328, R = 0.0406 and wR = 0.0876 for 4417 observed reflections （I〉 2σ（I）） Complex 1 consists of one-dimensional zigzag chains deriving from Zn（C12H9O3）2 units linked by 4,4′-bipy ligands, and lattice water molecules decorate between the chains. Non-covalent interactions, such as hydrogen-bonding and aromatic π-π interactions, lead to the formation of a 3D network structure. The thermogravimetric analysis （TGA） and luminescent property for 1 have also been studied in this paper.     

Syntheses and Crystal Structures of Two New Compounds： [Zn（2,2＇-bipy）（L）Cl]2 and [Zn（phen）（L2）]2 （HL = 3-Methylbenzoic Acid）

Compounds [Zn（2,2＇-bipy）（L）Cl]2 1 and [Zn（phen）（L2）]2 2 （2,2＇-bipy = 2,2＇-bipyridine, HL = 3-methylbenzoic acid, phen = 1,10-phenanthroline） have been synthesized under hydrothermal conditions. 1： monoclinic, space group C2/c, a = 20.240（4）, b = 9.2960（19）, c = 17.904（4）A, β = 92.63（3）°, V = 3365.1（12） A^3, C36H30Cl2N4O4Zn2, Mr = 784.32, Z = 4, Dc = 1.548 g/cm^3, μ = 1.631 mm^-1, F（000） = 1600, the final R = 0.0367 and wR = 0.1289 for 3867 observed reflections （I 〉 2σ（I））. 2： monoclinic, space group C2/c, a = 23.035（5）, b = 9.0395（18）, c = 23.799（5） A, β = 98.55（3）°, V = 4900.6（17）A^3, C56H44N4O8Zn2, Mr = 1031.73, Z = 4, Dc = 1.398 g/cm^3, μ = 1.039 mm^-1, F（000） = 2128, the final R = 0.0540 and wR = 0.1287 for 5002 observed reflections （I 〉 2σ（I））. The two compounds have the same space group and similar isolated dinuclear structure, but different space packing structures are formed by different weak intermolecular interactions. Mo- reover, IR and luminescence spectra are also employed to study the crystal structures and pro- perties of these two compounds.     

Crystal Structure and Magnetic and Fluorescent Properties of a New Copper（II） Complex Cu2（L）4（2,2＇-bipy）2（H2O）2

A new copper（II） complex Cu2（L）a（2,2＇-bipy）2（H2O）2 （1） has been synthesized with 2-benzoylbenzoic acid （HL） and 2,2＇-bipyridin as ligands. The crystal belongs to a monoclinic system with space group Cc, a = 13.9979（II）, b = 15.9888（13）, c = 30.306（3） A, β = 100.8700（10）°, V= 6661.1（10） A3, Dc= 1.372 g/cm3, Z = 8, F（000） = 2840, the final GOOF = 1.018, R= 0.0685, and wR= 0.1731. There are two mononuclear Cu（L）2（2,2＇-bipy）（H20） units in the crystal of 1. Each Cu（II） cation is coordinated by five atoms. The magnetic and fluorescent properties of 1 were studied. The results show that 1 exhibits weak paramagnetism, and when the excitation wavelength is at 616 nm, it has an intense fluorescent emission band around 482 nm.     

Ni（bpy）（H2O）（V2O6）和[Ni（bpy）2]2（V6O17）的水热合成与晶体结构

用NiCl2·6H2O,2,2＇-联吡啶（bpy）,NH4VO3,WO3在443K下通过水热反应法得到了两种多钒酸镍配合物Ni（bpy）（H2O）（V2O6）（1）和[Ni（bpy）2]2（V6O17）（2）．单晶X射线衍射结果表明化合物（1）属于正交晶系,空间群为Pcα2（1）,晶胞参数为0=0．91704（18）nm,b=1．0519（2）nm,c=1．4336（3）nm,V=1．3830（5）nm^3,Z=4;化合物（2）属于单斜晶系,空间群为P2（1）／c,晶胞参数为α=1．5467（3）nm,b=1．4740（3）nm,c=1．0457（2）nm,β=91．99（3）°,V=2．3826（8）nm^3,Z=4．化合物（1）由2,2’-联吡啶修饰的二维[Ni（V2O6）（H2O）]∞电中性层构成,而化合物（2）则由2,2＇-联吡啶修饰的、呈正弦波浪状的[Ni：（V6O17）]∞二维电中性层构成．