以方酸及咪唑基配体构筑的二维层状镉(Ⅱ)配位聚合物的合成和表征

水热条件下,以1,4-双(咪唑基-1-甲基)苯(bix)及方酸阴离子(C4O42-)为配体,合成了新的镉的配位聚合物[Cd(C4O4)(bix)(H2O)2]n(1)。单晶结构分析表明,该配合物为二维层状结构,镉中心为六配位八面体结构,赤道平面上4个配位原子分别来自方酸和bix配体,轴向2个配位原子来自配位水分子,镉原子通过双配体桥连形成四连接的二维(4,4)网络。同时,测定了配合物的热稳定性和荧光性质。     

4-(2-(4-咪唑)苯乙烯基)吡啶和三种芳香二羧酸的Cd(Ⅱ)配位聚合物的合成、结构及荧光性质

以4-(2-(4-咪唑)苯乙烯基)吡啶(ISPE)为配体,分别与间苯二甲酸(1,3-H_2BDC)、4,4′-联苯二甲酸(4,4′-H_2BPDC)和4,4′-二苯乙烯二甲酸(4,4′-H_2STDC)及过渡金属盐Cd(NO3)2·4H_2O通过溶剂热自组装形成了3种配位聚合物晶体{[Cd_2(ISPE)_2(1,3-BDC)_2]·DMF}_n(1)、[Cd(ISPE)(4,4′-BPDC)]_n(2)和[Cd(ISPE)_2(4,4′-STDC)(H_2O)_2]_n(3)。并用单晶X射线衍射、PXRD、红外光谱、元素分析、热重等对其进行了表征。单晶解析结果表明:配位聚合物1是二维层状网格结构,配位聚合物2是一个六重穿插的类金刚烷三维网格结构,配位聚合物3是由一维网格结构通过氢键和分子间作用力堆积形成的三维网格结构。另外还研究了它们的室温固态荧光性能。     

基于5-(4-(2,6-二(2-吡啶基)-4-吡啶基)苯氧基)间苯二甲酸的Ni(Ⅱ)和Cd(Ⅱ)配位聚合物的合成与晶体结构

用溶剂热法合成了2个以5-(4-(2,6-二(2-吡啶基)-4-吡啶基)苯氧基)间苯二甲酸(H_2L)为配体的金属-有机配位聚合物:{[NiL(H_2O)]·H_2O}_n(1),[Cd L(phen)]_n(2)。通过X-射线单晶衍射,元素分析和红外光谱进行了结构表征。结构分析表明,在1中,L~(2-)配体的2个羧基氧原子桥连相邻的2个Ni(Ⅱ)离子,形成平行于a轴的一维链,链间则通过吡啶氮原子与金属离子连接,最终形成具有(4,4)-连接三维网络结构。在2中,Cd(Ⅱ)为七配位的单帽三棱柱几何构型,L2-配体通过2个羧基和1个吡啶基与3个中心金属Cd(Ⅱ)相连,形成(3,3)-连接的二维层面结构,又通过面间的π…π堆积作用形成了3D超分子结构。测定了配位聚合物的热稳定性和2的荧光性质。     

由2-(4'-羧基苯基)咪唑-4,5-二羧酸构筑的过渡金属配位聚合物的合成、结构及性质

在溶剂热条件下,由2-(4′-羧基苯基)咪唑-4,5-二羧酸(H_4L,C_(12)H_8N_2O_6),合成了4个配位聚合物{[M(H_3L)_2]·2H_2O}_n(M=Zn(1),Cd(2),Co(3)),[Cd(H_2L)(H_2O)]_n(4)。用元素分析、红外光谱、热重分析和单晶X射线衍射对配合物进行了表征和结构分析。结构分析结果表明:1～3是异质同晶。配体失去1个质子以H_3L~-的形式通过单齿和N,O-双齿螯合的配位模式与中心金属离子配位,构成一个略有变形的八面体结构。对于配合物4来说,配体失去2个质子以H_2L~(2-)的形式分别通过单齿和N,O-双齿螯合的配位方式与Cd~(2+)配位,中心离子采取扭曲的七配位五角双锥配位模式,并且通过配体苯环上羧基氧原子的双齿桥联作用连接2个中心离子,形成四元环的双核结构;同时呈现双节点(3,6)-连接的二维拓扑网络(4.4.4)(4.4.4.4.4.4.5.6.6.6.6.6)。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。     

三个基于1,5-二(2-乙基苯并咪唑基)-戊烷柔性配体的镉配合物（英文）

通过设计柔性配体1,5-二(2-乙基苯并咪唑基)戊烷(bep),在二羧酸辅助配体的调控下成功制备了3个配位聚合物[Cd(bep)(sba)]_n(1),[Cd(bep)(bda)]_n(2),and{[Cd_2(bep)(ada)_2]·H_2O}_n(3)(H_2sba=4,4′-磺酰基二苯甲酸,H_2bda=4,4′-联苯二甲酸,H_2ada=1,3-金刚烷二乙酸)。配合物均呈现二维层状结构。配合物1由交替的Cd(Ⅱ)/bep/sba2-螺旋链构成。配合物2由Cd/bda2-单元构成二维结构,bep作为单齿配体与Cd(Ⅱ)配位。配合物3的二维层通过Cd/ada2-/H_2O氢键螺旋链拓展成三维超分子。此外,对配合物1~3的粉末X射线衍射、热稳定性以及荧光性质进行了研究。     

基于柔性多羧酸配体H3TCOPM构筑的Co(Ⅱ)配合物的合成与结构

以三苯甲烷-4,4′,4″-三羧酸(H_3TCOPM)为主配体,以含氮二齿配体4,4′-bipyridine(4,4′-bipy)为辅助配体,与Co(NO_3)_2·6H_2O通过溶剂热反应得到了2个配位聚合物{[Co_2(α-OH-TCOPM)(OH)(H_2O)_4]·DMF}_n(1)(α-OH-H_3TCOPM=三苯甲醇-4,4′,4″-三羧酸)和{[Co_3(α-OH-TCOPM)_2(4,4′-bipy)_3(H_2O)_6]·2H_2O}_n(2)。晶体结构分析表明,配合物1为四边形的二维层状结构,而配合物2为二维网状结构。采用红外光谱、粉末X射线衍射对配合物进行了表征,用热重分析仪研究了其热稳定性。     

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（英文）

以2-(4′-羧基苯基)咪唑-4,5-二羧酸(H_4CPhIDC,C_(12)H_8N_2O_6)为配体,用溶剂热合成了3种配位聚合物{[Cd2(CPhIDC)(bimb)]·H_2O}_n(1)、{[Cd_2(CPhIDC)(phen)_2]·3H_2O}_n(2)、{[Zn_2(CPhIDC)(bpp)]·1.5H_2O}_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CPhIDC4-的形式与中心金属离子形成以μ_4和μ_5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。     

以三(4-咪唑基苯基)胺为配体的镉配合物的合成、晶体结构和荧光性质

以三(4-咪唑基苯基)胺(TIPA)和碘化镉为原料,分别与环已二酸(H_2CDC)和5-甲基间苯二甲酸(H_2MPDA)在水热条件下反应,得到2个结构不同的配位聚合物[CdI(TIPA)(CDC)_(0.5)]_n(1)和{[Cd(TIPA)(MPDA)]·H_2O}_n(2)。对它们进行了元素分析、红外光谱分析,并利用X射线衍射测定了它们的单晶结构。单晶结构分析显示,配合物1拥有二维两重贯穿的(3,4)-连接的(4.5~2)(4.5~3.7~2)拓扑结构,层与层之间通过弱相互作用连接成三维超分子结构;而配合物2具有二维(3,5)-连接的(4~2.6~7.8)(4~2.6)拓扑的层状结构,层与层之间通过互锁方式连接成三维金属有机骨架。结果说明了有机羧酸在配合物组装过程中起着非常重要的作用。此外,在室温下对2个配合物进行了荧光性质分析。     

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(H_2hmph)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:{[Ni_2(hmph)_2(bib)_2(H_2O)_2]·3H_2O}_n(1)、[Cd(hmph)(bib)]_n (2)和{[Zn(hmph)(bip)]·H_2O}_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。     

5-氨基间苯二甲酸锰配位聚合物的合成、晶体结构及荧光传感性能

采用溶剂热法,以5-氨基间苯二甲酸为定向配体,与金属盐四水乙酸锰反应,构筑了1个新型的锰配位聚合物[Mn(C_8H_5NO_4)(H_2O)]_n·2H_2O.通过红外吸收光谱(IR)、元素分析和X-射线单晶衍射等方法对锰聚合物的结构进行表征.该锰配位聚合物属于三斜晶系,空间群为P_ī.结构中的中心离子Mn~Ⅱ与来自4个不同配体的4个羧酸O原子、1个氨基N原子和1个水分子上的O原子配位,形成了1个六配位的八面体构型MnO_5N.通过中心金属离子Mn~Ⅱ与5-氨基间苯二甲酸上的N,O原子配位不断延伸形成具有孔洞结构的2D网状构型.研究目标聚合物的荧光传感性能,可通过猝灭现象选择性的检测溶液中的Mn~(2+)离子.     

Synthesis and structures of two cobalt(II) coordination networks formed from aromatic polycarboxylates and 1,4-bis(imidazole-1-ylmethyl)benzene

Two Co(II) coordination polymers, [Co(Hbtc)(bix)] _n , (1) and [Co(1,4-bdc)(bix)H₂O] _n (2) (bix = 1,4-bis(imidazole-1-ylmethyl)benzene; H₃btc = benzene-1,3,5-tricarboxylic acid; 1,4-H₂bdc = benzene-1,4-dicarboxylic acid) have been synthesized under hydrothermal conditions and structurally characterized. X-ray structure analysis reveals that in polymer 1, 2D infinite grid-like frameworks are interconnected by hydrogen-bond interactions to result in a 3D supramolecular architecture, in which the three carboxylate groups of the H₃btc molecule adopt three different coordination modes. In polymer 2, 1,4-bdc ligands with cobalt atoms construct 1D zigzag chains which are bridged by bix ligands to form a 3D framework.     

Syntheses,Structures, and Magnetic Properties of Two Novel Cobalt(II) Coordination Polymers Constructed from Pyridine‐2,6‐dicarboxylic Acid N‐oxide (PDCO)

Two new cobalt(II) coordination polymers, [Co(PDCO)(H₂O)₂]_n ( 1 ) and [Co(PDCO)(bix)(2H₂O)₂·H₂O]_n ( 2 ) ( PDCO= pyridine‐2,6‐dicarboxylic acid N‐oxide, bix = 1,4‐bis(imidazol‐1‐ylmethyl)‐benzene) have been synthesized under hydrothermal conditions. Single‐crystal X‐ray analyses show that compound 1 is a 1D helical chainlike structure with 4₁ screw axes parallel to the crystallographic c‐axis and interchain hydrogen‐bonding interactions further result in a 3D framework; for compound 2 , each bix ligand connects two Co1 atoms (or two Co2 atoms) to give a zigzag chain structure and these 1D chains are connected by offset face‐to‐face π···π and hydrogen bond interactions to generate a 3D architecture. The thermogravimetric analyses were investigated for 1 and 2 . The determination of variable temperature magnetic susceptibilities indicates an antiferromagnetic interaction between the metal atoms for 1 and 2 .     

锌、镉配位聚合物的合成、晶体结构及荧光性质

通过水热法合成了2个金属-有机配位聚合物[Zn(boba)(bix)]n(1)和[Cd(L1)(L2)]2n·nH2O(2)(H2boba=4,4′-(丁烷-1,2-二氧基)-二苯甲酸,bix=1,4-双(咪唑基-1-基)苯,H2L1=4-(羧基甲氧基)苯甲酸,L2=2-(4-羟基)-1H-咪唑并[4,5-f][1,10]菲咯啉)。并对其进行了元素分析、红外光谱、热重和X-射线单晶衍射测定。配合物1为二维网状结构,配合物2为一维双链结构。此外,还研究了它们的荧光性质。     

甲酸及联吡啶配体构筑的三维网状镍（Ⅱ）/钴（Ⅱ）配位聚合物的合成及晶体结构

通过水热法合成两个新的混配的配位聚合物[M（bipy）（Metha）₂]_n·nH₂O（M=Ni,1;Co,2;bipy=4,4’-联吡啶;Metha=甲酸）,并对配合物进行了元素分析、红外光谱和X-射线单晶衍射测定。结果表明,2个配合物为单斜晶系,C2/c空间群。配合物1和2具有相似的三维网状结构。配体Metha以2种不同的类型与M²⁺离子配位,一种是Metha中的2个氧原子作为桥联配位原子,连接着由bipy作为双基配体连接2个不同的金属离子构成的链,另一个Metha中的羧基氧只有1个氧原子与金属离子配位,使配合物构成三维结构。     

Syntheses and crystal structures of two 2D coordination polymers of cobalt(II) and nickel(II) with the Malonate Dianion Ligand

Two 2D complexes, [Co(mal)(phen)(H₂O)₂] (1) and [Ni(mal)(phen)(H₂O)₂] (2) (mal?=?malonate dianion; phen?=?1,10-phenanthroline), have been synthesized by the reaction of Co(ClO₄)₂·6H₂O and Ni(ClO₄)₂·6H₂O with disodium malonate and 1,10-phenanthroline in MeOH/H₂O solution. Their crystal structures have been determined by X-ray diffraction. The structures of Complexes 1 and 2 show that each metal ion is coordinated by one 1,10-phenanthroline, two water molecules and a malonate ligand forming a distorted octahedral environment and each mononuclear fragment forms a 2D supramolecular network through H-bonding interactions.     

Syntheses,structures, and properties of two- and three-dimensional coordination polymers based on bis(imidazole) and glutarate ligands

Two new coordination polymers, [Zn(bix)_0.5(glu)]_n (1) and {[Co(bix)(glu)]·4H₂O}_n (2), were synthesized (bix = 1,4-bis(2-methylimidazol-1-ylmethyl)benzene, glu = glutarate). In 1, each Zn(II) is connected by four glu ligands and extend to form a [Zn(glu)]_n 2-D network. Adjacent [Zn(glu)]_n 2-D networks are bridged by bix ligands to construct a 6-connected 3-D network based on the Zn₂ unit. 2 shows an undulated 2-D (4,4) network. The interesting structural feature of 2 is that there are 1-D water chains. The O–H···O hydrogen bond interactions link the 2-D coordination networks and construct the 3-D supramolecular architecture in 2. The glu ligands are bis-(bidentate) bridges in 1 and bis-(monodentate) bridges in 2. The luminescence of 1 and thermal stability of 1 and 2 were investigated.     

Poly[(μ4‐biphenyl‐3,3′,4,4′‐tetracarboxylato)bis[μ2‐1,4‐bis(imidazol‐1‐ylmethyl)benzene]dicobalt(II)]

The asymmetric unit of the title two‐dimensional coordination polymer, [Co₂(C₁₆H₆O₈)(C₁₄H₁₄N₄)₂]_n, contains one Co²⁺ ion, half of a biphenyl‐3,3′,4,4′‐tetracarboxylate (bptc) anion lying about an inversion centre and one 1,4‐bis(imidazol‐1‐ylmethyl)benzene (bix) ligand. The Co^II atom is coordinated by three carboxylate O atoms from two different bptc ligands and two N atoms from two bix ligands constructing a distorted square pyramid. Each Co²⁺ ion is interlinked by two bptc anions, while each bptc anion coordinates to four Co atoms as a hexadentate ligand so that four Co^II atoms and four bptc anions afford a larger 38‐membered ring. These inorganic rings are further extended into a two‐dimensional undulated network in the (10) plane. Two Co^II atoms in adjacent 38‐membered rings are joined together by pairs of bix ligands forming a 26‐membered [Co₂(bix)₂] ring that is penetrated by a bptc anion; these components share a common inversion centre.     

Syntheses and structures of cobalt(II), nickel(II), and copper(II) complexes with N,N,N′,N′-tetraalkylpyridine-2,6-dicarboxamides (O-daap) containing nitrate as the counter ion

Reactions of M(NO₃)₂?·?xH₂O [M?=?Co(II), Ni(II), and Cu(II)] with N,N,N′,N′-tetraalkylpyridine-2,6-dicarboxamides(O-daap) in CH₃CN yield [Co(O-dmap)(NO₃)₂] (1), [Co(O-deap)(NO₃)₂] (2), [Co(O-dpap)(NO₃)₂] (3), [Ni(O-dmap)(H₂O)₃](NO₃)₂] (4), [Ni(O-deap)(H₂O)₂(NO₃)](NO₃)] (5), [Cu(O-deap)(NO₃)₂] (6), and [Cu(O-dpap)(NO₃)₂] (7). X-ray crystal structures of 1, 2, 4, 5, and 7 reveal that O-daap ligands coordinate tridentate to each metal, O–N–O, with nitrate playing a vital role in molecular and crystal structures of all the complexes. The coordination geometry in the two Co(II) complexes, 1 and 2, is approximately pentagonal bipyramidal with nitrate bonded in a slightly unsymmetrical bidentate chelating mode. [Ni(dmap)(H₂O)₃](NO₃)₂ (4) and [Ni(deap)(H₂O)₂(NO₃)](NO₃) (5) exhibit octahedral geometry, the former containing uncoordinated nitrate while the latter has one nitrate coordinated unidentate and the other nitrate outside the coordination sphere. The Cu(II) in [Cu(dpap)(NO₃)₂] (7) occupies a distorted square pyramidal geometry and is linked to two unidentate nitrates, although one nitrate is also involved in a weak interaction with the metal through its other oxygen. IR spectra and other physical studies are consistent with their crystal structural data. O-dmap?=?N,N,N′,N′-tetramethylpyridine-2,6-dicarboxamides; O-deap?=?N,N,N′,N′-tetraethylpyridine-2,6-dicarboxamides; and O-dpap?=?N,N,N′,N′-tetraisopropylpyridine-2,6-dicarboxamides.     

锌、镉配位聚合物的合成、晶体结构及荧光性质

通过水热法合成了2个金属-有机配位聚合物[Zn（boba）（bix）]_n=（1）和[Cd（L1）（L2）]_2n=·nH₂O（2）（H₂boba=4,4’-（丁烷-1,2-二氧基）-二苯甲酸,bix=1,4-双（咪唑基-1-基）苯,H₂L1=4-（羧基甲氧基）苯甲酸,L2=2-（4-羟基）-1H-咪唑并[4,5-f][1,10]菲咯啉）。并对其进行了元素分析、红外光谱、热重和X-射线单晶衍射测定。配合物1为二维网状结构,配合物2为一维双链结构。此外,还研究了它们的荧光性质。