由柔性双苯并咪唑取代乙醚配体和羧酸构筑的系列配合物

本文从两种结构相似的配体[2,2′．二（2．甲基苯并咪唑）乙醚（L1）和2,2′-二42．乙基苯并咪唑）乙醚（L2）]出发,合成了6种配位聚合物：[Cu（L1）（bz）2]（1）,[Cu（L2）（bz）2]（2）,[Zn2（L1）（m-bdc）2]（3）,[Cd2（L2）（优-bdc）2（H20）]2H20（4）,[Zn（L1）（OH—bdc）（H20）]（5）和[Zn2（L2）（btca）]（6）．其中,Hbz=苯甲酸,m—H2bdc=问苯二甲酸,OH—H2bdc=5．羟基间苯二甲酸,H4btca=1,2,4,5-苯四甲酸．在化合物1和2中,双齿含氮配体（L1和L2）桥连相邻的金属中心原子,形成了1D单链结构,bz阴离子位于链的两侧．在化合物3和4中,含氮配体（L1和L2）以顺式构型连接两个金属中心原子,形成了[M2（L1）]^4＋单元（M=Zn（Ⅱ）和Cd（Ⅱ））．邻近的[M2（L1）]^4＋单元进一步通过二羧酸配体连接形成了1D双链结构．在化合物5中,Zn（Ⅱ）阳离子由5-羟基间苯二甲酸阴离子桥连,形成了ID无限聚合的链状结构．其中,L1配体以单齿配体的形式悬于链的一侧．在化合物6中,两个Zn（Ⅱ）阳离子由两个L2配体桥连,形成了[ZnL2]2^4＋环状结构,这些环进一步由btca阴离子连接形成了2D层状结构．同时,本文中还探讨了化合物3．6及相关配体在常温条件下的荧光性质．     

异烟酰肼缩水杨醛Schiff碱配合物的合成与表征

采用直接合成法用异烟酰肼、水杨醛合成了异烟酰肼缩水杨醛Schiff碱,并以此为配体合成了Zn（Ⅱ）、Co（Ⅲ）、Ni（Ⅱ）的配合物．对配合物进行了元素分析,红外光谱,紫外光谱,差热-热重分析及摩尔电导的测试等表征,推测配合物的组成分别为[Zn（H2O）L],[Co（H2O）2（HL）2]NO3-H2O,[Ni（H2O）2HL]NO3,其中L=C13 H9O2N3．     

5-溴水杨醛缩三乙烯四胺Schiff碱配合物的合成与表征

合成了5-溴水杨醛缩三乙烯四胺Schiff碱（H2Y）,并制备了Cu（Ⅱ）,Co（Ⅱ）和Mn（Ⅱ）的配合物[Cu2Y（H2O）2]（NO3）2（1）,[Co2Y（H2O）。（NO3）2]（2）,[Cu2ClY]Cl·H2O（3）和[MnY]（4）,利用元素分析、摩尔电导、IR和UV光谱对配合物的结构进行了表征,研究了它们的热稳定性．     

Syntheses, Crystal Structures, and Properties of Two Mixed-ligand Coordination Polymers： [Zn（bdc）（1,3-bimb）]_n and {[Mn_2（ox）_2（1,3,5-tib）_（4/3）]·4H_2O}_n

Two new coordination polymers,[Zn（bdc）（1,3-bimb）]n（1） and {[Mn2（ox）2（1,3,5tib）4/3]·4H2O}n（2）（H2ox = oxalic acid,H2bdc = terephthalic acid,1,3-bimb = 1,3-bis（imidazol-1ylmethyl）benzene,1,3,5-tib = 1,3,5-tri（imidazol-1-yl）benzene）,were synthesized and characterized by elemental analysis,IR,powder X-ray diffraction（PXRD）,and thermogravimetric（TG） analyses.X-ray diffracation analysis reveals that two kinds of zigzag chains [Zn（bdc）]n and [Zn（1,3-bimb）]n in compound 1 are interweaved to form a 3D 4-fold interpenetrated 66-dia framework.In compound 2,Mn（1） and Mn（2） are linked via 1,3,5-tib ligands to form two different nets of [Mn6（1,3,5-tib）6 ]n along the ab plane with inner-or outer-shape N–Mn–N angles,which are connected by 1D infinite [Mn2（ox）2 ]n chains via Mn–O bonds to result in a（3,3,3,4,4）-connected（4·8·10）3（4·82）3（4·83·102）6（82·104·3）3（83）4 topology.Moreover,the photoluminescence of 1 has been investigated.The crystal of 1 crystallizes in orthorhombic,space group Pna2 with a = 13.2267（6）,b = 9.1717（4）,c = 17.4492（8）,V = 2116.79（16）3,Z = 4,C22 H18N4O4 Zn,Mr = 467.77,Dc = 1.468 g/cm3,F（000） = 960 and μ（MoKα） = 1.197 mm-1.The final R = 0.0280 and wR = 0.0618 for 3695 observed reflections with I 2（I） and R = 0.0389 and wR = 0.0653 for all data.The crystal of 2 crystallizes in rhombohedral,space group R-3 with a = 22.080（8）,c = 31.19（2）,V = 13167（11） 3,Z = 18,C24 H25 Mn2 N8 O13,Mr = 743.40,Dc = 1.688 g/cm3,F（000） = 6822 and μ（MoKα） = 0.945 mm-1.The final R = 0.0429 and wR = 0.1035 for 5160 observed reflections with I 2（I） and R = 0.0824 and wR = 0.1244 for all data.     

A Series of Mononuclear Complexes Constructed from Transition Metals and Amino Acid Derived Ligands: Syntheses, Structures and Photoluminescence

Eight neutral mononuclear complexes constructed from transition metals （M = Co（Ⅱ）, Ni（Ⅱ）, Cu（Ⅱ）, Zn（Ⅱ）, Cd（Ⅱ）） and ligands N-（2-pyridylmethyl）-L-phenylalanine （L-Hpmpa） and N-（2-pyridylmethyl）-L-tyrosine （L-Hpmtyr） have been synthesized by both hydrothermal and conventional room temperature reactions. Four of them have been structurally characterized by single-crystal X-ray diffractions. They are： [Co（L-pmpa）2·2H2O] 1, [Ni（L-pmpa）2·2H2O] 2, [Cu（L-pmpa）2·2H2O] 3 and [Cu（L-pmtyr）2·2H2O] 4. Single-crystal X-ray analysis, IR and elemental analysis revealed that complexes 1, 2 and 3 are isostructural. Powder X-ray diffraction, IR and elemental analysis revealed that complexes 4, 5 （Zn[L-pmtyr]2·2H2O）, 6 （Cd[L-pmtyr]2·2H2O）, 7 （Co[L-pmtyr]2·2H2O） and 8 （Ni[L-pmtyr]2·2H2O） are isostructural. The photoluminescence properties of L-Hpmtyr ligand, compounds 5 and 6 were also investigated.     

Imidazole Coordinated Sandwich-type Antimony Polyoxotungstates Na9[ {Na（H=O2}3{M（C3H4N2）}3（ Sb W9O33）2]·xH=O（M=Ni^Ⅱ, Co^Ⅱ, Zn^Ⅱ, Mn^Ⅱ）

The imidazole covalently coordinated sandwich-type heteropolymngstates Na9[ {Na（H=O2}3{M（C3H4N2）}3（ Sb W9O33）2]·xH=O（M=Ni^Ⅱ, Co^Ⅱ, Zn^Ⅱ, Mn^Ⅱ） were obtained by the reaction of Na2WO4·2H2O, SbCl3·6H2O, NiCl2·6H2O [MnSO4·H2O, Co（NO3）2·6H2O, ZnSO4·7H2O] and imidazole at pH≈7.5. The structure of Na9[{Na（H2O）2}3{Ni（C3H4N2）}3（SbW9O33）2]·32H2O was determined by single crystal X-ray diffraction. Polyanion [{Na（H2O）2}3{Ni（C3H4N2）}3（SbW9O33）2}3]^9- has approximate C3v symmetry, imidazole coordinated six-nuclear duster [{Na（H2O）2}3{Ni（C3H4N2）}3]^9＋ is encapsulated between two （α-SbW9O33）^9-, the three rings of imidazole in the polyanion are perpendicular to the horizontal plane formed by six metals （Na-Ni-Na-Ni-Na-Ni） in the central belt, and x-stacking interactions exist between imidazoles of neighboring polyanions with dihedral angel of 60%. The compounds were also characterized by IR, UV-Vis spectra, TG and DSC, and the thermal decomposition mechanism of the four compounds was suggested by TG curves.     

吡啶配位的夹心型杂多阴离子{[Na(H2O)2]3[Ni(C5H5N)]3(AsW9O33)2}9-的结构及磁学性质

The pyridine coordinated sandwich-type heteropolytungstate Na7[Ni（H2O）6] { [Na（H2O）2]3[Ni（C5H5N）]3（AsW9O33）2}·28H2O was obtained by the reaction of Na2WO4·2H2O, NaAsO2 and pyridine with NiCl2·6H2O at pH =7.0 and characterized by elemental analysis, IR, UV-Vis,^1H NMR spectra and magnetic measurement. The structure of this heteropolytungstate was determined by X-ray diffraction analysis, which crystallized in triclinic system, space group P1 with a= 1.3153（9） nm, b= 1.7228（12） nm, c=2.6866（19） nm, a=74.130（11）°,β=78.032（12）°, γ = 73.179（12）° and Z= 2, R1 = 0.0604, wR2 = 0.0915 [I〉 2σ（I）]. Polyanion {[Na（H2O）2]3[Ni（C5H5N）]3（AsW9O33）2}^9- has approximately C3 symmetry, and three pyridine coordinated Ni（C5H5N）^2＋ and three Na（H2O）2^＋ are encapsulated between two AsW9O33^9- . Magnetic measurements show that central Ni3 unit in the polyanion exhibits ferromagnetic Ni-Ni exchange interactions （J=6.17 cm^-1）.     

Construction of a 3D Co（II） Framework Based on Two Type of V-shaped Bidentate Ligands

A three-dimensional （3D） coordination polymer {[Co（bdc）（dpb）]·H2O}n （1） was prepared by solvothermal reaction of 1,3-dipyridyl benzene （dpb） with deprotonated 1,3-benzene- dicarboxylate （H2bdc）, and was characterized by elemental analysis, IR spectroscopy, and X-ray single-crystal diffraction. It crystallizes in the monoclinic system, space group C2/c with α = 15.478（6）, b = 12.865（5）, c = 24.091（10） ？, β = 95.599（5）°, V = 4774（3） ？3, C24H18CoN2O5, Mr = 473.34, Dc = 1.267 g/cm3, F（000） = 1864.0, μ = 0.748 mm-1 and Z = 8. Each Co（II） ion links three bdc2- anions to form an infinitely 1D ladder-shaped chain containing binuclear [（COO）Co]2 cluster, and dpb links adjacent 1D chains to form a 3D pcu framework. In addition, the UV-vis of 1 was also studied.     

基于Keggin阴离子链镍化合物的结构和质子导电性

由H+(H2O)2.5阳离子,[Ni(H2O)8]2+阳离子,[PW12O40]3-阴离子和异烟酸氮氧化物(HINO)自组装成一个具有质子导电性的化合物{[Ni(H2O)8][H(H2O)2.5](HINO)4(PW12O40)}n。293 K的单晶X-射线衍射分析表明标题化合物形成1个带有一维通道的三维氢键网络结构。[PW12O40]3-阴离子填充在一维通道内并且自组装成多阴离子链。热重分析表明在20~100℃范围内化合物没有失重,表明化合物结构单元内所有的水分子在100℃以下不易失去。标题化合物在85~100℃范围内表现出好的离子导电性(1×10-3~2×10-3S.cm-1)。     

Syntheses, Crystal Structures and Electrochemical Properties of Two Molybdophosphates

Two molybdophosphate compounds,[Ni(bim)3]2[H2P2Mo5O23]·2H2O 1 and [Zn(bpy)2]2[Zn(bpy)(H2O)]2Zn[Mo6O12(OH)3(HPO4)4]2·9H2O 2 (bim = 2,2'-biimidazole,bpy = 2,2'-dipyridyl),have been synthesized under hydrothermal conditions and structurally characterized by elemental analysis,TG,and IR. The single-crystal X-ray analysis exhibits that 1 consists of one [H2P2Mo5O23]4-,two [Ni(bim)3]2+ cations and two lattice water molecules,while 2 is constructed from one sandwich-type [ZnP4Mo6] anion modified by four Zn-bpy complexes and nine lattice water molecules. The electrochemical behaviors of compounds 1 and 2 have been studied in detail based on solid bulk modified carbon paste electrodes of compound (CPEs).     

[π-C5H5N（CH2）15CH3]3[PMoW3O24]／H2O2：高效的环境友好且可再生的烯烃环氧化磷钼钨杂多酸催化体系

研究了一种可循环并且环境友好的催化体系：[π-C5H5N（CH2）15CH3]3[PMoW3O24]／过氧化氢／乙酸乙酯／烯烃．此体系不仅可以催化烯烃的环氧化反应,而且避免了对含氯溶剂的使用．反应在过氧化氢／乙酸乙酯的两相体系中进行,可以将多种烯烃转化为相应的环氧化物,且产率较高．此催化剂具有反应控制相转移的特征,反应结束后可以回收再利用．采用Raman,IR,^31P MAS NMR和^31P NMR等手段对新鲜及重复使用过的催化剂进行表征．结果表明：新鲜催化剂[π-C5H5N（CH2）15CH3]3[PMoW3O24]是一种混合物,含有多种过氧磷钼钨酸盐,如{PO4[MoO（O2）2]4}^3-,[（PO4）{Mo3WO20}]^3-,[（PO4）{Mo2W2O20}]^3-,[（PO4）{MoW3O20}]^3-和{PO4[WO（O2）2]4}^3-．当过氧化氢被完全消耗后,这些小的活性物种就会聚合成具有混合多原子的Keggin型杂多阴离子,形成M-Ob—M（M=W或Mo）和M-Oc-M键．     

Construction of a 2D Cd（II） Coordination Polymer Based on a V-shaped Bidentate Ligand

A two-dimensional（2D）coordination polymer{[Cd（bdc）（dpb）]·H2O}n（1）has been prepared by solvothermal reaction of 1,3-dipyridyl benzene（1,3-dpb）with deprotonated1,4-benzenedicarboxylate（H2bdc）,and was characterized by elemental analysis,IR spectroscopy,and X-ray single-crystal diffraction.It crystallizes in the monoclinic system,space group C2/c with a=15.1839（12）,b=20.7585（17）,c=7.2989（6）,β=117.3450（10）°,V=2043.5（3）3,C24H18N2O5Cd,Mr=526.81,Dc=1.712 g/cm3,F（000）=1056.0,μ=1.110 mm-1and Z=4.The neighboring Cd（II）ions link the bdc2-anions and 1,3-dpb to form an infinite 2D sheet,and such two2D sheets are interlocked with each other to form a 2D→2D sheet.Two groups of interlocked sheets are further linked together by intermolecularπ···πinteraction,giving a 3D supramolecular network.In addition,the fluorescence property of 1 was also studied.     

6-四氮唑-2-吡啶甲酸配合物的原位合成与氢键拓扑网络研究

用2,6-二氰基吡啶与叠氮化钠在水热条件下原位合成了5种6一四氮唑．2-吡啶甲酸配合物：【Ni2（tepc）2（H2O）2】（1）,[CO2（tepc）2（H2O）4]·2H2O（2）,【CO2（tepc）2（H2O）4】·4H2O（3）,【Cu2（tepc）2（H2O）2]（4）和{【Mn（tepc）（H20）2]·2H2O}n（5）（tepc=6一（tetrazol-5-y1）picolinate）．这些配合物中配体均以三齿螯合的方式与金属离子配位．配合物1-4形成了双核离散型配合物,双核分子通过氢键作用连接成三维超分子结构．配合物5中的单核螯合单元间通过Mn-O配位键连接成为一维配位聚合物链,链间通过氢键连接成为整个配合物的晶体结构．氢键拓扑网络分析表明,配合物1和2可简化成NaCI型的6-连接pcu拓扑网,配合物3则可简化成一种8．连接hex拓扑网,配合物4可简化成一种新型双结点十连接拓扑网络（3^10．4^26·5^8·6）（3^8．4^26．5^10．6）,配合物5则可简化成一种新型的（5,10）双结点三维网络（3^2·4^7．5）（3^4．4^21．5^13．6^7）．本文不仅详细地分析了这些配合物晶体结构中氢键与拓扑网络之间的关系,而且还讨论了氰基的水解反应与四氮唑成环反应间的关系,以及金属离子的电子特征、结晶条件与晶体结构之间的关系．     

Zero-and One-dimensional Organic-inorganic Hybrid Compounds Based on Monovacant Keggin Polyoxotungstates

Two new organic-inorganic hybrid mono-transition-metal-substituted polyoxometalates [Ni（2,2′-bipy）3]3[Ni（H2O）SiW11O39]·11H2O 1 and [Cu（dien）（H2O）][Cu（dien）（H2O）2]2- [CuSiW11O39]·5.5H2O 2 （2,2′-bipy = 2,2′-bipyridine, dien = diethylenetriamine） have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, magnetic properties, and IR spectrum. Crystal data for 1： monoclinic, space group P21/n, a = 17.492（3）, b = 33.481（5）, c = 20.493（3）A^°, β = 101.894（3）°, Dc = 2.563 mg/A^°^3, F（000） = 8440, μ = 11.454 mm^-1 and Z = 4; and those for 2：monoclinic, space group P21/n, a = 11.114（3）, b = 22.803（7）, c = 22.468（7） A^°, β = 97.896（6）°, Dc = 4.036 mg/A^°^3, F（000） = 6140, μ = 23.942 mm^-1 and Z = 4. The study on the magnetic susceptibility of 2 demonstrates the presence of ferromagnetic interaction.     

Structural Characterization and Luminescence Properties of Two 4d-4fLn-Ag Coordination Compounds Based on Dinuclear Lanthanide Clusters

Two new compounds,[ErAg（INA）2（C2O4）]·2H2O（1）（HINA=nicotinic acid） and [Tb0.8Y0.2Ag2（IN）4·（H2O）5]·NO3·2H2O（2）（HIN=isonicotinic acid）,based on the {Ln2} building units,have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction,infrared spectroscopy,thermal analysis and powder X-ray diffraction（PXRD）.Single-crystal X-ray diffraction data reveal that both compounds crystallized in the low-symmetry triclinic space group P1-.Compound 1 is a 3D heterometallic coordination framework based on {Er2}clusters,oxalate ligands and bridging [Ag（INA）] linkers,while compound 2 consists of 0D [Tb0.8·Y0.2Ag2（IN）4（H2O）5]2 subunits that give a 3D supramolecular structure through hydrogen bond interaction.The photoluminescent properties of both compounds（1 and 2） were studied.     

Synthesis, Crystal Structure and Property of a Series of Supramolecular Polymers Based on Novel 3,5-Dimethyl- 2,6-bis（3-（pyrid-2-yl）-1,2,4-triazolyl）pyridine Ligand

Solvothermal reactions of 3,5-dimethyl-2,6-bis(3-(pyrid-2-yl)-1,2,4-triazolyl) pyridine (L), 1,4-benzendicarboxylic acid (H2bdc), and transitional metal cations of MII (M = Mn, Co, Cd) in the presence of oxalic acid (H2ox) afford three novel supramolecular polymers (CPs), namely, {[M2(ox)(L)2][bdc][M2(Hox)2(OH)2(H2O)4].3H2O}n (M=Mn for 1, Co for 2, Cd for 3). Single-crystal X-ray diffraction analysis reveals that complexes 1-3 are isostructural and the 3D supramolecular structure was connected through non-covalent interactions. With the help of H2ox, the L ligands cheated with center atoms forming a butterfly [M2(ox)(L)2]2+ building block. The bdc2- ligand linked with the unprecedented [M2(Hox)2(OH)2(H2O)4] units through strong O-H…O hydrogen bonds forming a zigzag chain, which are further connected through π…π interactions between L and bdc2- ligands to form a 3D supramolecular structure. Moreover, elemental analyses, IR, thermogravimetric, PXRD and luminescence have been investigated.     

两个三维柱层式Ce混合羧酸多孔金属-有机骨架配合物的合成、结构与磁性

采用水热法合成了两个新的混合羧酸铈多孔金属-有机骨架配合物[Ce2(fum)3 (H2O)4?(bdc)?(H2O)2]n（1）和[Ce2(suc)2(ox)(H2O)4?(H2O)4]n（2）,利用元素分析、红外光谱、热重分析和单晶X射线衍射对其组成和结构进行了表征,并通过磁性测量研究了其磁学性能. 单晶X射线衍射结果表明,配合物1和2均为三维柱层式多孔金属-有机骨架结构. 配合物1由Ce离子和富马酸（fumarate, fum）形成层,层与层之间再通过富马酸作为柱状配体支撑形成三维结构,并在层间的两个方向上形成相互交错的通道,未配位的中性对苯二甲酸分子（p-benzenedicarboxylate, bdc）和晶格水分子填充于孔道中. 与配合物1类似,配合物2由Ce离子和丁二酸（succinate, suc）形成层,层间通过草酸（oxalate, ox）作为柱状配体支撑形成三维结构,在层间的三个方向上具有相互交错的通道,晶格水分子填充于孔道中.     

Synthesis and Structure of a Novel Organic-Inorganic Hybrid Polyoxovanadate, [Ni（bpp）2]2（V4O12） （bpp= 1,3-bi-4-pyridylpropane）

A novel organic-inorganic hybrid polyoxovanadate, [Ni（bpp）2]2（V4O12） （bpp= 1,3-bi-4-pyridylpropane）, was hydrothermally synthesized from a mix.ture of NiCl2＊6H2O, NH4VO3, bpp, EtOH and H2O. The crystal structure consists of ∞^2[Ni（bpp）2]^2＋, two-dimensional networks interpenetrating perpendicularly with each other, and （V4O12）^4-, cyclic tetranuclear clusters linking the ∞^2[Ni（bpp）2]^2＋ networks to form a three-dimensional coordination framework. The crystal belongs to tetragonal space group I41/a with unit cell parameters, a= 2.14705 nm, c= 1.29293 nm. UV-Vis-NIR reflectance spectroscopy study revealed insulator nature for the crystal with an optical energy gap of 2.70 eV.     

The First Example of a Supramolecular Structure Containing [2-（1H-Pyrazol-3-yl）-pyridine] Complex and both α- and β-Octamolybdates

The title compound, [Ni（C8N3H7）3]4[Mo8O26]2·6H2O 1, has been synthesized from the reaction of 2-（1H-pyrazol-3-yl）-pyridine （L） with （NH4）2MoO4·2H2O and NiCl2·6H2O. Elemental analysis, IR, UV spectra and X-ray single-crystal diffraction were carried out to determine the composition and crystal structure of the compound. Crystal data： C96H96Mo16N36Ni4O58, Mr = 4451.97, monoclinic system, space group P21/n, a = 20.846（5）, b = 14.825（5）, c = 23.122（5） A ,β= 91.594（5）°, V = 7143（3）A^3, Z = 2, F（000） = 4344, Dc = 2.070 g/cm^3,μ = 1.968 mm^-1, R = 0.0452 and wR = 0.1056 for 17102 independent reflections （Rint = 0.0442） and 11074 observed reflections （I 〉 2σ（I））. Structural analysis indicates that two kinds of octamolybdates （[α-Mo8026]^4- and [β-Mo8026]^4-） co-exist in the compound. This is the first example of a supramolecular structure containing L complex as well as both α- and β-octamolybdate clusters.     

咪唑-金属配合物的合成、性质及其与DNA的作用机理

Three hexakis（imidazole）metallo complexes of Co, Cd and Ni were synthesized and spectroscopically characterized. The crystal and molecular structures have been determined by X-ray crystallography analysis. The metal ions have an octahedral geometry with the MN6 chromophore. The electrochemical experimental results indicate that both [Co（Im）6]C12·2HCl·2H2O （1） and [Ni（Im）6]C12·4H2O （3） [Im=imidazole] could interact with DNA mainly by intercalation.