二维配位聚合物[Cd(nicotinate)2(H2O)]n的水热合成、晶体结构及荧光性质

在中温水热条件下,用醋酸镉和烟酸自组装合成了二维配位聚合物[Cd(n icotinate)2(H2O)]n.对其进行了元素分析、红外光谱表征、热分析、荧光分析和X射线单晶衍射测定.该配位聚合物属正交晶系,Pbca空间群,晶胞参数为:a=1.144 6(7)nm,b=1.209 9(4)nm,c=1.742 2(4)nm,V=2.412 9(2)nm3,Z=8,Mr=374.62,Dc=2.062 g/cm3,F(000)=1 472,μ=1.832 mm-1,R1=0.023 4,wR2=0.061 0.     

三个低维Zn~Ⅱ-二膦酸配位聚合物的合成、结构及荧光性能研究

通过引入第二配体2,2′-联吡啶(2,2′-bipyridine,bipy),在水热条件下得到3个低维ZnⅡ-二膦酸配位聚合物:[Zn1.5(H2L)(bipy)(H2O)]·3H2O(1),[Zn(H3L)(bipy)]2(2),[Zn(H3L)(bipy)(H2O)]·H2O(3)(H5L=1-羟亚乙基-1,1-二膦酸,CH3C(OH)(PO3H2)2)。采用单晶X-射线衍射、粉末X-射线衍射(PXRD)、红外光谱(IR)、元素分析、热重(TG-DSC)等测试手段对产物的结构进行了表征。单晶X-射线衍射数据分析表明化合物1为一维梯形双链结构,结构中含有2个晶体学独立的锌离子,分别以四配位和六配位模式与配体连接。化合物2为O-P-O双桥连接三角双锥[ZnO3N2]而成的双核零维结构。化合物3为八面体[ZnO4N2]通过O-P-O单桥连接而成的一维链状结构。氢键和π-π堆积作用进一步将3个低维ZnⅡ-二膦酸化合物扩展为三维超分子。对化合物1~3进行荧光性能的研究,测试结果表明,3个化合物均发射出强度远大于配体bipy的荧光发射峰(λem=374nm(1)、388nm(2)、387nm(3),λex=252nm),该峰来源于第二配体bipy(λem=391nm,λex=252nm)分子内部的π*-π电荷转移。电化学测试结果显示3个化合物均表现出一步单电子氧化还原过程,与自由配体相比给电子能力增强,未来可作为空穴传输材料在光电领域得到应用。     

一个由吡嗪-2,3-二甲酸和咪唑构筑的锌配位聚合物的水热合成、晶体结构及荧光性质(英文)

A metal-organic coordination polymer [Zn2(pzdc)(im)3]n(H2pzdc=pyrazine-2,3-dicarboxylic acid,im= imidazole) 1 has been hydrothermally synthesized and characterized by elemental analysis,IR,fluorescence spectrum and single-crystal X-ray diffraction.Pale yellow crystals crystallize in the monoclinic system,space group P21/c,a=1.364 87(15) nm,b=1.389 43(15) nm,c=0.956 89(10) nm,β=102.354(2)°,V=1.772 6(3) nm3,C15H12N8O4Zn2,Mr=499.07,Dc=1.870 g·cm-3,F(000)=1 000,Z=4,μ(Mo Kα)=2.750 mm-1,the final R=0.032 2 and wR=0.087 8 for 3 208 observed reflections(I2σ(I)).1 shows green photoluminescent property at room temperature.     

两个镉的配位聚合物的原位水热合成、晶体结构与荧光性质

在水热条件下, 以3-氨基-1,2,4-三唑-5-甲酸(AmTHZAC)为配体, 原位反应得到了两个镉的配位聚合物 Cd(AmTAZ)Cl(1)和[Cd(AmTAZ)(BDC)(H2O)2]·1.25H2O(2)(AmTAZH=3-amino-1,2,4-triazole, H2BDC=benzene-1,4-dicarboxylic acid), 采用红外光谱、差热-热重、CHN元素分析及单晶X射线衍射等手段对晶体结构进行了表征, 并研究了化合物1和2的荧光性质. 化合物1属正交晶系, P2(1)2(1)2(1)空间群, a=0.6452(3) nm, b=0.7848(5) nm, c=1.0449(6) nm, V=0.5291(5) nm3, Z=4, 最后一致性因子[I＞2σ(I)], R1=0.0226, wR2=0.0377, GOF=1.087. 化合物2属正交晶系, Pmc2(1)空间群, a=0.7100 nm, b=0.9920 nm, c=1.2561 nm, V=0.8847 nm3, Z=8, 最后一致性因子[I＞2σ(I)], R1=0.0934, wR2=0.2456, GOF=1.031.     

两个基于柔性双苯并咪唑配体的锌配位聚合物的合成、晶体结构和荧光性质

以1,4-双(2-甲基苯并咪唑-1-亚甲基)苯(bmb)和2个芳香多羧酸1,2,4,5-均苯四酸(H4btec)、4-(3,4-二羧基苯甲酰)邻苯二甲酸(H4dcbp)为配体,在水热条件下合成了2个锌配位聚合物{[Zn(bmb)_(0.5)(btec)_(0.5)(H_2O)]·H_2O}_n(1)和{[Zn_2(bmb)_2(dcbp)]·5H_2O}_n(2),并用X射线单晶衍射、红外光谱、元素分析和粉末衍射对其结构进行了表征。晶体结构测试表明2个聚合物均为复杂的三维框架结构,配体bmb在2个配合物中均为μ_2-η~1∶η~1的配位模式。此外还研究了2个配合物的荧光性质和热稳定性。     

二维配位聚合物[Zn(PDC)(phen)]n的合成、晶体结构及荧光性质

合成了锌(II)与3,4-吡啶二羧酸和1,10-邻菲啰啉形成的配位聚合物[Zn(PDC)(phen)]_n (1) (H₂PDC＝3,4-吡啶二羧酸, phen＝1,10-邻菲啰啉), 对其进行了元素分析、红外光谱和X射线单晶衍射表征, 测定了晶体结构. 该聚合物属单斜晶系, P2(1)/n空间群, a＝0.77136 nm, b＝1.9757(4) nm, c＝1.0680(2) nm, β＝95.36(3)°, V＝1.6205(6) nm³, Z＝4, D_c＝1.683 Mg/m³, M_r＝410.68, F(000)＝832, μ＝1.55 mm^－1, 最终偏离因子R₁＝0.0608, wR₂＝0.0967. 该化合物中Zn原子与来自两个PDC的三个羧基氧原子, 另外一个PDC的吡啶氮原子, 以及phen的两个氮原子配位, 形成的ZnN₃O₃八面体通过PDC桥联形成二维层状网络结构. 此外还研究了该聚合物的热性质和荧光性质.     

两个二维Cd(Ⅱ)配位聚合物的合成、晶体结构和荧光性质

具有d^10电子结构的简单金属配合物是不发光的。然而,采用具有π共轭芳香类有机物为配体所构建的Zn(Ⅱ)和Cd(Ⅱ)配合物,特别是具有重复单元结构的配位超分子和配位聚合物,能够发射较强的荧光,由于它们的配位数和结构的多样性,如[Cd4(betc)2(phen)2(H2O)]n(bete=1,2,4,5-benzenetetracarboxyl),[Cd(isonicotinate)2(EtOH)](EtOH),使这类化合物往往显示出一些新奇的功能。本文分别采用均苯四甲酸根和烟酸根为桥配体,合成了两种具有二维无限结构的Cd(Ⅱ)配位聚合物,它们在紫外光照射下,可以发出较强的蓝色荧光。     

一个晶态铅配位聚合物的合成、晶体结构、剥离及荧光性质

通过水热反应合成了1个二维层状结构的铅配位聚合物,[Pb(4-NPA)(H₂O)]_n(1)(4-H₂NPA=4-硝基邻苯二甲酸)。对化合物1进行了红外光谱、元素分析、热重性质以及单晶、粉末X射线衍射表征。在化合物1中,有机配体4-NPA₂-阴离子采用(κ¹-κ¹)(κ²-κ²)-μ₄桥连方式连接了4个Pb(Ⅱ)离子形成一维链状结构,该链状结构再通过1个羧酸基团形成一个二维无机层结构。利用"自上而下"的方法将该化合物在甲醇中进行了剥离实验。此外,我们还研究了化合物1的块状样品、剥离样品以及分散在甲醇中的样品的荧光性质。     

一个晶态铅配位聚合物的合成、晶体结构、剥离及荧光性质

通过水热反应合成了1个二维层状结构的铅配位聚合物,[Pb(4-NPA)(H₂O)]_n(1)(4-H₂NPA=4-硝基邻苯二甲酸)。对化合物1进行了红外光谱、元素分析、热重性质以及单晶、粉末X射线衍射表征。在化合物1中,有机配体4-NPA²-阴离子采用(κ¹-κ¹)(κ²-κ²)-μ₄桥连方式连接了4个Pb(Ⅱ)离子形成一维链状结构,该链状结构再通过1个羧酸基团形成一个二维无机层结构。利用"自上而下"的方法将该化合物在甲醇中进行了剥离实验。此外,我们还研究了化合物1的块状样品、剥离样品以及分散在甲醇中的样品的荧光性质。     

配位聚合物[Zn(PDA)(obix)]的合成、晶体结构和荧光性质

Hydrothermal reaction between 1,4-phenylenediacetic acid (H₂PDA) and Zn(NO₃)₂·6H₂O at the presence of the second ligand of 1,2-bis((1H-imidazol-1-yl) methyl)benzene (obix) yields a new 2D metal-organic coordination polymer [Zn(PDA)(obix)] (1), which has been characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy and thermal analysis. Complex 1 presents a two-dimensional (2D) sheet structure and displays strong luminescent emission at room temperature. CCDC: 716984.     

具有(6，3)拓扑构造的镝配合物的水热合成、晶体结构和荧光光谱

用水热合成的方法得到了配合物{[Dy(1,2-pda)_3/2(H₂O)]·H₂O}_n(1,2-pda=1,2-邻苯二乙酸根),用X-射线衍射单晶结构分析确定了该配合物的晶体结构。该晶体属于单斜晶系,C2/c空间群。配合物中每个Dy³⁺离子被6个1,2-邻苯二乙酸根环绕,相邻的6个Dy³⁺离子被6对1,2-邻苯二乙酸根连接,形成具有六角形的[Dy(1,2-pda)₆]₂团簇,这些团簇进一步被1,2-邻苯二乙酸根桥联而得到具有(6,3)拓扑构造的3D网络结构。所有的1,2-邻苯二乙酸根配体用桥联/螯合-桥联五齿和螯合-桥联/螯合-桥联六齿两种配位模式与Dy³⁺离子配位。每个Dy³⁺还键合1个水分子。九配位的Dy³⁺离子的配位环境可描述为扭曲的单帽四方反棱柱。在配合物的荧光光谱的481和574 nm处出现了2条谱线,分别对应于Dy³⁺离子的 ⁴F_5/2 → ⁶H_15/2和 ⁴F_5/2 → ⁶H_13/2的跃迁。     

铀-钾异核配位聚合物的合成及晶体结构

在水热反应条件下合成了1种新颖的U(Ⅵ)-K异核配位聚合物[UO2K2(pdc)2(H2O)3]n(H2pdc=吡啶-2,6-二羧酸),通过元素分析、红外、紫外光谱及热重对该配合物进行了表征。单晶结构表明:配合物属于单斜晶系,C2/c空间群;晶胞参数分别为a=1.888 5(6)nm,b=1.490 0(5)nm,c=0.740 2(2)nm,β=111.104(10)°。中心铀及钾原子通过2个氮原子和6个氧原子与吡啶-2,6-二羧酸配体结合。不同的[UO2K2(pdc)2].3H2O单元通过氧原子桥联组成三维链状配位聚合物。配位聚合物中存在π…π相互作用及氢键作用。     

Hydrothermal Synthesis, Crystal Structure and Photoluminescent Property of a Zinc(II) Coordination Polymer Assembled by Phthalate and 4,4''-Bipyridine

A metal-organic coordination polymer {[Zn(Pht)(4,4′-bipy)(H2O)2]·2H2O}n (Pht = phthalate, 4,4′-bipy = 4,4′-bipyridine) 1 has been hydrothermally synthesized and characterized by elemental analysis, IR, TG, fluorescence spectrum and single-crystal X-ray diffraction. Yellow crystals crystallize in the monoclinic system, space group P2/n, a = 7.6346(14), b = 11.316(2), c = 10.8133(19) (A), β = 92.444(3)o, V = 933.3(3)(A)3, C18H20N2O8Zn, Mr = 457.73, Dc = 1.629 g/cm3, F(000) = 472, Z = 2, μ(MoKα) = 1.367 mm-1, the final R = 0.0323 and wR = 0.0821 for 1859 observed reflections (I > 2σ(I)). The structure of 1 exhibits a two-dimensional bilayer framework formed by hydrogen bonding interactions. Furthermore, 1 shows yellow photoluminescent pro- perty at room temperature.     

三聚氰酸钴配合物的合成、晶体结构及荧光性质

本文合成了一个新的配合物Co(H2CA)2(H2O)2(H3CA=三聚氰酸),并通过元素分析、红外、荧光和单晶X-Ray射线进行了表征。标题化合物属于三斜晶系,P1空间群,a=0.503 83(7)nm,b=0.699 82(10)nm,c=0.911 08(13)nm,α=90.107(2)°,β=98.032(2)°,γ=110.788(2)°,V=0.296 92(7)nm3,Z=1,R=0.038 2。在配合物中,Co(Ⅱ)离子与三聚氰酸配体上的N原子,配位水的O原子配位,形成规则的平面正方形配位构型。相邻的2个Co(Ⅱ)平面四边形单元通过配体三聚氰酸上的氢键形成三维网状结构。室温荧光光谱测定表明该化合物在420 nm处有强的荧光发射。     

Hydrothermal Synthesis, Crystal Structure and Photoluminescent Property of a Zinc(II) Coordination Polymer Assembled by Phthalate and 4,4′-Bipyridine

1 INTRODUCTION Inorganic coordination polymers or solid-state po- lymers have received considerable attention in the past few years due to their possible applications as new materials in catalysis, adsorption, ion exchange, separation, magnetic devices, etc.[1] Metal coordina- tion polymers containing dicarboxylate ions as the organic spacer have been the subject of particular interest due to their fascinating architectures and ad- vantageous properties, such as bulk magnetic beha- vior, h…     

含磷钼酸及2,2’-联吡啶-3,3’-二羧酸配体的铜配位聚合物的合成、晶体结构与电化学性质

在水热条件下合成了一个新的化合物{[Cu4(PMo12O40)(H2O)5(H2bpdc)(Hbpdc)(bpdc)2].6H2O}n(H2bpdc=2,2′-联吡啶-3,3′-二羧酸),并用元素分析、IR、TG和X-射线衍射等手段进行了表征。结果表明本化合物的晶体结构中,最小不对称单元包含1个[Cu4(H2O)5(H2bpdc)(Hbpdc)(bpdc)2]3+阳离子,1个[PMo12O40]3-阴离子和6个结晶水分子。Cu(Ⅱ)与相邻[PMo12O40]3-的桥氧原子配位,形成一维链状结构。电化学研究表明,化合物存在三步氧化还原过程。     

由邻苯二甲酸和Medpq配体构筑的锌的配合物的水热合成及晶体测定

A metal-organic coordination polymer [Zn(Pht)(Medpq)]_n (Pht=phthalic acid, Medpq=2-methyldipyrido[3,2-f:2′,3′-h]quinoxaline) (1) has been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, TG and X-ray single-crystal structure analysis. Title complex crystallizes in the monoclinic system, space group Cc, with a=1.027 4(4) nm, b=2.955 7(11) nm, c=0.685 2(3) nm, β=112.941°, V=1.916 3(13) nm³, C₂₃H₁₄N₄O₄Zn, M_r=475.75, D_c=1.649 g·cm^-3, μ(Mo Kα)=1.324 mm^-1, F(000)=968, Z=4, the final R=0.038 8 and wR=0.071 7 for 2 697 observed reflections (I>2σ(I)). In the crystal structure, the Zinc atom is six-coordinated with four carboxylate oxygen atoms from two different carboxylate groups and two nitrogen atoms from Medpq ligand, showing a slightly distorted octahedral geometry. Furthermore, it exhibits a one-dimensional structure with Pht-Zn-Medpq as building units. CCDC: 716600.     

Synthesis and Crystal Structure of a Novel Manganese Coordination Polymer Constructed by 3,5-Dimethylbenzoic Acid with 4,4'-Bipyridine

1 INTRODUCTION There has been extensive interest in manganese complexes containing carboxylate ligands due to the richness in structural chemistry and potential appli- cations in catalysis[1～6], for example, some highly efficient manganese catalysis mimics[7, 8]. Further- more, 4,4?-bipy is an excellent bridging ligand, and so far a number of one-, two- and three-dimensional infinite metal-4,4?-bipy frameworks have already been generated[9, 10]. However, of the above-mentio- ned framework…     

Hydrothermal Synthesis, Crystal Structure and Fluorescence Property of a Novel Coordination Polymer [Eu2(C6H8O4)3(H2O)2]n·n(4,4''-bpy)

A novel coordination polymer [Eu2(C6H8O4)3(H2O)2]n·n(4,4’-bpy) (Mr = 928.51) was synthesized by the hydrothermal reaction of EuCl3·6H2O, adipic acid and 4,4’-bpy, and determined by elemental analysis, IR spectroscopy, thermal gravimetric analysis, single-crystal diffraction and fluorescence property. X-ray analysis reveals that a three-dimensional network has been formed between Eu3+ by carboxyl of adipic acid. The crystal is of orthorhombic, space group Pbcn with a = 21.870(7), b = 7.652(2), c = 19.624(6) (A), V = 3284.1(17)(A)3, Z = 4, Dc = 1.878 g/cm3, μ = 3.854 mm-1, F(000) = 1824, R = 0.0345 and wR = 0.0565. The coordination polymer exhibits intensive red light under UV excitation at room temperature, which is attributed to the 5D0→7F2 transition of Eu(Ⅲ) ions.