波浪形一维链状镉配合物的合成、结构及分子识别性能

以四水合硝酸镉(Cd(NO_3)_2·4H_2O)与2-(邻溴)苯基-4,5-咪唑二羧酸(o-BrPhH_3IDC)和草酸铵通过水热反应,合成了一个波浪形一维链状配合物{[Cd(o-BrPhH_2IDC)_2(H_2O)]·H_2O}_n(1)。并通过元素分析、傅里叶变换红外光谱、热重分析和单晶X射线衍射等技术手段对配合物1进行了表征。结果表明,配合物1为正交晶系,Pbca空间群。配合物1在316 nm波长激发下,在356 nm处有最大的荧光发射峰。配合物1对小分子具有识别性能,乙腈使配合物荧光强度明显增强,甲醇、乙醇使配合物荧光强度明显减弱,而吡啶处理后的样品在356 nm附近的发射峰消失,显示对吡啶有识别作用。     

基于双咪唑配体的一维银配位聚合物的合成、晶体结构和表征

通过水热法合成了1个一维配位聚合物[Ag(1,2-bix)].HL,并对该化合物进行了元素分析、红外和单晶X-射线表征(1,2-bix=1,2-(二亚甲基苯)二咪唑配体,HL=反式-4,4′-二羧基偶氮苯阴离子)。该化合物属于三斜晶系,空间群P1,晶胞参数a=0.937 80(5)nm,b=1.119 91(16)nm,c=1.356 36(10)nm,α=102.923(8)°,β=91.751(5)°,γ=110.792(10)°,V=1.288 5(2)nm3,Z=2,C28H23AgN6O4,Mr=615.39,Dc=1.586 g.cm-3,F(000)=624,μ(Mo Kα)=0.829 mm-1,R=0.040 7,wR=0.102 0。在该化合物中,双咪唑配体连接着中心的Ag(Ⅰ)原子形成了一维链状结构。二羧酸配体之间通过O-H…O键形成另一种一维链状结构,两种类型的链以相互垂直的方式延伸。此外,我们还仔细研究了该化合物的荧光性质。     

两个一维镁配位聚合物的合成、晶体结构和荧光性质

本文以Mg(NO3)2.6H2O分别与4,5-咪唑二羧酸(4,5-imidazoledicarboxylic acid,H3imdc)和3,5-吡唑二羧酸(3,5-pyrazoled-icarboxylic acid,H3pdc)通过水热反应合成了2个新型镁的一维配位聚合物[Mg(Himdc)(DMF)(H2O)]n(1)和[Mg(Hpdc)(H2O)2]n(2),并对配位聚合物1和2进行了元素分析、FTIR、热重分析和X-射线单晶结构解析等表征。X-射线单晶结构解析表明配位聚合物1和2的晶体分别属于正交晶系与单斜晶系,空间群分别为P212121和P21/c。配合物1为一维Z字型链状结构,配合物2为一维线型链状结构,2个配合物中的链与链之间均通过氢键相互作用堆积成三维结构。对1和2进行固态荧光光谱分析,结果显示,1和2的荧光发射峰与各自的配体的荧光发射峰峰形一致,说明2个配合物的荧光发射峰应归属于各自配体内的π→π*电子跃迁。     

一维链状锰配位聚合物的合成、晶体结构与性能研究

本文合成了1个新的一维链状锰的配位聚合物{[Mn(HL)(phen)(H2O)2].1.5H2O}n,(H3L=2-羟基-5-羧基苯磺酸),并且进行了元素分析、红外、热重、荧光、紫外、粉末XRD及单晶X射线衍射等表征及研究。标题化合物属于单斜晶系,C2/c空间群,a=0.840 57(17)nm,b=1.757 5(4)nm,c=2.873 4(6)nm,β=92.54(3)°,V=4.240 7(16)nm 3,Z=4,R=0.027 0。每个Mn(Ⅱ)离子与邻菲咯啉配体的2个N原子、磺酸配体中的1个磺酸基O原子和羧基O原子以及2个配位水分子配位,展示出扭曲的八面体几何构型。2个相邻的Mn(Ⅱ)八面体单元通过1个磺酸基氧原子和1个羧基氧原子连接形成一维链状结构,该一维链进一步通过氢键作用构筑成三维网状结构。     

咪唑二羧酸构筑的铕配合物的合成、晶体结构及发光性能

2-(邻溴)苯基-4,5-咪唑二羧酸(o-BrPhH₃IDC)与六水合硝酸铕(Eu(NO₃)₃·6H₂O)在对苯二甲酸存在下,在乙睛和水的混合溶剂中,通过溶剂热反应,合成了一个三维超分子配合物(H₃O)[Eu(o-BrPhH₂IDC)₄](1)。 采用单晶X射线衍射对配合物1的晶体结构进行了测试,结果表明,配合物1为立方晶系,I-43d空间群;中心铕离子处于一个八配位的体系中。 对配合物1的固态荧光研究发现:在395 nm的激发波长下,标题配合物显示出特征的铕发射光谱。 这说明所采用的有机配体具有良好的天线效应,对铕离子有很好的敏化效应。     

系列Ag-Ln配位聚合物的合成、结构及发光性能

采用水热合成法,以吡嗪-2-羧酸(2-Hpzc)、3,5-吡啶二羧酸(3,5-H_2PDA)和草酸(H_2ox)为配体,合成9种Ag-Ln配位聚合物:{[LnAg(2-pzc)_2(ox)]·H_2O}_n(Ln=Pr(1),Nd(2),Sm(3),Eu(4)),[LnAg(3,5-PDA)(ox)(H_2O)]_n(Ln=Pr(5),Nd(6)),[LnAg(3,5-PDA)(3,5-HPDA)(ox)_(0.5)(H_2O)_2]_n(Ln=Sm(7),Dy(8),Ho(9))。配位聚合物1～4是同构的,由2-pzc~-和ox~(2-)连接,而配位聚合物5～9是以3,5-PDA~(2-)和ox~(2-)为桥联配体,均呈现3D网状结构。光物理性能研究表明配位聚合物均表现出Ln(Ⅲ)的特征发射,这可归因于Ag-配体部分(d-block)的敏化作用。另外,在晶体场和Ag(1)离子4d轨道的共同作用下,Ln(Ⅲ)离子的4f轨道被调谐,使部分能级发生明显的位移,表现为相应NIR发射带的位移,在其UV-Vis-NIR吸收光谱中可以得到佐证。     

一维链状锰配位聚合物的合成、晶体结构及热稳定性研究

A manganese coordination polymer, [Mn(C₇H₂I₃O₂)₂(CH₃OH)₂]_n was synthesized and characterized by the element analysis, IR, TG and single crystal X-ray diffraction structure analysis. The title complex crystallizes in monoclinic system with space group P2₁/c, a=0.461 66(9) nm, b=1.716 6(3) nm, c=1.647 5(3) nm, β=91.84(3)°, and V=1.305 2(4) nm³, Z=2, R=0.026 2, wR=0.063 4. Each manganese(Ⅱ) ion exists in an octahedral geometry with four O atoms from three different triiodobenzoate groups and two O atoms from two methanol molecules. Two adjacent manganese(Ⅱ) atoms are bridged by two triiodobenzoate groups in bis-monodentate mode, constructing a one-dimensional chain structure along a axis, with the adjacent Mn…Mn distance being 0.461 7(5) nm. Moreover, the weak interactions between the iodine atoms lead to a three-dimensional supramolecular network. CCDC: 666558.     

3,5-吡啶二羧酸镍配位聚合物的合成与晶体结构

采用水热法合成了3个新的3,5-吡啶二羧酸镍配位聚合物[Ni(3,5-Pydc)(H₂O)₄·H₂O]_n(1), [Ni₂(3,5-Pydc)₂(H₂O)₈·(H₂O)₂]_n(2)和[Ni(3,5-Pydc)(H₂O)₂]_n(3), 并通过X射线单晶衍射、FTIR及热重分析对其结构和组成进行了表征. 单晶衍射结果表明, 化合物1和2是一维折线型链状结构, 而化合物3是二维层状结构. 化合物1是由3,5-Pydc配体将中心镍离子连接起来形成的折线型一维链. 在化合物2中存在着两条各自独立的折线型一维链, 但它们的配位方式却完全相同, 每一条链都是由3,5-Pydc配体将镍离子连接而成. 而化合物3则是由3个镍离子和3个3,5-Pydc配体形成的二十元环构成的二维网格. 3个化合物分别通过链间或层间氢键作用(O-H…O)形成三维超分子结构, 化合物1和2中的客体水分子被氢键限域在超分子结构之中.     

一维链状铜配位聚合物的合成、晶体结构与热稳定性研究

本文合成了1个新的一维配位聚合物[Cu(apy)(sal)2]n(apy=2-氨基嘧啶,sal=水杨醛),并对其进行了元素分析、红外、热重、紫外、核磁、粉末XRD及单晶X-射线衍射表征。该聚合物为三斜晶系,空间群P1,a=0.726 87(15)nm,b=0.914 41(18)nm,c=1.382 0(3)nm,α=108.74(3)°,β=94.13(3)°,γ=96.64(3)°,V=0.858 2(3)nm 3,Z=2,R=0.087 8。Cu(Ⅱ)离子分别与来自2个不同水杨醛配体中的4个氧原子以及2个不同2-氨基嘧啶配体中的2个氮原子配位,形成了1个八面体配位构型。2-氨基嘧啶配体桥联相邻的Cu(Ⅱ)离子形成了沿bc平面的一维折叠链状结构,其相邻Cu(Ⅱ)离子之间的距离为0.6954 nm。此外,相邻的链中水杨醛的芳环之间存在着π-π堆积作用,该芳环堆积作用使得配合物构筑成二维超分子层状结构。     

新型薁磺酸镉配位聚合物的合成及其晶体结构

以薁磺酸钠为配体,通过溶液法合成了一种新型一维链状聚合物（1）,其结构和性能经IR, X-射线单晶衍射和热重分析表征。1属单斜晶系,空间群P2₁/c,晶胞参数a=2.349 6(7) nm, b=0.562 48(18) nm, c=1.148 7(4)nm。 1的中心Cd（Ⅱ）与4个薁磺酸阴离子的4个氧原子及两个水分子的两个氧原子配位,形成六配位八面体构型。配合物1通过磺酸基桥连作用将相邻的两个Cd（Ⅱ）形成一维链状结构。     

Zinc(II) and manganese(II) coordination polymers constructed by 2-naphthyl imidazole dicarboxylate: syntheses,structures and properties

Three coordination polymers [Zn(μ₃-HNIDC)(CH₃OH)]_n (H₃NIDC = 2-(2-naphthyl)-1H-imidazole-4,5-dicarboxylic acid) (1), [Mn(μ₂-HNIDC)(4,4′-bipy)]_n (4,4′-bipy = 4,4′-bipyridine) (2) and [Mn₂(μ₂-HNIDC)₂(phen)₂]_n (phen = 1,10-phenanthroline) (3) have been solvothermally synthesised and structurally characterised by single-crystal X-ray diffraction, elemental analyses, thermal analyses and IR spectra. Polymer 1 displays a three-dimensional open architecture with one-dimensional (1D) channels. Polymer 2 exhibits a sheet structure containing infinite rectangles. Polymer 3 presents a 1D wave chain structure. The solid-state photoluminescence of 1 has been investigated as well.     

Syntheses,structural diversity and properties of three coordination polymers built by chlorophenyl imidazole dicarboxylate

Two 2D coordiantion polymers, [Sr(p-ClPhHIDC)(H₂O)]_n (p-ClPhH₃IDC = 2-(4-chlorophenyl)-1H-imidazole-4,5-dicarboxylic acid) (1) and [Cd₃(p-ClPhH₂IDC)₂(p-ClPhHIDC)₂(H₂O)₂]_n (2) and one 3D polymer {[Co₃(p-ClPhHIDC)₃(H₂O)₃]·6H₂O}_n (3) have been prepared successfully under solvothermal conditions and structurally characterised by elemental analyses, IR and XRPD determinations, and have been further analysed by single-crystal X-ray diffraction. Polymer 1 exhibits a graceful 2D grid sheet structure. Polymer 2 can be regarded as a (3,3,4)-coordinated 2D network. Polymer 3 exhibits a 3D motif with 1D open channels and [Co₁₂(p-ClPhHIDC)₉] bihexagonal rings. The coordination features of the newly prepared imidazole dicarboxylate ligand, p-ClPhH₃IDC, have been discussed from both theoretical and experimental aspects. Furthermore, the solid-state photoluminescence and thermal properties of the polymers have also been investigated.     

Pyridine effected tunable luminescence properties of a 1D cadmium(II) polymer with tetranuclear second building units

One novel 1D polymer, [Cd₂(m-BrPhHIDC)₂(4,4′-bipy)(H₂O)₂]_n (1) (m-BrPhH₃IDC = 2-(3-bromophenyl)-1H-imidazole-4,5-dicarboxylic acid; 4,4′-bipy = 4,4′-bipyridine), has been hydrothermally synthesised and characterised by single-crystal X-ray diffraction, elemental analysis, IR, powder X-ray diffraction (PXRD) and thermogravimetric analysis. Polymer 1 composed of tetranuclear square [Cd₂(m-BrPhHIDC)₂] second building units and 4,4′-bipy bridges shows the interesting tunable luminescence properties aroused by pyridine. A luminescence enhance mechanism has been proposed.     

Two tetranuclear Ni(II) complexes from substituted imidazole dicarboxylates: syntheses,structures, thermal and magnetic properties

Two tetranuclear nickel(II) complexes, [Ni₄ (p-BrPhHIDC)₄(py)₄(H₂O)₄]·CH₃OH (p-BrPhH₃IDC = 2-(p-bromophenyl)-1H-imidazole-4,5-dicarboxylic acid) (1) and [Ni₄(p-ClPhHIDC)₄ (CH₃CN)₄(H₂O)₄]·4H₂O (p-ClPhH₃IDC = 2-(p-chlorophenyl)-1H-imidazole-4,5-dicarboxylic acid, py = pyridine) (2), have been solvothermally synthesised and structurally characterised. Both compounds consist of similar tetranuclear Ni(II) cores, in which the imidazole dicarboxylate ligands adopt the similar coordination mode. The thermal properties of 1 and 2 have been investigated. Also, it is discovered that there exists antiferromagnetic coupling between the Ni(II) ions in 1 and 2; the best fittings to the experimental magnetic susceptibilities gave J = ? 9.89 cm^? 1 and g = 2.18 for 1, and J = ? 10.54 cm^? 1 and g = 2.14 for 2.     

Luminescent sensing of Fe3+ and K+ by three novel imidazole dicarboxylate-based MOFs

In this paper, three luminescent metal–organic frameworks, namely: [Zn(p-IPhHIDC)]_n (1), {[Cd(p-IPhIDC)(H₂O)]·CH₃OH}_n (2) and [Zn(p-TIPhHIDC)]_n (3), bearing two novel substituted imidazole dicarboxylate ligands, 2-(p-N-imidazol-1-yl)-phenyl-1H-imidazole-4,5dicarboxylic acid (p-IPhH₃IDC) and 2-p-(1H-1,2,4-triazol-1-yl)-phenyl-1H-imidazole-4,5dicarboxylic acid (p-TIPhH₃IDC), have been prepared and characterised through infrared spectra, X-ray powder diffraction, elemental analyses, thermogravimetric analyses and single-crystal X-ray diffraction. Ignoring the free methanol molecule and coordinated water in 2, 1–3 are similar structures. Moreover, the luminescent properties of the MOFs have been explored. It was found that MOFs 1 and 2 show good luminescent sensing of Fe³⁺ in varying degrees, and 3 of K⁺.     

由2-(对溴)苯基-4,5-咪唑二羧酸构筑的镍(Ⅱ)配位聚合物的合成、结构及性质研究

本文首先合成了多功能有机桥联配体:2-(对溴)苯基-4,5-咪唑二羧酸(p-BrPhH₃IDC),使之与Ni(Ⅱ)在溶剂热条件下自组装,得到了一个二维配位聚合物{[Ni(p-BrPhH₂IDC)₂]·2H₂O}_n (1)。采用红外光谱、元素分析以及X-ray单晶衍射表征了这个配合物的分子结构。结果表明:H3BrPhIDC配体表现出比较强的配位能力,这和通过量子化学计算给出的预测一致。研究了此配聚物在空气气氛下的热稳定性以及采用变温磁化率研究了在2.0~300 K范围内的磁性质。结果表明:在配合物1中,相邻镍离子间存在着弱的反铁磁偶合作用。     

由2-(对溴)苯基-4,5-咪唑二羧酸构筑的镍(Ⅱ)配位聚合物的合成、结构及性质研究

本文首先合成了多功能有机桥联配体:2-(对溴)苯基-4,5-咪唑二羧酸(p-BrPhH3IDC),使之与Ni(Ⅱ)在溶剂热条件下自组装,得到了一个二维配位聚合物{[Ni(p-BrPhH2IDC)2].2H2O}n(1)。采用红外光谱、元素分析以及X-ray单晶衍射表征了这个配合物的分子结构。结果表明:H3BrPhIDC配体表现出比较强的配位能力,这和通过量子化学计算给出的预测一致。研究了此配聚物在空气气氛下的热稳定性以及采用变温磁化率研究了在2.0~300 K范围内的磁性质。结果表明:在配合物1中,相邻镍离子间存在着弱的反铁磁偶合作用。     

Syntheses,structures and properties of four metal-organic frameworks from chlorophenyl imidazole dicarboxylates

Four metal-organic frameworks, [Sr(o-ClPhHIDC)(H₂O)₂]_n (o-ClPhH₃IDC = 2-(o-chlorophenyl)-1H-imidazole-4,5-dicarboxylic acid) (1), [Mg(m-ClPhHIDC)(H₂O)₂]_n (2), [Sr(m-ClPhHIDC)(H₂O)]_n (3) and {[Co₃(m-ClPhIDC)₂(H₂O)₆]·2H₂O}_n (m-ClPhH₃IDC = 2-(m-chlorophenyl)-1H-imidazole-4,5-dicarboxylic acid) (4), have been solvothermally synthesized and structurally characterized. Single-crystal X-ray analyses reveal that 1–3 show 2-D architectures and 4 exhibits a 3-D structure. The o-ClPhH₃IDC and m-ClPhH₃IDC ligands in the polymers can be partly deprotonated and coordinate to metal ions by various modes. The metal ions of 1–4 are coordinated only to oxygens. The thermal and luminescence properties of the polymers have also been investigated.