基于衣康酸配体构筑的两个锌配合物的合成、结构和荧光性质（英文）

通过水热法合成了两种锌配位聚合物{[Zn(ic)(bip)]·2H_2O}_n(1)和[Zn(ic)(bpe)]_n(2)(H_2ic=衣康酸,bip=3,5-二(1-咪唑基)吡啶,bpe=1,2-二(4-吡啶基)乙烯),并通过X射线单晶衍射和元素分析对其结构进行了表征。配合物1和2均为含有一维金属-羧酸链的二维(4,4)格子层结构。此外,对它们的热重、粉末X射线衍射和固体荧光性能进行了考察。与配体bip相比,1的发射光谱发生了明显的蓝移(~78 nm),可能归因于配体到金属的电荷转移;2显示与游离的bpe配体相似的荧光性质,轻微的红移可能是因为与金属离子之间的配位作用导致的。     

基于琥珀酸配体的锌/镉配合物的合成、结构及性质

在水热条件下获得了2个过渡金属配合物[Zn (suc)(HL)]_n(1)和[Cd (suc)0.5(L)]_n(2)(H₂suc=琥珀酸,HL=3-(2-吡啶基)吡唑),并通过元素分析、IR光谱、单晶X射线衍射、热重分析、荧光光谱和粉末X射线衍射对结构进行了表征。在配合物1中,羧基配体suc^2-通过双齿和单齿模式桥联金属中心形成了二维网络结构。在2中,suc^2-和L-配体连接Cd (Ⅱ)离子也形成了二维框架。此外,通过基于Gaussian16程序的PBE0/LANL2DZ方法,对从1和2的晶体结构中选出的“分子碎片”进行了量子化学计算。计算结果表明,配位原子与Zn (Ⅱ)离子、Cd (Ⅱ)离子之间存在着明显的共价相互作用。     

两个以3-硝基邻苯二甲酸为配体构筑的锌和钴配位聚合物的合成、晶体结构和性质

通过水热法合成了2种配位聚合物{[Zn(3-Nbdc)(bpmp)]·H₂O}_n (1)和{[Co(3-Nbdc)(bpmp)(H₂O)]·H₂O}_n (2)(3-Nbdc^2-=3-硝基邻苯二甲酸根, bpmp=1, 4-二(4-吡啶甲基)哌嗪), 并通过X-射线单晶衍射、元素分析和红外光谱对其结构进行了表征。配合物1和2均为二维(4, 4)格子层结构, 其中1含有双核单元, 2含有螺旋金属羧酸链。此外, 对它们的热重、粉末X-射线衍射、固体荧光和磁性性能进行了考察。1显示与游离的3-硝基邻苯二甲酸相似的荧光性质, 锌离子的配位环境和配体之间的耦合作用对其荧光性能几乎没有影响。2在低温区表现出铁磁耦合作用, 高温区的χ_MT值降低主要是由于八面体钴的自旋轨道耦合导致的。     

两个以3-硝基邻苯二甲酸为配体构筑的锌和钴配位聚合物的合成、晶体结构和性质

通过水热法合成了2种配位聚合物{[Zn(3-Nbdc)(bpmp)]·H₂O}_n (1)和{[Co(3-Nbdc)(bpmp)(H₂O)]·H₂O}_n (2)(3-NbdC₂-=3-硝基邻苯二甲酸根, bpmp=1, 4-二(4-吡啶甲基)哌嗪), 并通过X-射线单晶衍射、元素分析和红外光谱对其结构进行了表征。配合物1和2均为二维(4, 4)格子层结构, 其中1含有双核单元, 2含有螺旋金属羧酸链。此外, 对它们的热重、粉末X-射线衍射、固体荧光和磁性性能进行了考察。1显示与游离的3-硝基邻苯二甲酸相似的荧光性质, 锌离子的配位环境和配体之间的耦合作用对其荧光性能几乎没有影响。2在低温区表现出铁磁耦合作用, 高温区的χ_MT值降低主要是由于八面体钴的自旋轨道耦合导致的。     

基于柠康酸构筑的三个配合物的合成、结构与性能

在水热条件下,制备出3个配位聚合物,即{[Zn（ca）（iimb）]·0.75H₂O}_n（1）,{[Cd（ca）（iimb）（H₂O）]·0.75H₂O}_n（2）和{[Zn（ca）（bpe）_0.5（H₂O）]·H₂O}_n（3）（H₂ca=柠康酸,iimb=1-（1-咪唑基）-4-（咪唑基-1''-甲基）苯,bpe=1,2-二（4-吡啶基）乙烯）,并通过单晶X射线衍射、红外光谱和元素分析进行结构表征。配合物1是含有一维金属羧酸链的二维网状层。2是具有羧酸桥连双核的一维准梯形链状结构。3是二维波浪层。其中2和3的三维超分子结构由丰富的氢键相互作用形成;而1的三维超分子结构通过范德华力堆积而成。研究了3个配合物的热重分析（TGA）,粉末X射线衍射（PXRD）和荧光性质。固态荧光光谱表明3个配合物的发射光谱与相应的辅助配体相似。此外,配合物3在紫外光照射下,在H₂O₂存在时对亚甲基蓝（MB）的降解表现出良好的光催化活性。     

以吡嗪四甲酸为配体的配合物的合成及表征

合成了两种金属配合物{[Cu₂(pztc)(4,4'-bpy)(H₂O)₄]·6H₂O}_n (1),{(H₂bpe)[Cd(pztc)(H₂O)₂]·2.5H₂O}_n (2)(H₄pztc=吡嗪-2,3,5,6-四甲酸,bpy=4,4'-联吡啶,bpe=1,2-二(4-吡啶基)乙烯),测定了其晶体结构,并对其进行了红外光谱、荧光光谱和热重分析等表征。两种配合物均为二维层状结构,但其中吡嗪四酸的配位方式不同。配合物2具有蓝色的荧光,最大荧光发射峰在475 nm。测试了配合物1的电子顺磁共振谱,结果显示Cu²⁺的特征谱带。     

2,2'-硫代-二(苯甲酸)和双吡啶配体构筑的三个双核锌配位聚合物

用水热法合成了3个配位聚合物并测定了其晶体结构,分子式分别为[Zn₂(tba)₂(bpy)]_n(1),[Zn₂(tba)₂(bpe)]_n(2)和[Zn(tba)(bpp)]n(3),(tba=2,2''-thiobis(benzoic acid),bpy=4,4''-bipyridine,bpe=1,2-bis(4-pyridyl)ethylene,bpp=1,3-bis(4-pyridyl)propane)。tba是由2-(2-cyanophenylthio)benzoicacid原位水解得到的。X射线单晶衍射分析表明配合物1含双核锌单元,由tba和bpy连成二维(4,4)网。配合物2是基于[Zn₂(tba)₂]_n子链,由bpe连接而成的钻石拓扑三维结构。有趣的是,配合物3是一个由(4,4)网交缠形成的二维到二维的聚索烃。Tba配体构型和各双吡啶辅助配体引起了3个化合物的结构各异性。此外,研究了3个配位聚合物的荧光性质。     

基于半刚性的4-羧基苯乙酸和富氮共配体组装的Zn(Ⅱ)/Cd(Ⅱ)配位聚合物的合成、结构和性质

采用溶剂热法合成了一系列Zn（Ⅱ）/Cd（Ⅱ）配位聚合物：{[Zn（cbaa）（bpmp）_0.5（H₂O）]·2H₂O}_n（1）、[Zn（cbaa）（bip）]_n（2）、[Cd（cbaa）（Hizb）]_n（3）和[Cd₂（cbaa）₂（itmb）（H₂O）]_n（4）（H₂cbaa=4-羧基苯乙酸;bpmp=1,4-二（4-吡啶甲基）哌嗪;bip=3,5-双（1-咪唑基）吡啶;Hizb=2-（4-咪唑-1-基苯基）-1H-苯并咪唑;itmb=1-（咪唑-1-基）-4-（1,2,4-三唑-1-基甲基）苯）。X射线单晶衍射结果表明,半刚性的4-羧基苯乙酸和富氮辅助配体构筑形成了4个多样化拓扑结构的配位聚合物。化合物1和2是Zn（Ⅱ）配位聚合物：1是由2个Zn-羧酸盐链之间通过富氮配体桥连形成的一维梯形结构,而2是由Zn-羧酸盐链之间通过富氮配体拓展形成的二维单层结构;化合物3和4是Cd（Ⅱ）配位聚合物：3是由Cd-O无机链之间通过羧酸配体的桥连拓展形成的二维单层结构,富氮配体作为伸出层平面的悬臂仅仅起到结构修饰作用,而4则形成了Cd-羧酸盐空旷双层结构,富氮配体填充在层内空腔中,从而导致了致密双层结构的产生。另外,考察了4个化合物的热稳定性和光致发光性能。     

2, 2'-硫代-二(苯甲酸)和双吡啶配体构筑的三个双核锌配位聚合物

用水热法合成了3个配位聚合物并测定了其晶体结构, 分子式分别为[Zn₂(tba)₂(bpy)]_n (1), [Zn₂(tba)₂(bpe)]_n (2)和[Zn(tba)(bpp)]_n (3), (tba=2, 2''-thiobis(benzoic acid), bpy=4, 4''-bipyridine, bpe=1, 2-bis(4-pyridyl)ethylene, bpp=1, 3-bis(4-pyridyl)propane)。tba是由2-(2-cyanophenylthio)benzoic acid原位水解得到的。X射线单晶衍射分析表明配合物1含双核锌单元, 由tba和bpy连成二维(4, 4)网。配合物2是基于[Zn₂(tba)₂]_n子链, 由bpe连接而成的钻石拓扑三维结构。有趣的是, 配合物3是一个由(4, 4)网交缠形成的二维到二维的聚索烃。Tba配体构型和各双吡啶辅助配体引起了3个化合物的结构各异性。此外, 研究了3个配位聚合物的荧光性质。     

三种二酸Cd(Ⅱ)混配聚合物的结构与荧光性质

本文以刚性间苯二酸(IP),对苯二酸(TP)及柔性丁二酸(SU)为桥联配体,溶剂热法合成了3个配合物[Cd(TP)(DPQ)(H₂O)]_n (1),[Cd(IP)(DPPZ)]_n (2)和[Cd(SU)(DPPZ)]_n(3)(DPQ=吡嗪[2,3-f][1,10]菲咯啉,DPPZ=二吡啶[3,2-a∶2′,3′-c]并吩嗪)。通过X射线单晶衍射分别测定了它们的结构。3个配合物均为单斜晶系,空间群分别为P2₁/c(配合物1和3)和C2/c(配合物2)。配合物荧光性质的表征表明,采用刚性二酸有利于配位聚合物荧光的增强。     

基于衣康酸配体构筑的两个锌配合物的合成、结构和荧光性质

通过水热法合成了两种锌配位聚合物{[Zn（ic）（bip）]·2H₂O}_n（1）和[Zn（ic）（bpe）]_n（2）（H₂ic=衣康酸,bip=3,5-二（1-咪唑基）吡啶,bpe=1,2-二（4-吡啶基）乙烯）,并通过X射线单晶衍射和元素分析对其结构进行了表征。配合物1和2均为含有一维金属-羧酸链的二维（4,4）格子层结构。此外,对它们的热重、粉末X射线衍射和固体荧光性能进行了考察。与配体bip相比,1的发射光谱发生了明显的蓝移（⁷8 nm）,可能归因于配体到金属的电荷转移;2显示与游离的bpe配体相似的荧光性质,轻微的红移可能是因为与金属离子之间的配位作用导致的。     

Zinc coordination polymers with rigid dicarboxylates and semirigid 3,5-bis(imidazole-1-yl) pyridine: syntheses,structural topologies,and luminescent properties

Two metal coordination polymers, {[Zn(bpdc)(bip)]·2H₂O}_n (1) and [Zn(tdc)(bip)] (2) [H₂bpdc?=?biphenyl-4,4’-dicarboxylate, H₂tdc?=?thiophene-2,5-dicarboxylate, bip?=?3,5-bis(imidazole-1-yl)pyridine], have been synthesized and characterized by IR, elemental analysis, XRD, and X-ray single-crystal diffraction. In 1, bpdc and bip link Zn(II) ions into a corrugated 2D layer. The corrugated 2D layers polycatenate each other, yielding a 2D→3D polycatenation net. In 2, dinuclear Zn(II) units are formed by bip and further connected by tdc to construct a 2D 3-connected framework. The luminescent properties of 1 and 2 are investigated in the solid state at room temperature.     

ZnII and CdII Metal Organic Frameworks Based on 2-Methyl-6-oxygen-1,6-dihydro-3,4'bipyridine-5-carbonitrile

To investigate the coordination chemistry of modbc (2-methyl-6-oxygen-1,6-dihydro-3,4'-bipyridine-5-carbonitrile) with Zn^II and Cd^II salts under the solvothermal conditions, six new MOFs with the formulas [Zn(modbc)₂(mpa)]_n ( 1 ), [Zn(modbc)(mpa)(H₂O)]_n ( 2 ), [Zn(modbc)(pa)_0.5(H₂O)]_n ( 3 ), [Cd(modbc)(pa)_0.5(H₂O)]_n ( 4 ), [Zn(modbc)₂(tpa)]_n ( 5 ), and [Cd(modbc)₂(pda)(H₂O)]_n ( 6 ) (mpa = m-phthalic acid; pa = pyromellitic acid; tpa = terephthalic acid; pda = pentane diacid) were successfully synthesized by solvothermal reaction and fully characterized by elemental analysis, IR spectroscopy, single crystal, powder X-ray diffraction, thermal and photoluminescence properties. Though MOFs 3 and 4 have the same structure, we have obtained three different kinds of coordination configurations by the X-ray diffration analysis. Compared with 1 and 2 , coordination water has no effect on the solid fluorescence emission of MOFs. It is worth noting that the fluorescence intensity of 3 containing central Zn^II atoms is very strong, whereas that of isomorphism 4 containing central Cd^II atoms has almost no fluorescence emission, showing that metal ions have very important influence on the fluorescence emission. Further, we found that solvents had an important effect on the fluorescence emission in liquid fluorescence of MOFs 1 – 6 .     

Design and syntheses of two threefold interpenetrating 2-D networks

Two new interpenetrating networks, [Ni(2,2′-bpy)(5-npa)(bpe)_0.5(H₂O)] _n (1) and [Ni(2,2′-bpy)(5-npa)(bpa)_0.5(H₂O)] _n (2) (2,2′-bpy?=?2,2′-bipyridine, 5-npa?=?5-nitroisophthalato, bpe?=?1,2-bis(4-pyridyl)ethylene, bpa?=?1,2-bis(4-pyridyl)ethane), have been synthesized and characterized by elemental analyses, IR spectroscopy, thermogravimetric analyses, X-ray powder diffraction, and single-crystal X-ray diffraction. Complexes 1 and 2 have similar structures and show a threefold interpenetrating topology constructed by three 2-D wave-like networks. Secondary building unit (SBU), [Ni(2,2′-bpy)(5-npa)(H₂O)] _n , was used as starting material of the multistep reaction. Replacing one coordination bond of chelating carboxyl group of SBUs by bpe and bpa afford the two threefold interpenetrating complexes.     

基于柔性的高酞酸和双咪唑型配体的Ni(Ⅱ)/Cd(Ⅱ)/Zn(Ⅱ)配位聚合物的合成、结构和性质（英文）

基于柔性的高酞酸(H2hmph)和双咪唑型配体,通过溶剂热法合成了3种新的配位聚合物:{[Ni2(hmph)2(bib)2(H2O)2]·3H2O}n(1)、[Cd(hmph)(bib)]n(2)和{[Zn(hmph)(bip)]·H2O}n(3),其中bib=1,4-双(1-咪唑基)苯、bip=3,5-双(1-咪唑基)吡啶。配合物1是由Ni-羧酸链之间通过bib配体桥联而成的二维单层结构;配合物2为Cd-羧酸双股链之间通过bib配体拓展而成的二维双层结构,并含有由羧基连接的双核单元;配合物3是由羧酸连接而成的双核Zn单元通过bip配体拓展形成的双股链。3个配合物都具有较高的热稳定性。磁性分析表明在配合物1中存在铁磁性交换偶合作用。另外,配合物2和3的荧光性质与相应的配体相比都表现出明显的蓝移。     

Crystal structures and magnetic properties of three cobalt(II)–organic frameworks with nanoscale channels

Three cobalt(II) coordination polymers, {[Co(nip)(4,4′-bpy)] · 3H₂O} _n (1), [Co(nip)(bpe)] _n (2), and [Co(nip)(bpp)(H₂O)] _n (3), were hydrothermally synthesized by the reaction of cobalt nitrate hexahydrate and nip with 4,4′-bpy, bpe, and bpp [nip = 5-nitro-1,3-benzenedicarboxylato, 4,4′-bpy = 4,4′-bipyridine, bpe = 1,2-bis(4-pyridyl)ethane, bpp = 1,3-bis(4-pyridyl)propane], respectively. Co(II) displays different coordination in the three complexes, resulting in different structures with nanoscale channels. Compounds 1 and 2 form 2-D layer structures, but 3 has a two-fold interpenetrated 3-D framework. The magnetic properties associated with their crystal structures were investigated.     

Hydrothermal Syntheses and Characterizations of Three ZnII Coordination Polymers Tuned by pH Value and Base

Three new Zn^II coordination polymers, [Zn(bpe)(HL)₂(H₂O)]_n ( 1 ), {[Zn(bpe)(L)] · H₂O}_n ( 2 ), and [Zn₂Ca(bpe)(HL)₂(L)₂]_n ( 3 ) [H₂L = 5‐methoxyisophthalic acid and bpe = 1,2‐dis(4‐pyridyl) ethylene], were hydrothermally synthesized under different pH values and bases. Their structures were determined by single‐crystal X‐ray diffraction and further characterized by elemental analyses and IR spectroscopy. Polymer 1 is formed at pH = 4 and has a 1D chain structure. These 1D chains are linked by hydrogen bonds to afford a 1D double chain and further to form a threefold interpenetrating network. At pH = 7, a 2D layer structure of 2 with sql topology is formed. By using calcium hydroxide as base for the synthesis of 3 , a 3D network with pcu topology is obtained. These structural differences among 1 – 3 indicate that pH value and the identity of the base play important role in defining the overall structures of metal‐organic frameworks. In addition, the fluorescent properties of 1 – 3 are discussed.     

Two Zinc(II) Coordination Polymers Based on Terphenyl‐2,2′,4,4′‐tetracarboxylate and Dipyridyl Ligands: Syntheses,Crystal Structures,and Luminescent Properties

Two coordination polymers, {[Zn₂(L)(bpy)] · 2H₂O}_n ( 1 ) and [Zn₂(L)(bpe)]_n ( 2 ) [H₄L = terphenyl‐2,2′,4,4′‐tetracarboxylic acid, bpy = 4,4′‐bipyridine, and bpe = 1,2‐bis(4‐pyridyl)ethane], were hydrothermally synthesized under similar conditions and characterized by elemental analysis, IR spectroscopy, TGA, and single‐crystal X‐ray diffraction analysis. Compound 1 has a 3D framework containing Zn–O–C–O–Zn 1D chains. Compound 2 exhibits a 3D framework, which features tubular channels. The channels are occupied by bpe molecules. The differences in the structures demonstrate that the auxiliary dipyridyl‐containing ligand has a significant effect on the construction of the final framework. Additionally, the fluorescent properties of the two compounds were also studied in the solid state at room temperature.     

Synthesis,structures and magnetic properties of two isomeric coordination polymers constructed from pamoic acid and 1,2-di(4-pyridyl)ethane

Two isostructural compounds, [Co(pam)(bpe)(H₂O)₂]_n (1) and [Mn(pam)(bpe)(H₂O)₂]_n (2) (H₂pam = pamoic acid, bpe = 1,2-di(4-pyridyl)ethane), have been solvothermally synthesized and characterized by elemental analyses, IR, and powder X-ray diffraction. Single-crystal X-ray analysis reveals that 1 and 2 are isostructural and feature a threefold interpenetrated cds topological framework. Magnetic investigations reveal that both 1 and 2 exhibit antiferromagnetic properties.