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。     

一维异核配合物[KNd(bta)2(H2O)6]·H2O的水热合成，晶体结构和荧光性质

以双四唑胺(H₂bta)、NdCl₃·6H₂O、KOH为原料,用水热法合成了1个一维异核的Nd³⁺配合物[KNd(bta)₂(H₂O)₆]·H₂O。通过X-射线单晶衍射、元素分析、红外光谱对该配合物进行了结构表征。该化合物属于单斜晶系,P2₁/m空间群。每个Nd³⁺与2个来自bta^2-离子的4个氮原子和5个水分子形成了1个盖帽的四方双锥,通过bta^2-和水分子桥联配体把Nd³⁺和K⁺连接成一维链状结构,链与链之间通过O-H…N和N-H…O氢键作用形成三维超分子结构。紫外吸收光谱和荧光光谱表征结果显示该配合物的水溶液在292和412 nm表现出双四唑胺的特征吸收峰和荧光发射特征峰。     

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。     

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。     

一种双肟四核铜(Ⅱ)配合物的合成、结构及热稳定性研究

由螯合双肟配体3,3′-二甲氧基-2,2′-[(1,3-亚丙基)二氧双(氮次甲基)]二酚(H₂L)与四水合苦味酸铜作用,合成了一种新的四核铜(Ⅱ)配合物 [Cu₄L₂(pic)₄(H₂O)₂]·2CH₃COCH₃·2H₂O(pic^-=苦味酸根)。用X-射线单晶衍射仪测定了该配合物的晶体结构：配合物属单斜晶系,P2₁/c空间群,由4个Cu^Ⅱ离子,2个四齿的L2-单元,4个配位的苦味酸根(pic^-),2个配位的水分子,2个结晶的丙酮分子和2个结晶的水分子组成。Cu^Ⅱ离子的配位数为6,都具有稍微扭曲的八面体结构。且配合物分子通过分子间O-H…O氢键作用形成了1个二维超分子结构。     

一维配位聚合物{[Co(dpa)(H2O)4] ·(dpdo)·(H2O)}n(H2dpa=2, 2′-联苯二酸, dpdo=N, N′-二氧化-4, 4′-联吡啶)的晶体结构和光谱性质

采用水热合成法制备了一个一维配位聚合物{[Co(dpa)(H₂O)₄] ·(dpdo)·(H₂O)}_n (1)(H₂dpa=2, 2′-联苯二酸, dpdo=N, N′-二氧化-4, 4′-联吡啶), 通过红外光谱、紫外光谱、元素分析、XRPD、TGA和X-射线单晶衍射进行了表征。Co(Ⅱ)原子采取了畸变的八面体构型, 6个配位氧原子分别来自于2个dpa^2-配体和4个配位水分子。每一个dpa^2-配体桥联2个Co(Ⅱ)中心, 每一个Co(Ⅱ)原子与2个dpa^2-配体配位进而形成了2₁螺旋链结构。借助溶剂水分子的连接作用, 螺旋链之间通过多种O-H…O氢键作用形成了2D网格, 通过dpdo和2D网格之间多种类型的氢键作用形成了三维超分子结构。测定了室温下聚合物1的固体荧光光谱。     

以还原型钼磷酸盐[P4MoV6O28(OH)3]9-为建筑单元构筑新型多维延展结构材料

向MoO₃, H₃PO₄和bpy(4,4′-bipyridine)组成的反应体系中分别引入Cd(OAc)₂·2H₂O 和MnCl₂·4H₂O, 在水热条件下合成了两种基于还原型钼磷酸盐[P₄Mo₆O₂₈(OH)₃]^9-(简称{P₄Mo₆})为建筑单元构筑的新型多维延展型无机-有机杂化材料(H₂bpy)₂[Cd(H₂O)]₃[Cd(HPO₄)₆(PO₄)₂(OH)₆(MoO₂)₁₂]·5H₂O(1)和 (H₂bpy)₃[Mn(H₂O)₂]₂ [Mn(HPO₄)₆(PO₄)₂(OH)₆(MoO₂)₁₂]·10H₂O(2), 并通过元素分析、红外光谱、热重分析和X射线单晶衍射对其进行了表征。结果表明, 化合物1和2均属于三斜晶系, P1 空间群。化合物1的阴离子[Cd(H₂O)]₃[Cd(HPO₄)₆(PO₄)₂(OH)₆(MoO₂)₁₂]^2-是由二聚体 Cd[P₄Mo₆]₂通过{Cd₃}簇依次连接形成的一维无机链状结构; 化合物2的阴离子[Mn(H₂O)₂]₂[Mn(HPO₄)₆(PO₄)₂(OH)₆(MoO₂)₁₂]^3-则是由二聚体Mn[P₄Mo₆]₂通过Mn²⁺离子连接形成的二维无机层状结构。这2种无机延展结构均同质子化的bpy通过氢键作用形成不同的三维超分子网络。同时还探讨了化合物2的电化学性质。     

[M(en)3] (ndt)•H2O的水热合成、晶体结构和光学性能 ( M=NiⅡ, CoⅡ, MnⅡ and ndt=1,5-naphthalenedithiolate )

水热条件下，合成了三个新的配合物[Ni(en)₃] (ndt) ·H₂O 1, [Co(en)₃] (ndt) ·H₂O 2 和[Mn(en)₃] (ndt) ·H₂O 3。晶体结构通过X-射线单晶衍射进行了表征。三个配合物均属于单斜晶系，Cc空间群。[M(en)₃]²⁺阳离子、ndt阴离子和结晶水分子通过氢键自组装出相同结构的三维网。通过紫外-可见-近红外漫反射光谱对这三个配合物的光吸收性能和能带进行了测定。     

基于4-(2，4-二羧基苯氧基)邻苯二甲酸配体的锌配位聚合物的合成、结构及其荧光传感性能

基于H₄dpa和bpy (H₄dpa=4-(2,4-二羧基苯氧基)邻苯二甲酸,bpy=4,4''-联吡啶)为配体,在水热条件下设计、合成了金属锌配位聚合物(Zn-CP)[Zn(H₂dpa)(bpy)_1.5]_n (1),并用元素分析、红外光谱、X射线单晶衍射等对其进行了结构表征。在1中相邻Zn²⁺与H₂dpa^2-离子和bpy配位形成一维双链结构,相邻的一维双链通过氢键作用扩展形成三维超分子网结构。荧光研究表明：1是一种灵敏度高、选择性好、多响应的荧光传感器,可用于农药和硝基爆炸物的检测。有趣的是,2,4,6-三硝基苯(TNP)和嘧霉胺(Pth)对1的荧光发射显示出明显的猝灭效果,而抑霉唑(Ima)对1有荧光增强效果。此外,通过紫外可见吸收光谱、荧光寿命以及X射线光电子能谱探究了1的荧光传感机理。     

基于4-(2,4-二羧基苯氧基)邻苯二甲酸配体的锌配位聚合物的合成、结构及其荧光传感性能

基于H₄dpa和bpy(H₄dpa=4-(2,4-二羧基苯氧基)邻苯二甲酸,bpy=4,4''-联吡啶)为配体,在水热条件下设计、合成了金属锌配位聚合物(Zn-CP)[Zn(H₂dpa)(bpy)_1.5]_n (1),并用元素分析、红外光谱、X射线单晶衍射等对其进行了结构表征。在1中相邻Zn²⁺与H₂dpa^2-离子和bpy配位形成的一维双链结构,相邻的一维双链通过氢键作用扩展形成三维超分子网结构。荧光研究表明:1是一种灵敏度高、选择性好、多响应的荧光传感器,可用于农药和硝基爆炸物的检测。有趣的是,2,4,6-三硝基苯(TNP)和嘧霉胺(Pth)对1的荧光发射显示出明显的猝灭效果,而抑霉唑(Ima)对1有荧光增强效果。此外,通过紫外可见吸收光谱、荧光寿命以及X射线光电子能谱探究了1的荧光传感机理。     

Three Dicyanidometallate(I)‐based Complexes Incorporating Hydrogen‐bonding, π–π Packing and d10–d10 Interactions with Auxiliary 2,2′‐Bipyridyl‐like Ligands

To investigate the influence of the non‐covalent interactions, such as hydrogen‐bonding, π–π packing and d¹⁰–d¹⁰ interactions in the supramolecular motifs, three cyanido‐bridged heterobimetallic discrete complexes {Mn(bipy)₂(H₂O)[Ag(CN)₂]}[Ag(CN)₂] ( 1 ), {Mn(phen)₂(H₂O)[Au(CN)₂]}₂[Au(CN)₂]₂ · 4H₂O ( 2 ), and {Cd(bipy)₂(H₂O)[Au(CN)₂]}[Au(CN)₂] ( 3 ) (bipy = 2,2′‐bipyridine, and phen = 1,10‐phenanthroline), which are based on dicyanidometallate(I) groups with 1:2 stoichiometry of metal ions and 2,2′‐bipyridyl‐like co‐ligands were synthesized and structurally characterized. In compound 1 , hydrogen bonding and π–π interactions governed the supramolecular contacts. In compound 2 , the incorporation of aurophilic, hydrogen bonding and π–π interactions result in a 3D supramolecular network. In compound 3 , hydrogen bonding and π–π stacking interactions result in a 2D supramolecular layer. In the three complexes, hydrogen‐bonding, π–π packing and/or d¹⁰–d¹⁰ interactions can play important roles in increasing the dimensionality of supramolecular assemblies.     

Supramolecular Architectures with Open Frameworks Constructed by Transitional Metal Ions,Linear Dicarboxylic Acid,and 2,2′‐Bipyridine

Four new transitional metal supramolecular architectures, [Zn(cca)(2,2′‐bpy)]_n · n(2,2′‐bpy) ( 1 ), [Cu(cca)(2,2′‐bpy)]_n ( 2 ), [Zn(bpdc)(2,2′‐bpy)(H₂O)]_n · 0.5nDMF · 1.5nH₂O ( 3 ), and [Co(bpdc)(2,2′‐bpy)(H₂O)]_n · nH₂O ( 4 ) (H₂cca = p‐carboxycinnamic acid; H₂bpdc = 4,4′‐biphenyldicarboxylic acid; 2,2′‐bpy = 2,2′‐bipyridine) were synthesized by hydrothermal reactions and characterized by single crystal X‐ray diffraction, elemental analyses, and IR spectroscopy. Although the metal ions in these four compounds are bridged by linear dicarboxylic acid into 1D infinite chains, there are different π–π stacking interactions between the chains, which results in the formation of different 3D supramolecular networks. Compound 1 is of a 3D open‐framework with free 2,2′‐bpy molecules in the channels, whereas compound 2 is of a complicated 3D supramolecular network. Compounds 3 and 4 are isostructural. Both compounds have open‐frameworks.     

Cadmium(II) Complexes with Mixed cis‐Epoxysuccinate and 2,2′‐Bipyridyl‐Like Ligands: Syntheses,Crystal Structures,and Luminescent Properties

Two new Cd^II complexes, [Cd( ces )(phen)]_∞ ( 1 ) and {[Cd( ces )(bpy)(H₂O)](H₂O)}₂ ( 2 ), were prepared by slow solvent evaporation methods from mixtures of cis‐epoxysuccinic acid and Cd(ClO₄)₂ · 6H₂O in the presence of phen or bpy co‐ligand ( ces = cis‐epoxysuccinate, phen = 1,10‐phenanthroline, and bpy = 2,2′‐bipyridine). Single‐crystal X‐ray diffraction analyses show that complex 1 has a one‐dimensional (1D) helical chain that is further assembled into a two‐dimensional (2D) sheet, and then an overall three‐dimensional (3D) network by the interchain C–H ··· O hydrogen bonds. Complex 2 features a dinuclear structure, which is further interlinked into a 3D supramolecular network by the co‐effects of intermolecular C–H ··· O and C–H ··· π hydrogen bonds as well as π ··· π stacking interactions. The structural differences between 1 and 2 are attributable to the intervention of different 2,2′‐bipyridyl‐like co‐ligands. Moreover, 1 and 2 exhibit intense solid‐state luminescence at room temperature, which mainly originates from the intraligand π→π* transitions of aromatic co‐ligands.     

Cadmium(II) Complexes with a Bulky Anthracene‐based Carboxylate Ligand: Syntheses,Crystal Structures,and Luminescent Properties

To explore the coordination possibilities of anthracene‐based ligands, three cadmium(ιι) complexes with anthracene‐9‐carboxylate ( L ) and relevant auxiliary chelating or bridging ligands were synthesized and characterized: Cd₂( L )₄(2bpy)₂(μ‐H₂O) ( 1 ), Cd₂( L )₄(phen)₂(μ‐H₂O) ( 2 ), and {[Cd₃( L )₆(4bpy)]}_∞ ( 3 ) (2bpy = 2,2′‐bipyridine, phen = 1,10‐phenanthroline, and 4bpy = 4,4′‐bipyridine). Structural analyses show that complexes 1 and 2 both take dinuclear structures by incorporating the chelating 2bpy or phen ligand, which are further interlinked by intermolecular hydrogen‐bonding, π ··· π stacking, and/or C–H ··· π supramolecular interactions to generate higher‐dimensional supramolecular frameworks. Complex 3 has a one‐dimensional (1D) ribbon‐like structure, which is further assembled into a two‐dimensional (2D) layer, and a three‐dimensional (3D) framework by the co‐effects of interchain C–H ··· O hydrogen‐bonding and C–H ··· π supramolecular interactions. Moreover, the luminescent properties of these complexes were further investigated in detail.     

Synthesis,Crystal Structures,and Thermal Analyses of ­Copper(II) and Manganese(II) Mixed‐Ligand Coordination Polymers Constructed from Benzimidazole‐5, 6‐dicarboxylic Acid and N‐Donor Ligands

The coordination polymers, {[Cu(Hbidc)(2, 2′‐bpy)(H₂O)] · 2H₂O}_n ( 1 ) and {[Mn(Hbidc)(2, 2′‐bpy) (H₂O)₂] · 2H₂O}_n ( 2 ) (H₃bidc = benzimidazole‐5, 6‐dicarboxylic acid, 2, 2′‐bpy = 2, 2′‐bipyridine), were synthesized in solution and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis (TGA), and single‐crystal X‐ray diffraction. Complexes 1 and 2 consist of different 1D chain structures. In both compounds, 2, 2′‐bpy is chelating in a bidentate manner, whereas the Hbidc ligands in complexes 1 and 2 display chelating‐bridging tridentate and bridging bidentate coordination modes. The two complexes are further extended into 3D supramolecular structures through O–H ··· O and N–H ··· O hydrogen bonds. The thermal stabilities of complexes 1 and 2 were studied by thermogravimetric analyses (TGA).     

Modified polyoxometalate: a novel monocapped bi‐supporting and reduced α‐Keggin structure {PMo12O40[Cu(2,2′‐bpy)]}[Cu(2,2′‐bpy)(en)(H2O)]2

A novel modified polyoxometalate, {PMo₁₂O₄₀[Cu(2,2′‐bpy)]}[Cu(2,2′‐bpy)(en)(H₂O)]₂ [2,2′‐bpy is 2,2′‐bipyridyl (C₁₀H₈N₂) and en is ethylenediamine (C₂H₈N₂)], has been synthesized hydrothermally and structurally characterized by elemental analysis, TG, IR, XPS and single‐crystal X‐ray diffraction. The structural analysis reveals that the compound contains the reduced Keggin polyanion [PMo₁₂O₄₀]^6? as the parent unit, which is monocapped by [Cu(2,2′‐bpy)]²⁺ fragments via four bridging O atoms on an {Mo₄O₄} pit and bi‐supported by two [Cu(2,2′‐bpy)(en)(H₂O)]²⁺ coordination cations simultaneously. There exist strong intramolecular π–π stacking between the capping and supporting units, which play a stabilizing role during the crystallization of the compound. Adjacent POM clusters are further aggregated to form a three‐dimensional supramolecular network through noncovalent forces, hydrogen bonding and π–π stacking interactions. In addition, the photocatalytic properties were investigated in detail, and the results indicated that the compound can be used as a photocatalyst towards the decomposition of the organic pollutant methylene blue (MB).     

Benzene‐1,4‐diboronic acid–4,4′‐bipyridine–water (1/2/2)

In the presence of water, benzene‐1,4‐diboronic acid (1,4‐bdba) and 4,4′‐bipyridine (4,4′‐bpy) form a cocrystal of composition (1,4‐bdba)(4,4′‐bpy)₂(H₂O)₂, in which the molecular components are organized in two, so far unknown, cyclophane‐type hydrogen‐bonding patterns. The asymmetric unit of the title compound, C₆H₈B₂O₄·2C₁₀H₈N₂·2H₂O, contains two 4,4′‐bpy, two water molecules and two halves of 1,4‐bdba molecules arranged around crystallographic inversion centers. The occurrence of O—H...O and O—H...N hydrogen bonds involving the water molecules and all O atoms of boronic acid gives rise to a two‐dimensional hydrogen‐bonded layer structure that develops parallel to the (01) plane. This supramolecular organization is reinforced by π–π interactions between symmetry‐related 4,4′‐bpy molecules.     

The heterometallic cadmium–silver complex cis‐bis[dicyanidoargentato(I)‐κN]bis(5,5′‐dimethyl‐2,2′‐bipyridyl‐κ2N,N′)cadmium(II) monohydrate

In the title complex, [Ag₂Cd(CN)₄(C₁₂H₁₂N₂)₂]·H₂O or cis‐[Cd{Ag(CN)₂}₂(5,5′‐dmbpy)₂]·H₂O, where 5,5′‐dmbpy is 5,5′‐dimethyl‐2,2′‐bipyridyl, the asymmetric unit consists of a discrete neutral [Cd{Ag(CN)₂}₂(5,5′‐dmbpy)₂] unit and a solvent water molecule. The Cd^II cation is coordinated by two bidentate chelate 5,5′‐dmbpy ligands and two monodentate [Ag^I(CN)₂]⁻ anions, which are in a cis arrangement around the Cd^II cation, leading to an octahedral CdN₆ geometry. The overall structure is stabilized by a combination of intermolecular hydrogen bonding, and Ag^I...Ag^I and π–π interactions, forming a three‐dimensional supramolecular network.     

Packing effects in 4,4′‐bis(4‐hydroxy­butyl)‐2,2′‐bi­pyridine and 4,4′‐bis(4‐bromo­butyl)‐2,2′‐bi­pyridine

Structure analyses of 4,4′‐bis(4‐hydroxy­butyl)‐2,2′‐bi­pyridine, C₁₈H₂₄N₂O₂, (I), and 4,4′‐bis(4‐bromo­butyl)‐2,2′‐bi­pyridine, C₁₈H₂₂Br₂N₂, (II), reveal intermolecular hydrogen bonding in both compounds. For (I), O—H·N intermolecular hydrogen bonding leads to the formation of an infinite two‐dimensional polymer, and π stacking interactions are also observed. For (II), C—H·N intermolecular hydrogen bonding leads to the formation of a zigzag polymer. The two compounds crystallize in different crystal systems, but both mol­ecules possess C_i symmetry, with one half mol­ecule in the asymmetric unit.     

Two New Solvent‐modulated Zinc(II) Metal‐Organic Hybrid Materials based on Rigid Tripodal Carboxylate Ligand and 2,2′‐Bipy Co‐ligand: Crystal Structures and Luminescent Properties

The zinc(II) coordination polymers [Zn(Htatb)(2,2′‐bipy) · (NMP) · H₂O] ( 1 ) and [Zn₃(tatb)₂(2,2′‐bipy)₃ · H₂O] ( 2 ) (H₃tatb = 4,4′,4′′‐s‐triazine‐2,4,6‐triyl‐tribenzoic acid; 2,2′‐bipy = 2,2′‐bipyridyl, NMP = N‐methyl‐2‐pyrrolidon), were synthesized hydrothermally, and characterized by infrared spectroscopy (IR), powder X‐ray diffraction (PXRD), and single‐crystal X‐ray diffraction. Both compounds 1 and 2 possess expectant low dimensional coordination structures, which further connected into interesting 3D networks by hydrogen bond and strong π–π interactions. Moreover, the thermal stabilities and fluorescent properties of 1 and 2 were investigated.