两种4-溴苯甲酸铽配合物的合成、晶体结构及性质

合成了两种双核铽配合物[Tb(4-BrBA)₂(Phen)(NO₃)]₂ (1)和[Tb(4-BrBA)₃(2,2′-bipy)(H₂O)]₂·2H₂O (2)(4-BrBA=4-溴苯甲酸根,Phen=1,10-邻菲咯啉,2,2′-bipy=2,2′-联吡啶),并用X-射线单晶衍射结构分析方法测定了其晶体结构。这2种配合物均是具有反演中心的二聚体。在四元混配配合物1中,2个Tb³⁺离子被4个4-溴苯甲酸根以双齿桥联和三齿桥联两种方式联结;每个Tb³⁺离子与邻菲咯啉的2个氮原子、硝酸根的2个氧原子和4个桥联4-溴苯甲酸根的5个氧原子配位;Tb³⁺离子的配位数为9。在配合物2中,2个Tb³⁺离子被4个4-溴苯甲酸根以双齿桥联方式联结;每个Tb³⁺离子与2,2′-联吡啶的2个氮原子、水分子的1个氧原子、4个双齿桥联4-溴苯甲酸根的4个氧原子以及1个单齿配位4-溴苯甲酸根的1个氧原子配位;Tb³⁺离子的配位数为8。配合物2中游离水分子与配位水分子以及4-溴苯甲酸根之间形成了氢键,氢键将双核分子2连接成一维链状结构。配合物1和2在紫外灯照射下均发出强烈的绿光,它们的荧光光谱在490、545、585和621 nm处出现4条谱线,这是由Tb³⁺离子的 ⁵D₄ → ⁷F_j(j=6～3)跃迁产生的。     

4-(1,2,4-三唑-1-基)苯酚铜(Ⅱ)/镍(Ⅱ)配合物的晶体结构及荧光性质

合成并通过单晶和粉末X射线衍射、元素分析、红外光谱、热失重以及荧光光谱技术表征了含有4-（1,2,4-三唑-1-基）苯酚（hptrz）配体的2个过渡金属配合物{[Ni（H₂O）₂（hptrz）₂（tp）]·2DMF}_n（1）和[Cu（hptrz）₂（SCN）₂]·2H₂O（2）（H₂tp为对苯二甲酸）。配合物1中八面体的Ni（Ⅱ）离子由tp^2-阴离子拓展形成线性的一维链状结构;而配合物2则呈现中心对称的单核结构。配合物中,中性的hptrz配体呈现端基配位模式,并通过形成O-H…O氢键相互作用将低维结构拓展为高维超分子网络。此外,配体内的电荷转移使这2个配合物均在紫外区发射出强的荧光发射峰。     

以3, 5-二甲基-1-羧甲基-4-吡唑甲酸为配体的两个锌的配合物的合成、晶体结构和荧光性能

以3, 5-二甲基-1-羧甲基-4-吡唑甲酸和4, 4'-联吡啶为配体, 合成了1个单核锌(II)配合物[Zn(4,4'-bpy)(Hcmdpca)₂(H₂O)₃]·2H₂O (1)和1个锌(II)的一维配位聚合物[Zn(4, 4'-bpy)(Hcmdpca)₂(H₂O)]·3H₂O (2)(H₂cmdpca=3, 5-二甲基-1-羧甲基-4-吡唑甲酸;4, 4'-bpy=4, 4'-联吡啶), 并用元素分析、红外光谱、X-射线单晶衍射结构分析、热重分析等对其进行了表征。配合物1和2都属于单斜晶系, 空间群为P2₁/c。配合物1的锌离子都位于一个畸变的八面体构型中。配合物1中的独立结构单元间通过分子间氢键作用构成一个三维的超分子结构。而在2中, 锌离子位于一个畸变的四方锥构型中, 每个4, 4'-联吡啶分子桥联2个相邻的 锌(II)离子, 形成一个一维链;这些一维链和水分子通过分子间氢键进一步形成一个三维的结构。此外还考察了1和2的热稳定性和固体荧光性质。     

4-磺基苯甲酸镍配合物结构多样性与性质研究

本文报道2个镍/4-磺基苯甲酸/1,10-邻菲咯啉配合物的合成、表征、结构和性质。配合物[Ni(4-sb)(phen)(H₂O)₂]·(2H₂O) (1)是单核结构,配合物[Ni(phen)₃]·(4-Hsb)(OH)(8H₂O) (2)是1个阳离子与阴离子复合物。在这2个配合物中金属镍的配位形式均是六配位八面体构型,Ni-N键长相近。2个配合物的扩展结构均为三维网络结构。配合物2中阳离子占据由阴离子与水分子形成的三维网络孔道。配合物2是一个羧基氢未脱去同时又有氢氧根的分子。     

两个新的4-羧基苯氧乙酸铜配合物的水热合成

由于CPOA^2-和HCPOA^-阴离子在反应体系中存在平衡关系，氯化铜与4-羧基苯氧乙酸和4,4¢-联吡啶在水热条件下反应得到了两个新的配位聚合物[Cu(CPOA)(4,4′-bpy)(H₂O)₂]·1.5H₂O (1) 和 [Cu₂(HCPOA)₄(4,4′-bpy)₄] (2) (H₂CPOA=4-羧基苯氧乙酸, 4,4′-bpy=4,4¢-联吡啶) 。研究结果表明配合物1具有三重穿插的CdSO₄-型网络结构，同时形成一维孔道，晶格水分子填充在孔道中。配合物2具有由配位键和O-H···N氢键组装形成的一维梯形链状结构。     

基于3，3′，4，4′-四羧基偶氮苯构筑的三个金属配合物的合成、晶体结构及性质

在水热条件下利用H₄ddb配体合成了3个过渡金属配合物[Co₂（ddb）（phen）₂（H₂O）₆]·3H₂O（1）,[Co（ddb）_0.5（bpy）_0.5（H₂O）₃]_n（2）和{[Ag（dpe）]·0.5（H₂ddb）·H₂O}_n（3）（H₄ddb=3,3'',4,4''-四羧基偶氮苯,bpy=4,4''-联吡啶,dpe=1,2-二（4-吡啶基乙烯））,并用元素分析、红外光谱、X射线粉末衍射、X射线单晶衍射对其进行了表征。配合物1为双核结构,基于丰富的氢键作用扩展形成三维超分子网结构。配合物2为基于钴离子通过ddb^4-配体以μ₄：η¹,η¹,η¹,η¹的配位模式连接而成的二维网结构。配合物3是由Ag（Ⅰ）离子与dpe配体形成的直链结构,客体分子H₂ddb^2-通过氢键作用将其扩展为三维超分子结构。此外还研究了配合物1~3的荧光性质和热稳定性。     

基于2,4,6-吡啶三羧酸配体桥连的铁(Ⅱ)/镍(Ⅱ)配位聚合物的水热合成及结构表征

在水热反应条件下FeCl₂·6H₂O、2,4,6-吡啶三羧酸(H₃pyta)和NaOH反应合成了1种一维链状铁配位聚合物[Fe₃(pyta)₂(H₂O)₈] (1);同样条件下Ni(OAc)₂·4H₂O、2,4,6-吡啶三羧酸(H₃pyta)、NaOH和4-氨基-3,5-二(4-吡啶基)-1,2,4-三氮唑(abpt)反应合成了1种二维网状镍配合物[Ni₃(pyta)₂(abpt)₂(H₂O)₃]·2H₂O (2)。通过元素分析和红外光谱对这2个配位聚合物进行了表征。单晶结构表明：配合物1的晶体属于单斜晶系,Cc空间群;配合物2的晶体属于单斜晶系,P2₁/c空间群。在配合物1中,pyta^3-配体采取μ₂-和μ₄-pyta^3- 2种桥连模式将Fe原子连成了沿c轴方向延伸的Fe-pyta链。而在配合物2中,pyta^3-配体仅采取μ₂-桥连模式将Ni原子连成线型三核[Ni₃(pyta)₂]单元,这些三核单元进一步通过abpt辅助配体桥连成二维 (4,4)层状结构。     

Phen-铜(II)-氨基酸配合物的合成、表征及其SOD活性

合成了3个新的SOD模拟配合物：[Cu(Phen)(L-Gln)(H₂O)]Cl·2H₂O (1)、[Cu(Phen)(L-Ala)(H₂O)]Cl·4H₂O (2)、[Cu(Phen)(L-Thr)(H₂O)]Cl·2H₂O (3) [Phen(1，10-邻菲咯啉)、L-Gln(谷氨酰胺)、L-Ala(丙氨酸)、L-Thr(苏氨酸)]。用元素分析、摩尔电导、红外光谱、紫外-可见光谱对配合物进行了表征。用X-射线衍射对配合物[Cu(Phen)(L-Gln)(H₂O)]Cl·2H₂O的晶体结构进行了测定。用氯化硝基四氮唑蓝(NBT)光还原法对这3个配合物催化歧化超氧阴离子自由基(O₂^{- ·})的能力进行了测定。结果表明：这些配合物具有较高的SOD活性， 催化速率常数K_Q分别为1.58 × 10⁷ mol^-1·L·s^-1、5.65 × 10⁷ mol^-1·L·s^-1、0.83 × 10⁷ mol^-1·L·s^-1。     

基于2-(4'-羧基苯基)咪唑-4,5-二羧酸构筑的三个镉/锌配位聚合物的合成、拓扑结构、荧光光谱及DNA作用

以2-（4''-羧基苯基）咪唑-4,5-二羧酸（H₄CPhIDC,C₁₂H₈N₂O₆）为配体,用溶剂热合成了3种配位聚合物{[Cd₂（CPhIDC）（bimb）]·H₂O}_n（1）、{[Cd₂（CPhIDC）（phen）₂]·3H₂O}_n（2）、{[Zn₂（CPhIDC）（bpp）]·1.5H₂O}_n（3）（bimp=1,4-双咪唑基-丁烷,phen=1,10-菲咯啉,bpp=1,3-双（4-吡啶基）-丙烷）。用元素分析、红外光谱、粉末X射线衍射和单晶X射线衍射对配合物进行了表征和结构分析。结构分析表明,主配体以完全去质子化CPhIDC^4-的形式与中心金属离子形成以μ₄和μ₅为配位模式的二维及三维聚合物。配合物1和3是三维网络结构,同时呈现（3,4,5）-连接的（5·6·7）（4·5²·6·7²）（4·5²·6·7⁴·8²）拓扑结构,两者的不同之处是中心离子和辅助配体。配合物2是二维波纹状渔网结构,呈现4⁴·6²拓扑结构,在其空间填充上又类似于DNA双螺旋链的单螺旋结构。测定了产物的固体荧光光谱;用EtBr荧光探针法研究了配体及配合物与ct-DNA的相互作用。     

1,2,4-苯三甲酸铜二维网状配合物的合成及结构表征(英)

在室温下,MnSO₄·H₂O和1,2,4-苯三甲酸(H₃BTC)反应得到化合物[Mn(H₂BTC)₂(H₂O)₄]·2H₂O (1),化合物1和CuSO₄·5H₂O反应得到化合物[Cu(HBTC)(H₂O)_1.5]·H₂O (2)。化合物1是一个单核分子化合物。在化合物1中,每个锰离子和两个H₂BTC^－离子及四个水分子配位。化合物2中,每个铜离子和三个HBTC^2－及两个水分子配位,其中的一个水分子起桥联作用从而形成二维网状结构。     

Syntheses and Crystal Structures of Four New Complexes [Mn(4,4''-bip)2(OH2)4](DBA)·4H2O and [M(OH2)(HDPA)2]·3H2O (M = Mn, Co, Ni)

Four new transition metal complexes, [Mn(4,4'-bip)2(OH2)4](DBA)·4H2O 1(4,4'-bip = 4,4'-bipyridine, H2DBA = benzene-1,3-dicarboxylic acid) and [M(OH2)(HDPA)2]·3H2O (M = Mn 2, M = Co 3, M = Ni 4,H2DPA = 2,6-pyridine-dicarboxylic acid), have been prepared from the reaction of transition metals and carboxylic acids, and characterized by X-ray and elemental analyses. For compound 1, the packing diagram shows that a three-dimensional network is formed via hydrogen bonds and strong π-π interactions. For compounds 2, 3 and 4,a double-helical chain is formed through hydrogen bonds. Moreover, a three-dimensional network is constructed from chains via complicated hydrogen bonds between crystal water molecules and oxygen atoms of HDPA-.     

Metal complexes as templates: syntheses, structures, and luminescent properties of two zinc phosphonocarboxylates with ABW-zeolite topology

Two novel zinc phosphonocarboxylates, Zn(3)(pbc)(2)(bpy)(H(2)O)·H(2)O (1) and Zn(2)(pbc)(2)·Zn(bpy)(H(2)O)(4)·2H(2)O (2) (pbc = 4-phosphono-benzoic acid, bpy = 2,2'-bipyridine), were hydrothermally synthesized and structurally characterized. Both of them exhibit zeolitic ABW topology in which double-zigzag inorganic chains are cross-linked by the organic parts. It is notable that the metal complex Zn(bpy)(H(2)O)(x) plays different roles in the two compounds. In 1, the Zn(bpy)(H(2)O) units coordinate with the phosphonate and carboxylate oxygen atoms and participate in the construction of the three-dimensional framework. In 2, the in situ generated [Zn(bpy)(H(2)O)(4)](2+) cation acts as a template, which directs the ABW-type open-framework by strong hydrogen bonds. It is the first example where a metal complex is used as a template in the synthesis of metal phosphonates. The luminescent properties of 1 and 2 are also investigated.     

含2-苯氧基丙酸根的镍、锌配位聚合物的合成与晶体结构

用溶液法和水热法分别合成了2个含2-苯氧基丙酸配体(HL)的聚合物{[NiL2(H2O)2(bipy)].2H2O}n(1)、{[ZnL2(bipy)].2H2O}n(2)(bipy=4,4′-联吡啶),用元素分析、红外光谱、热重和单晶X-射线衍射对产物进行了表征。在化合物1中,镍原子与2个羧基氧原子、2个配位水氧原子及2个4,4′-联吡啶的2个氮原子配位,配位数为6,镍原子的配位构型为畸变的八面体;而在化合物2中,锌原子与2个羧基氧原子及2个4,4′-联吡啶中的2个氮原子配位,锌原子的配位构型为畸变的四面体。在这2个化合物里,4,4′-联吡啶通过氮原子连接金属原子形成一维链状。链间氢键与π-π堆积作用又将一维链链接成二维层状结构。     

1，2-环己二羧酸及芳香含氮配体的双核镉、锰配合物的合成和晶体结构

用水热法合成了两种新的配合物[Cd2(e,e-trans-chdc)2(bipy)2(H2O)2].H2O(1)和[Mn2(e,a-cis-chdc)2(phen)2(H2O)2].2H2O(2)(chdc=1,2-环己二羧酸,bipy=2,2′-联吡啶和phen=1,10-邻菲咯啉),用X-射线单晶衍射分析确定了配合物的晶体结构。配合物1和2均为双核分子。配合物1中,2个镉髤离子由2个1,2-环己二羧酸根以e,e-trans配位方式桥联,每个镉髤离子与1个2,2′-联吡啶的2个氮原子、2个1,2-环己二羧酸根的4个氧原子及1个水分子中的氧原子配位,形成了单帽变形三棱柱构型。配合物2中,2个锰髤离子由2个1,2-环己二羧酸根以e,a-cis配位方式桥联,每个锰髤离子与1个1,10-邻菲咯啉的2个氮原子、2个1,2-环己二羧酸根的3个氧原子及1个水分子中的氧原子配位,形成了畸变的八面体构型。配合物1和2分子之间都存在π-π堆积和O-H…O、C-H…O弱作用,进而将双核分子连接成三维超分子网络结构。配合物的荧光均来自于配体的荧光。     

Syntheses and Crystal Structures of Four New Complexes [Mn(4,4′-bip)_2(OH_2)_4](DBA)·4H_2O and [M(OH_2)(HDPA)_2]·3H_2O (M = Mn,Co,Ni)

1 INTRODUCTION During the past years, dicarboxylic acids have been widely used as one polydentate ligand invo- lved in various metal chelation reactions to form transition or rare earth metal complexes with inter- esting properties in material science[1] and biological systems[2]. For example, Kim Y and his coworkers focused on the synthesis of copper(II) complexes containing malonate and pyrazine ligands to study their magnetic property and electronic conducti- vity[3]. The importance o…     

Syntheses and Structures of Two Isomorphous Metal-organic Coordination Complexes Based on 4-Pyrimidin-5-ylbenzoic Acid

The reactions of 4-pyrimidin-5-ylbenzoic acid （HL） with Co（NO3）2·6H2O and Ni（NO3）2·6H2O gave rise to two isomorphous mononuclear coordination complexes, namely, [CoL2（H2O）4] （1） and [NiL2（H2O）4] （2）. Both compounds were characterized by IR spectroscopy and single-crystal X-ray diffraction. X-ray crystallographic analyses reveal that they crystallize in monoclinic, space group P21/n. In the crystal structures of these two complexes, only one nitrogen atom of L coordinates to the metal center, and neither carboxylate group nor another nitrogen atom of L links to Co（Ⅱ） or Ni（Ⅱ）. 2D Layers with significant hydrogen bonds can be observed, and they are further linked by L to form a 3D supramolecular network. Nitrogen atoms are not involved in forming hydrogen bonds, but carboxylic groups of the ligands play an important role in the configuration of this hydrogen-bond layer.     

Solvothermal Synthesis and Structure Characterization of a 3D Hydrogen-bonded Copper Compound [Cu(H_2dhpmc)_2]·2H_2O

1 INTRODUCTION The controlled assembly of inorganic and coordination polymers from simple building blocks is an important challenge in the design of high- dimensionality systems. In the crystal engineering 'toolbox'[1], hydrogen bonding moieties are perhaps the implements used the most in the design of such supramolecular systems[2], and have been particularly strongly applied towards the synthesis of molecular magnetic materials[3~6]. Copper complexes play an important role in catalyzin…     

Metal carboxylate-phosphonate hybrid layered compounds: synthesis and single crystal structures of novel divalent metal complexes with N-(phosphonomethyl)iminodiacetic acid

Two novel divalent metal complexes with N-(phosphonomethyl)iminodiacetic acid, H(2)O(3)PCH(2)N(CH(2)CO(2)H)(2) (H(4)PMIDA), [Co(2)(PMIDA)(H(2)O)(5)] x H(2)O, 1, and [Zn(2)(PMIDA)(CH(3)CO(2)H)] x 2H(2)O, 2, have been synthesized and structurally characterized. The structure of complex 1 features two different kinds of Co(II) layers, namely, a cobalt phosphonate layer along the <100> plane and a cobalt carboxylate layer along the <300> plane. The Co(II) atoms in the phosphonate layer are octahedrally coordinated by 4 aqua ligands and 2 oxygen atoms from two phosphonic acid groups. Two Co(II) octahedra are bridged by a pair of phosphonic groups into a dimeric unit, and such dimers are interconnected into a layer through hydrogen bonding between aqua ligands. The Co(II) atoms in the carboxylate layer are octahedrally coordinated by a chelating PMIDA ligand, one aqua ligand, and one phosphonic oxygen atom from the neighboring PMIDA ligand. These Co(II) octahedra are interlinked by bridging carboxylic groups into a one-dimensional chain along the c-axis; such chains are held together by hydrogen bonds formed between carboxylic oxygen atoms and lattice water molecules, in such a way as to form a layer along the <300> direction. Two such layers are interconnected into a double layer via hydrogen bonding. These double layers are further interconnected with the Co(II) phosphonate layers through phosphonate tetrahedra along the a direction, resulting in the formation of a complicated three-dimensional network. The crystal structure of 2 contains a metal phosphonate and metal carboxylate hybrid layer along the <202> plane. One of the two zinc atoms in the asymmetric unit is tetrahedrally coordinated by four oxygen atoms from two phosphonic acid groups and two carboxylic groups; the other zinc atom is 5-coordinated by three oxygen atoms and a nitrogen atom from a chelating PMIDA ligand and one oxygen atom from the acetic acid. The above two types of zinc metal ions are interconnected by bridging carboxylic and phosphonic groups, resulting in the formation of a layered structure.     

萘氧乙酸及咪唑构筑的锌(Ⅱ)和铜(Ⅱ)配合物的水热合成、晶体结构及荧光性质

通过水热的方法合成得到2个由萘氧乙酸及咪唑配体构筑的配合物Zn(2-naph)₂(imi)₂ (1)和2Cu(2-naph)₂(imi)₂(H₂O)·Cu(2-naph)₂(imi)₂(H₂O) (2)(2-naph=2-naphthoxyacetate,imi=imidazole),它们的结构通过X射线晶体衍射、红外光谱和元素分析得到确定。在配合物1中,锌原子与来自不同2-萘氧乙酸配体中的2个羧酸氧原子和不同的咪唑分子中的2个氮原子形成了变形的四面体的几何构型。单个分子通过N-H…O氢键连接形成了一维链,然后在C-H…π弱作用下形成了三维结构。配合物2有2个独立的铜中心,它们有几乎相同的配位环境。每个铜中心都是变形的四方锥的配位构型。来自不同的2-萘氧乙酸配体中的2个羧酸氧原子和不同的咪唑分子中的2个氮原子形成了一个相对规则的四方锥赤道平面,配位水分子位于平面上方。配合物2的分子通过N-H…O和O-H…O氢键连接形成了二维结构。2个配合物的热稳定和固体荧光性质在本文中也得到了研究和讨论。     

Molecular, supramolecular and solution structures of peroxovanadium complexes with ON and O3N donor set ligands: two new types of cationic-anionic peroxovanadium(V) peroxovanadates(V)

The complexes, [VO(O(2))(pa)(2)]ClO(4).3H(2)O (1), [VO(O(2))(pa)(2)][VO(O(2))(2)(pa)].3H(2)O (2), [VO(O(2))(pa)(2)][VO(O(2))(ada)].2H(2)O (3) and [VO(O(2))(pa)(pca)].H(2)O (4)[pa = picolinamide, ada = carbamoylmethyliminodiacetate(2-) and pca = 2-pyrazinecarboxylate(1-)], were synthesized. 2 and 3 are new types of peroxovanadium complexes: monoperoxovanadium diperoxovanadate (2) and monoperoxovanadium monoperoxovanadate (3). The complexes were characterized by chemical analysis and IR spectroscopy, and 1, 3 and 4 also by X-ray analysis. The structure of 1 is disordered, with alternating positions of the oxo and peroxo ligands. The peroxo oxygen atoms, O(p), in 1 are involved in weak hydrogen bonds with water molecules and close intramolecular C-HO...(p) bonds [d(HO(p)) approximately 2.0 A]. The supramolecular structure of 1 is formed by a network of hydrogen bonds and strong attractive intermolecular pi-pi interactions between the pyridine rings. The supramolecular architecture in 4 is constructed by (N,O)-H...O hydrogen bonds between the neutral complex molecules and water of crystallization. The peroxo oxygen atoms in 4 form intramolecular C-H...O(p) bonds [d(H...O(p))= 2.303 A]. The pa and pca ligands are ON coordinated via the oxygen atoms of the C(NH(2))=O and COO(-) groups, respectively, and nitrogen atoms of the heterocyclic rings, and ada as a tetradentate O(3)N ligand. The thermal analysis of 4 showed that the loss of water of crystallization and the active oxygen release (T(min)/ degrees C 82, T(max)/degrees C 165) are, under given conditions, individual processes separated by the temperature interval 90-132 degrees C. The solution structures and stability were studied by UV-VIS and (51)V NMR spectroscopies.