Aromatic Multicarboxylate Ligands Tuned One-and Three-dimensional Zn(Ⅱ) Coordination Polymers Based on 3-(1H-pyrazol-4-yl)-5-(pyridin-3-yl)-1,2,4-triazole

Two aromatic multicarboxylate ligands tuned Zn(Ⅱ) coordination polymers, namely, {[Zn_(0.5)(H_2L)(tp)_(0.5)(H_2O)]H_2O}_n(1) and {[Zn_2(HL)(btc)(H_2O)]H_2O}_n(2)(H_2L = 3-(1 Hpyrazol-4-yl)-5-(pyridin-3-yl)-1,2,4-triazole, H_2tp = terephthalic acid; H_3 btc = 1,3,5-benzenetricarboxylic) have been synthesized. Their structures were characterized by single-crystal X-ray diffraction analysis, elemental analyses and infrared spectra. Compound 1 possesses a one-dimensional chain structure and is finally extended into a three-dimensional supramolecular architecture though hydrogen bonding interactions. Compound 2 shows a three-dimensional framework. Meanwhile, compounds 1 and 2 exhibit luminescent emission in the solid, and can be investigated as potential luminescent materials.     

3,5-二(吡啶-4-甲氧基)苯甲酸和芳香二羧酸配体构建的具有3,4-连接四重和三重穿插的d~(10)金属配位聚合物（英文）

以3,5-二(吡啶-4-甲氧基)苯甲酸(HL)与芳香二羧酸为配体,在水热条件下与Zn(Ⅱ)或Cd(Ⅱ)盐反应得到4个具有3,4-连接多重穿插结构的配位聚合物:[Zn_2L_2(tdc)]_n(1),{[Zn_4L_4(Hhdc)_2]·H_2O}n(2),{[Zn_2L_2(Hhdc)]·H_2O}n(3),{[Cd_2L_2(bdtc)(H_2O)]·0.5H_2O}n(4)(H_2tdc=2,5-噻吩二甲酸,H_3hdc=5-羟基间苯二甲酸,H_2bdtc=1,4-苯二硫乙酸)。晶体结构分析表明,聚合物1~3具有3,4-连接四重穿插的三维网络结构,拓扑符号分别为(4.82)(4.85)(1)、(63)(65.8)(2)和(63)(65.8)(3)。4为3,4-连接三重穿插的二维平面结构,拓扑符号为(6~3)(6~6)。测定了配位聚合物1、3和4的热稳定性和荧光性质。     

4,4′-联吡啶桥联的三个铜有机膦酸配合物的合成、结构及磁性（英文）

在水热条件下,以N-氧化-2-吡啶膦酸(H2L)为主配体,4,4′-联吡啶(bpy)为桥联配体,合成了3个铜有机膦酸配合物:{[Cu(L)(bpy)0.5(H_2O)]·2H_2O}n(1),{[Cu(HL)2(bpy)]·4H_2O}n(2)和{[Cu2(L)2(bpy)]·3H_2O}n(3)。配合物1中,相邻的铜离子由2个膦酸根连成二聚体,二聚体之间通过bpy桥联成一维链。配合物2中,单核[Cu(HL)2]被bpy连接成一维链。配合物3中,四聚体[Cu2(L)2]2被bpy连接成"砖块状"结构的二维层。磁性研究表明,配合物1和3中铜离子之间存在反铁磁性耦合。     

基于半刚性双(噻唑基苯并咪唑)和不同羧酸的五个一维配合物的合成和表征

通过水热或溶剂热合成的方法制备了5个一维配合物{[Zn(btbb)_(0.5)(m-phda)]·0.5H_2O}_n(1),{[Cd_2(btbb)(adtda)_2(H_2O)]·H_2O}_n(2),[Mn_2(btbb)(tbi)_2]_n(3),{[Cd(btbb)_(0.5)(3-Nitro-o-bdc)(H_2O)]·H_2O}_n(4)和[Cd_2(btbb)(tbi)_2]_n(5)(btbb=1,4-双(2-(4-噻唑基)苯并咪唑-1-基甲基)苯,m-H_2phda=间苯二甲酸,H_2adtda=1,3-金刚烷二羧酸,H_2tbi=5-叔丁基间苯二甲酸,3-Nitro-o-H_2bdc=3-硝基-1,2-苯二甲酸)。配合物1是一个包含22元环的一维链。配合物2是一个包含8元环的一维链,并且氮配体在这个一维链中仅仅起到装饰作用。配合物3是一个一维双链结构。配合物4是一个包含14元环的一维链。配合物5是一个阶梯状的一维双链结构。     

杂金属杯[4]配位聚合物的合成与表征（英文）

合成了4个杂金属杯[4]配位聚合物{[Cd(L)(tpa)]·3H_2O}n(1),{[Zn_2(L)_2(tpa)_2]·3H_2O}n(2),{[Co(L)(oba)]·2DMA·0.5H_2O}_n(3)和{[Zn(L)(oba)]·DMA}n(4)(L=2-(1H-咪唑基-甲基)-6-(3-(1H-咪唑基-甲基)-5-叔丁基-2-羟基)苄基-4-叔丁基苯酚,H2tpa=对苯二甲酸,H2oba=4,4′-二苯醚二甲酸),并通过元素分析、热重、红外光谱、固态紫外、单晶X射线衍射和粉末X射线衍射对其进行了表征。单晶结构分析表明晶体1是单斜晶系,P21/n空间群,而晶体2,3和4均为三斜晶系,P1空间群。化合物1,2,3和4是由0维[M(N_4O_2C_(29)H_(36))](M=Zn,Co,Cd)的杂金属杯[4]与配体对苯二甲酸和4,4′-二苯醚二甲酸形成的一维配位聚合物。     

Syntheses,Crystal Structures and Characterization of Two Coordination Polymers Based on Mixed Ligands

Two new coordination polymers,namely,{[Cd_(1.5)(bc)_2(HL)](13)H_2O}_(2n)(1) and [Mn(ip)(H_2L)(H_2O)]_n(2)(H_2L = 3-(1 H-pyrazol-4-yl)-5-(pyridin-2-yl)-1,2,4-triazole,Hbc = benzoic acid,H_2 ip = isophthalic acid) were constructed by solvothermal reaction.The compounds were characterized by elemental analysis,FT-IR spectroscopy,and single-crystal X-ray diffraction.Compound 1 displays a two-dimensional plane structure consisting of [Cd_3(bc)_2(HL)] subunits.Compound 2 possesses a one-dimensional chain structure and is further extended into a 3-D supramolecular architecture via hydrogen bonds.Moreover,photoluminescence studies showed compound 1 exhibits luminescent emissions with emission maxima at 375 nm.Magnetic susceptibility measurements of 2 indicate that domain antiferromagnetic interactions exist between Mn(Ⅱ) ions.In addition,thermogravimetric properties of 1 and 2 were also measured.     

由芳香羧酸构筑的系列Ni(Ⅱ)配合物的合成、结构及光电性能

采用水热法设计合成了6个基于芳香羧酸的Ni(Ⅱ)配合物:[Ni(pz)_4(H_2O)_2]·2H_2btc·H_2O(1),{[Ni_2(pz)_8(btec)]·4H_2O}n(2),{[Ni (H_2btec)(phen)]·2H_2O}n(3),[Ni (Hbdc)_2(pz)_4](4),{[Ni_3(bdc)_3(pz)_(12)]·2H_2O}n(5)和[Ni(bdc)(pz)_2(H_2O)]n(6)(pz=吡唑,H_3btc=1,3,5-苯三甲酸,H_4btec=1,2,4,5-苯四甲酸,phen=1,10-邻菲罗啉,H_2bdc=邻苯二甲酸).通过单晶X射线衍射、红外光谱(IR)、紫外-可见-近红外吸收光谱、元素分析、粉末X射线衍射(XRD)和表面光电压光谱(SPS)对其进行了结构和性质表征. 6个配合物的金属Ni(Ⅱ)中心呈五或六配位.配合物1和4具有完全由氢键网联成的2D超分子结构;配合物2和3是通过采取单齿/桥双齿配位模式的btec4-构筑的2D配位骨架结构;配合物5和6是由采取单齿/螯合双齿配位模式的bdc2-构筑的1D配位骨架结构,并由氢键连接成2D结构. 6个配合物在紫外和可见光诱导下均呈现出一定的光-电转换性能.当对配合物施加外加电场时,6个配合物的光电响应因配合物组成、结构键连方式以及配体种类的不同而呈现规律性变化.     

基于3,5-二(3-吡啶)-4-氨基-1,2,4-三唑配体的Co(Ⅱ)和Cu(Ⅱ)配合物的合成与晶体结构（英文）

利用3,5-二(3-吡啶)-4-氨基-1,2,4-三唑(L)配体与Co(Ⅱ)/Cu(Ⅱ)盐室温下反应得到了一维的配位聚合物{[CoL(H_2O)_4]SO_4·H_2O}n(1)和单核配合物[Cu(hfac)2L2](2,hfac=hexafluoroacetylacetonate)。通过红外、元素分析及X射线单晶衍射等检测手段对所合成的配合物进行了表征。结构研究表明,配合物1中,配体L呈顺式构型,采取双齿配位方式桥联Co(Ⅱ)离子形成一维正弦链状结构,一维链通过多种氢键相互作用连接进一步形成三维网状结构;溶剂水分子和硫酸根阴离子通过氢键连接在框架上。配合物2中,配体L则采取单齿配位方式,与Cu(Ⅱ)离子形成离散型的单核结构,通过多重氢键作用进而连接成三维网状结构。     

3,5-二(2′，5′-苯二羧酸)苯甲酸构筑的金属有机配合物的荧光识别及磁性（英文）

设计合成了3种新颖的金属有机配合物(MOCs):{[Pb_2(HL)(phen)]·2H_2O)_n(1),{[Ni(H_3L)(4,4'-bipy)_(1.5)(H_2O)_4]·(6H_2O}_n(2)和{[Ni_2(HL)(1,4-bibb)(H_2O)]·(CH_3CN)·H_2O)}_n(3)(H_5L=3,5-二(2',5'-苯二羧酸)苯甲酸,phen=1,10-菲咯啉,4,4'-bipy=4,4'-联吡啶,1,4-bibb=1,4-二(苯并咪唑)苯),并通过单晶X射线衍射、红外光谱(IR)、热重分析(TG)和粉末衍射对它们进行结构表征。结构分析表明1是基于[Pb_2(μ_2-COO)_2(μ_1-COO)_4] SBUs的一维链状结构;2是二维层状结构,其拓扑符号为{4.6~2)_2{4~2.6~2.8~2};3是一个3D网络结构,其拓扑符号为{6~2.8~4}{6~4.8~2}_2。进一步研究了配合物荧光和磁性能。荧光检测显示,配合物1在水溶液中可以高灵敏识别Fe~(3+)和Cr_2O_7~(2-)离子。同时研究了配合物1对Fe~(3+)和Cr_2O_7~(2-)猝灭机理。磁性分析表明配合物3中的Ni(Ⅱ)离子之间存在反铁磁相互作用。     

Syntheses,Structures and Characterizations of Two New Zinc(Ⅱ) Coordination Polymers Constructed from 3-(1H-Pyrazol-4-yl)-5-(pyridin-2-yl)-1,2,4-triazole and Different Carboxylate Ligands

Two new zinc(Ⅱ) coordination polymers, [Zn(ph)(H2 L)·H_2O]2 n(1) and [Zn(ip)(H2 L)-(H_2O)]n(2)(H2 ph = phthalic acid, H2 ip = isophthalic acid, H2L = 3-(1 H-pyrazol-4-yl)-5-(pyridin-2-yl)-1,2,4-triazole), have been successfully synthesized via hydrothermal reaction. It has been structurally characterized by X-ray single-crystal analysis, IR spectra, fluorescence spectroscopy and thermogravimetry analysis. The single-crystal X-ray diffraction studies reveal that compounds 1 and 2 both exhibit 1D chain structures, and assemble into 2D and 3D supermolecules through hydrogen bonds or π-π interactions. Moreover, the thermal stability and luminescent properties of compounds 1 and 2 were also studied.     

Three Co(Ⅱ) Coordination Polymers Incorporated with a Bent Connector: Crystal Structures and Magnetic Properties

Based on the bent ligand 1 H-3-(3-pyridyl)-5-(4-pyridyl)-1,2,4-triazole(3,4?-Hbpt) with Co(Ⅱ) ions as well as a series of polycarboxylate co-ligands, three new coordination polymers were yielded, namely, {[Co(op)(3,4?-Hbpt)(H_2O)_3]?2 H_2O}n(1), [Co(cyc)(3,4′-Hbpt)(H_2O)]n(2) and [Co(pro)(3,4′-Hbpt)(H_2O)]n(3)(here, op = o-phthalic anion, cyc = 1,1-cyclobutanedicarboxylic anion, pro = propanedioic anion). In cooperation with the auxiliary polycarboxylate co-ligands, a variety of Co(Ⅱ) coordination networks, such as 1-D chain 1 and 2-D layer 2 and 3 have been assembled. The magnetic behaviors of compounds 1～3 were studied. All of them indicated the existence of interesting spin-canting behavior.     

基于双吡啶脲类Cd(Ⅱ)、Zn(Ⅱ)、Hg(Ⅱ)配合物的合成及晶体结构

间苯二胺和3-吡啶异氰酸酯在甲苯中加热回流得到双吡啶脲类配体L,然后将配体分别与CdSO_4·8H_2O,ZnI_2,HgI_2,HgCl_2进行配位反应,得到4个配合物{[Cd(L)(SO_4)(H_2O)_3]·H_2O}n(1),{[Zn(L)I_2]·2C_2H_5OH}n(2),{[Hg(L)I_2]·C_2H_5OH}n(3),[Hg(L)Cl_2]·H_2O(4),并用元素分析、FT-IR、X射线单晶衍射、粉末衍射对其进行了表征。配合物1形成一维螺旋链结构,配合物2和3形成一维"之"字链结构,配合物4形成32元环状结构。     

Syntheses and Anti-lung Cancer Activities of Zn(Ⅱ) and Cu(Ⅱ) Complexes Based on Triazole and Tetrazole,respectively

The reactions of 4H-1,2,4-triazole(Htrz) with ZnCl_2, 1H-tetrazole(Htez) and Cu(NO_3)2·6H_2O afford two novel coordination polymers respectively, {[Zn_2(trz)_2(ox)](H_2O)_3}n(1) and {[Cu_3(tez)_3(OH)_2(H_2O)_2](NO_3)(DMF)_4}_n(2)(H_2ox =(COOH_)2, DMF = N,N-dimethylformamide). 1 shows 1D channels along the a axis filled with water molecules and 2 features a 2D bi-layered framework based on trinuclear Cu(II) units bridged by two μ3-OH groups. In addition, in vitro antitumor activities of compounds 1 and 2 on four human lung cancer cells(16HBE, NCI-H1299, NCI-H460 and NCI-H292) were further determined.     

基于单-和双-三唑衍生物的三个Cu(II)和Cu(I)多金属氧簇基配合物的水热合成及光催化性能

在水热条件下，利用多齿的单-和双-三唑衍生物，制备了3种基于多金属氧簇基（POM）的Cu（Ⅱ）和Cu（I）杂化材料，即{[Cu（L₁）₂（Mo₄O₁₃）]·2H₂O}_n（1），{[Cu_1.5（L₂）（HL₂）（H₂O）（Mo₄O₁₃）]·2H₂O}_n（2），{[Cu₂（L₃）_1.5（Mo₄O₁₃）]·H₂O}_n（3）（L₁=4-pyridine-2-1，2，4-triazole，HL₂=3-（4H-1，2，4-triazol-4-yl）benzoic acid，L₃=trans-4，4''-azo-1，2，4-triazole）。通过单晶X射线衍射、傅里叶变换红外光谱和粉末X射线衍射分析确定了它们的结构。在1中，Mo₄O₁₃^2-阴离子和Cu（Ⅱ）中心通过双齿L₁相互连接，最终形成了二维（2D）POMs基的Cu（Ⅱ）杂化金属-有机骨架。在2中，Mo₄O₁₃^2-阴离子和Cu（Ⅱ）中心通过桥接水原子（O18），双齿HL₂和三齿L₂^-相互连接，最终形成了三维（3D）POMs基的Cu（Ⅱ）微孔金属-有机骨架。在3中，L₃配体桥接相邻的Cu（I）中心和Mo₄O₁₃^2-阴离子，最终形成独特的双重穿插结构的3DPOMs基的Cu（I）杂化配位框架。光催化实验研究表明，样品1~3对于不同有机染料罗丹明B（RhB）、亚甲基蓝（MB）和甲基橙（MO）都具有很好的光催化降解能力。     

基于单-和双-三唑衍生物的三个Cu（Ⅱ）和Cu（Ⅰ）多金属氧簇基配合物的水热合成及光催化性能

在水热条件下,利用多齿的单-和双-三唑衍生物,制备了3种基于多金属氧簇基（POM）的Cu（Ⅱ）和Cu（Ⅰ）杂化材料,即{[Cu（L¹）₂（Mo₄O₁₃）]·2H₂O}_n（1）,{[Cu_1.5（L²）（HL₂）（H₂O）（Mo₄O₁₃）]·2H₂O}_n（2）,{[Cu₂（L₃）_1.5（Mo₄O₁₃）]·H₂O}_n（3）（L₁=4-pyridine-2-1,2,4-triazole,HL₂=3-（4H-1,2,4-triazol-4-yl）benzoic acid,L₃=trans-4,4''-azo-1,2,4-triazole）。通过单晶X射线衍射、傅里叶变换红外光谱和粉末X射线衍射分析确定了它们的结构。在1中,Mo₄O₁₃^2-阴离子和Cu（Ⅱ）中心通过双齿L₁相互连接,最终形成了二维（2D）POMs基的Cu（Ⅱ）杂化金属-有机骨架。在2中,Mo₄O₁₃^2-阴离子和Cu（Ⅱ）中心通过桥接水原子（O18）,双齿HL₂和三齿L₂^-相互连接,最终形成了三维（3D）POMs基的Cu（Ⅱ）微孔金属-有机骨架。在3中,L₃配体桥接相邻的Cu（Ⅰ）中心和Mo₄O₁₃^2-阴离子,最终形成独特的双重穿插结构的3DPOMs基的Cu（Ⅰ）杂化配位框架。光催化实验研究表明,样品1~3对于不同有机染料罗丹明B（RhB）、亚甲基蓝（MB）和甲基橙（MO）都具有很好的光催化降解能力。     

3-((5-(3-吡啶基)-2-(1,3,4-噁二唑基))硫代)-2,4-戊二酮Cu(Ⅱ)/Zn(Ⅱ)/Mn(Ⅱ)配合物的合成及其晶体结构

将配体3-((5-(3-吡啶基)-2-(1,3,4-噁二唑基))硫代)-2,4-戊二酮(HL)与Cu(OAc)_2·H_2O、Zn(OAc)_2·2H_2O和Mn(OAc)_2·4H_2O分别进行配位反应,得到3个配位聚合物{[Cu_2(L)_4]·CHCl_3}_n(1)、{[Zn(L)_2]·4CHCl_3}_n(2)和{[Mn(L)_2]·4CHCl_3}_n(3),并通过元素分析、红外光谱、粉末X射线衍射、单晶X射线衍射等对配合物的结构进行了表征。在固体状态下,配位聚合物1形成1D螺旋链状结构,配位聚合物2和3形成2D网状结构。     

Crystal Engineering of Co(Ⅱ) Metal-organic Frameworks Based on the Hydrolysis Product of Letrozole and Coligands

The cyanide groups of letrozole(1-[bis(4-cyanophenyl)methyl]-1,2,4-triazole) were hydrolyzed into the carboxylic groups under alkaline conditions. Then the hydrolysis product(1-[bis(4-carboxylphenyl)methyl]-1,2,4-triazole, H_2ltzda) reacted with Co(NO_3)_2·6H_2O in the presence of different bipyridl-typed ligands under hydrothermal conditions. As a result, two new Co(Ⅱ) MOFs were obtained, formulated as [Co_2(ltzda)_2(bpp)_2]_n(1) and {[Co_2(ltzda)_2(bpy)]·4H_2O}_n(2)(bpp = 1,3-di(4-pyridyl)propane, bpy = 4,4'-bipyridine). Two MOFs have been characterized by single-crystal X-ray diffraction, thermogravimetric analysis and magnetic measure. 1 displays a 2D metal-organic framework containing wave layers and 2 shows a pillared-layer structure existing in a 2-fold interpenetrated mode.     

一个基于[Cu_4(μ_2-OH)_2N_(12)]的10-连接3D配合物的合成、结构和光催化性质（英文）

通过扩散法合成了一个新的配位聚合物{[Cu_2(OH)(btre)_(1.5)(1,2,4-btc)]·13H_2O}_n (1·13H_2O)(btre=1,2-二(4H-1,2,4-三唑)乙烷,1,2,4-btc=1,2,4-苯三甲酸根)。测试了1·13H_2O的晶体结构,并用红外光谱、元素分析、粉末X射线衍射对其进行表征。单晶X射线衍射表明1是基于四核铜簇[Cu_4(μ_2-OH)_2N_(12)]构筑的10-连接的3D框架,其拓扑符号为3~(12)·4~(28)·5~5。研究了1·13H_2O的热稳定性以及对甲基橙的催化降解作用。     

Water-induced reversible dissolution/reorganization transformations of Cu(Ⅱ)-K(I) heterometallic coordination polymers

Three new heterometallic coordination compounds, namely, [KCu(I3)(L)2(H2O)2]n(1), [KCu(I3)(L)2(H2O)]n(2) and [CuK4(I3)2(L′)4]n(3), were prepared and characterized(HL=5-methylpyrazine-2-carboxylic acid, HL′=p-tolylacetic acid). Structural studies revealed that 1 and 2 exhibit 3D frameworks with rectangular channels occupied by triiodide ions. Both compounds can be symbolized as a 5-connected net with pcu topology. In compound 3, a one-dimensional polyhedral chain is connected by hexanuclear mask like clusters [Cu2K4O8]. These chains are further linked each other via rare(1,1,3,3)-triiodide ion-bridging units to generate a 3D(4,5,6)-connected net with the point symbol of {12}2{4·122}4{46}{48·62}4{49·66}4. It is noteworthy that water-induced reversible dissolution/reorganization processes occur between 1/2 and [Cu(L)2(H2O)]n·3nH2O. The thermal and photoluminescence properties of compounds 1, 2, and 3 were investigated as well.     

金属离子导向的2,2′-联苯甲酸和1,4-二(1-苯并咪唑基甲基)苯构筑的配合物的合成、结构和性质（英文）

在溶剂热条件下合成并表征了2个基于2,2′-联苯甲酸(H_2dpa)和1,4-二(1-苯并咪唑基甲基)苯(bbix)的配位聚合物:[Cu_2(bbix)(dpa)_2(C_2H_5OH)_2]_n(1),{[Cd(bbix)_(0.5)(dpa)]·0.5H_2O}_n(2)。两者均显示二维结构。1中含有Cu-dpa螺旋链,bbix进而将螺旋链连接形成以Cu(Ⅱ)离子为3-连节点的6~3波浪状网格。而在配合物2中,dpa~(2-)与Cd(Ⅱ)形成四元环和八元环交替连接而成的带状一维链,并由bbix连接得到二维网格。此外,还研究了1和2的热稳定性以及室温下2的荧光性能。