两例Ni(Ⅱ)/Cu(Ⅱ)配位聚合物的合成、晶体结构及热稳定性研究

在溶剂热的条件下,合成了两例金属-有机配位聚合物:{[Ni(H2O)2(1,3-BIP)2]·TFBDC}n(1)和{[Cu3(H2O)4(1,3-BIP)6]·(BTC)2·(H2O)15}n(2)(1,3-BIP为1,3-二(咪唑)丙烷,H2TFBDC为2,3,5,6-四氟对苯二甲酸和H3BTC为1,3,5-均苯三酸),并利用红外光谱、元素分析和X-射线单晶衍射等技术手段对其结构进行了表征.X-射线单晶衍射结果表明配位聚合物1呈现一维环形链构型,并通过分子间氢键作用进一步连接形成三维超分子网络结构.配位聚合物2呈现出(4,4)拓扑的二维层状结构.此外,研究了两例配位聚合物的热稳定性能.     

1,2,3-三唑二羧酸镉(II)配位聚合物的合成、晶体结构与性质

利用低温水热法合成了两个新的镉配位聚合物:[Cd(L1)(H2O)2]n(1)和[Cd(L2)(H2O)]n(2)(H2L1=1-羧甲基-4-(2-羧甲氧基苯基)-2H-1,2,3-三唑,H2L2=2-羧甲基-4-(2-羧甲氧基苯基)-2H-1,2,3-三唑,利用X-射线单晶衍射、红外光谱、核磁共振(1H NMR)、元素分析、X-射线粉末衍射和热重分析对配体和配位聚合物进行了表征.晶体结构分析表明配位聚合物1和2为二维结构;两种完全去质子化的配体以μ4为配位模式分别与镉离子形成二维配位聚合物,配位聚合物1呈现双节点(4,4)连接的{44·62}拓扑结构,配位聚合物2则呈现{43·63}拓扑结构.同时,在室温下研究了配体和配位聚合物的固体荧光性质.     

1,3-间苯咪唑及间苯二甲酸根一维镍(Ⅱ)配位聚合物的合成、晶体结构及性质

以间苯咪唑(1,3-bib)和间苯二甲酸(H2MPA)为配体,采用水热法合成了1个一维镍(Ⅱ)配位聚合物[Ni(1,3-bib) (MPA)·2H2O]n(1).并对该配位聚合物进行了元素分析、红外光谱、固体紫外、热重(TGA)和Ⅹ-射线粉末衍射(PXRD)等表征,并用Ⅹ-射线单晶衍射法测定了它的单晶结构.该配位聚合物属于正交晶系,Pnma空间群,为一维结构.室温下固体紫外测试结果显示,配位聚合物具有强的紫外吸收.     

以1,2,5-噻二唑-3,4-二酸为配体的碱土金属配合物的合成、晶体结构及配位模式

以1,2,5-噻二唑-3,4-二酸为单一配体与第二主族碱土金属离子通过水热法合成了三个配合物,对其进行了元素分析及单晶衍射结构解析,并对H2tdzdc配体的配位能力、配位模式等特性作了初步研究.结果表明:单核配合物1,[Mg(tdzdc)(H2O)4]属于三斜晶系,空间群为P1;配位聚合物2,[Ca(tdzdc)(H2O)2]n,具有二维层状结构,属于单斜晶系,空间群为C2/c;配位聚合物3,[Sr(tdzdc)(H2O)3]n,具有二维层状结构,属于三斜晶系,空间群为P1.通过研究发现,当使用ⅡB主族的碱土金属与1,2,5-噻二唑-3,4-二酸根进行配位时,随着金属离子半径的增加和电子层数的增多,金属离子的配位数增多,得到的Mg、Ca、Sr的配合物结构愈加复杂,即从单核配合物到配位聚合物.     

锌(Ⅱ)配位聚合物{[Zn(CPGA)(DPPP)]H2O}n的合成和晶体结构

采用水热法合成了一个锌的新型配位聚合物{[Zn(CPGA)(DPPP)]·H2O｝n(1),[CPGA=3-(4-氯苯基)戊二酸根,DPPP=l,3-二(4-吡啶基)丙烷],用元素分析、红外光谱和X-射线单晶结构等进行了表征.结果表明该配位聚合物属于单斜晶系,P21/n空间群.晶胞参数为:a=1.3775(2) nm,b=1.20745(19) nm,c=1.4854(2) nm,F(000)=1080,Dc=1.419 g·cm-3,V=2.4446(7) nm3,Mr=522.28,Z=4,μ=1.151 mm-1,月1=0.0389,ωR2=0.1253.该配位聚合物晶体中,Zn(Ⅱ)与配体3-(4-氯苯基)戊二酸根和DPPP连接形成一维波浪面结构,水分子和3-(4-氯苯基)戊二酸根中未参与配位的氧原子形成的氢键将相邻的两层连接形成双层结构,双层结构没有进一步连接.     

1,3,5-三(羧基甲氧基)苯镍配位聚合物的合成、晶体结构及性质研究

采用溶剂热法,1,3,5-三(羧基甲氧基)苯为定向配体和乙酸镍反应构筑了一个新型的金属配位聚合物[Ni(TB)2(H2O)2]n·2H2O,其中H3TB=1,3,5-三(羧基甲氧基)苯,通过元素分析、IR及X射线单晶衍射对配合物结构进行表征,并研究其荧光性质、热稳定性及Hirshfeld表面作用力.单晶结构分析表明,该...     

二2-(2'-吡啶基)苯并咪唑一水合锌(Ⅱ)配合物的合成和结构表征

采用水热法合成了新配合物二2-(2'-吡啶基)苯并咪唑一水合锌(Ⅱ)配位聚合物{[Zn(L)2·H2O]}n(1),[L=2-(2'-吡啶基)苯并咪唑],用元素分析、红外光谱和X射线单晶结构等进行了表征,结果表明该配位聚合物属于单斜晶系,P21/c空间群.晶胞参数为:a=1.25188(19) nm,b =1.30095(19) nm,c=1.3300(2) nm,β =102.676(3)°,F(000) =968,Dc=1.483 g · cm-3,V=2.1133(5) nm3,Mr=471.81,Z=4,μ=1.192 mm-1,R1=0.0539,wR2=0.0819.该配位聚合物晶体是由配位水与苯并咪唑上的氮原子形成氢键以及配体2-(2'-吡啶基)苯并咪唑之间的π-π堆积作用连接而成的无限延伸的一维链状结构.     

2-呋喃甲醛水杨酰腙及其三维镉(Ⅱ)配位聚合物的晶体结构和热稳定性

以2-呋喃甲醛水杨酰腙HL为配体与Cd(NO3)2·4H2O在乙醇和DMF的混合溶剂中反应,采用溶剂挥发法得到配位聚合物[CdL2]n.通过FT-IR、热分析和X-射线单晶衍射等手段对其进行表征.结构表征表明配体2-呋喃甲醛水杨酰腙HL属于单斜晶系,空间群为P2(1)/n,晶胞参数为n=0.49864(9) nm,b=2.0673(4) nm,c=1.0694(2) nm;β=101.394(3)°,V=1.0806 (4) nm3,Z=4.配位聚合物[CdL2]n属于四方晶系,空间群为P41212,晶胞参数为a=0.9710(3) nm,b =0.9710(3) nm,c =2.3162(11) nm,α=β=γ=90°,V=2.1838(14) nm3,Z=1.热重分析表明,该配位聚合物具有很高的热稳定性.     

4,5-二腈基乙硫基-1,3-二硫代环戊烯-2-硫酮及其Ag(Ⅰ)配合物的合成和晶体结构

由二硫化碳、二甲基甲酰胺(DMF)、金属钠、3-溴丙腈和三氟甲基磺酸银等合成了4,5-二腈基乙硫基-1,3-二硫代环戊烯-2-硫酮(bcdt)(1)及其Ag(Ⅰ)配位聚合物[Ag4(bcdt)4(CF3SO3)2]·(CF3SO3)2·acetone(2),并使用溶剂扩散法得到了它们的单晶.通过元素分析、红外光谱和X射线单晶衍射分析等对配体和配合物的组成和结构进行了表征.X射线单晶衍射分析表明:配体1通过S…S相互作用形成了一维的链状结构;配位聚合物2则借助配位键构建出一个新颖的三维网络结构,分子内存在着广泛的面对面和肩并肩的S…S相互作用.配体1是绝缘体,而配合物2室温电导率σRT＝6.46×10-8S·cm-1.     

锰(Ⅱ)与5-[(蒽-9-亚甲基)-氨基]-间苯二甲酸的超分子配位聚合物的合成、表征及性能研究

以桥联配体5-[(蒽-9-亚甲基)-氨基]-间苯二甲酸和Mn(CH3COO)2·4H2O 为原料,通过溶剂热法成功合成了一个新型三维超分子结构的配位聚合物{[Mn2(H2O)4(CH3OH)(C2H5OH)(L)2]·(CH3OH)2·H2O}n(H2L=5-[(蒽-9-亚甲基)-氨基]-间苯二甲酸),并通过红外光谱、元素分析、X射线粉末衍射、单晶 X 射线衍射和热重分析,对配位聚合物的单晶结构进行了表征.该配位聚合物属于三斜晶系,空间群P-1,晶胞参数:a=9.6850(19) nm,b=14.278(3) nm,c=17.666(4) nm,α=87.15(3)°,β=89.99(3)°,γ=83.96(3)°,V=2426.3(8) nm3,Z=2.该晶体结构为一维配位链,通过链与链之间的π…π相互作用和氢键形成了三维超分子结构.此外,在室温条件下,固态荧光测试表明配体及其配位聚合物分别在456 nm (λex=417 nm)和506 nm (λex=402 nm)具有较强的荧光.     

A two-dimensional Zn(II) coordination polymer with a three-dimensional supramolecular architecture comprising 5-dimethylamino-isophthalic acid and 1,3-bis(4-pyridyl)propane

A new zinc coordination polymer, [Zn(L)(bpp)·H₂O]_n, was synthesized using 5-dimethylamino-isophthalic acid (H₂L) and 1,3-bis(4-pyridyl)propane (bpp) as organic linkers. In the complex, adjacent Zn²⁺ ions are linked by L^2? anions to form a one-dimensional (1D) [ZnL]_n chain. Then bpp ligands expand the 1D chains into a corrugated two-dimensional (2D) layer network by linking neighboring Zn²⁺ ions. These adjacent layers are further stacked together by direct C?H···π supramolecular interactions, generating a three-dimensional (3D) supramolecular structure. From the viewpoint of topology, the 2D network can be rationalized to a uninodal four-connected non-interpenetrated sql/Shubnikov tetragonal plane net with {4⁴.6²} topology. Moreover, the solid state properties such as thermogravimetric analysis and luminescence were also investigated.     

N-(4-吡啶甲基)-L-丝氨酸铜配合物的合成、晶体结构和磁性

氨基酸还原希夫碱HL (N-(4-吡啶甲基)-L-丝氨酸)与CuCl2·2H2O在室温条件通过扩散法合成了配位聚合物{[Cu2(L)2(Cl)2]·H2O}n(I).采用元素分析、红外光谱、X-射线单晶衍射、粉末衍射和热重分析进行了表征.两个结晶学独立Cu(II) 包含于其晶体结构中,Cu1为变形八面体CuO2N2Cl2几何构型;Cu2则呈现略有变形的四方锥结构.Cu1和Cu2通过配体L-的吡啶氮原子以及氯离子的桥连作用连接为2D网状结构.变温磁化率实验表明在温度为2~300 K,配合物I表现为铁磁性耦合.     

Construction of one new two-dimensional Zn(II) coordination polymer based on thiophene-2,5-dicarboxylate and bis(imidazole) mixed ligand

Under hydrothermal conditions, a new two-dimensional (2D) zinc coordination polymer, [Zn(tdc)(bimm)]_n, was synthesized based on thiophene-2,5-dicarboxylic acid (H₂tdc) and 1,2-bis(imidazol-1′-yl)methane (bimm) mixed ligands. Single crystal X-ray structural analysis shows adjacent Zn²⁺ ions are connected by tdc^2? anions to form a one-dimensional (1D) [ZnL]_n chain in the complex. Then flexible bimm ligands expand 1D chains into a 2D layer by linking neighboring Zn²⁺ ions. These adjacent layers are further stacked together by direct C?H···π supramolecular interactions, generating a double-layer 2D supramolecular structure. In topology, the 2D lay could be rationalized to a uninodal 4-connected non-interpenetrated sql net with {4⁴.6²} topology. In addition, solid state properties such as thermogravimetric analysis and luminescence were also investigated.     

Structural characterization of a zinc(II) complex of a tris(oxime)amine ligand

The ligand tris(1-propan-2-onyl oxime)amine (TRISOXH₃) binds to zinc(II) acetate as a tridentate N₃ donor, with a third oxime group remaining unbound and extending into the crystal lattice. The crystal structure shows a distorted trigonal bipyramidal geometry around the zinc center. An intramolecular hydrogen bonding interaction between a coordinated oxime donor and an oxygen of a bound acetate is observed. This structure is similar to that of a previously reported zinc(II) complex of a related bis(oxime)amine ligand. However, the structure of Zn(TRISOXH₃)(OAc)₂ is different in ligand coordination mode and metal coordination number from those of the previously reported complexes Ni(TRISOXH₃)Cl₂ or [Ni(TRISOXH₃)(NO₃)(H₂O)]NO₃.     

Two Zinc Porphyrin Complexes Obtained by One-port Reaction

Two zinc porphyrin complexes were synthesized by one-port reaction. Compound 1 is a mononuclear complex. The zinc ion is bound in the cavity of the ligand and it is coordinated by five atoms in a square pyramidal geometry. Whereas in 2, the metal ion is coordinated by six nitrogen atoms in an octahedral conformation. The porphyrin ligand is coordinated to three zinc ions with a η1–η1–η4–μ3 coordination mode. Six neighboring zinc atoms constitute a six-numbered ring in a chair structure. Besides, three neighboring zinc atoms form another triangle helical structure and the structure extends into a three-dimensional metallic polymer.     

Synthesis and structure of a HgI2 coordination polymer with novel rigid N-donor ligand

Solution reaction of mercury iodide with organic multifunctional ligand 2, 3-di (4-pyridyl)-2, 3-butanediol (dpb) generated a 1D polymer [(HgI₂)₂(dpb)₂(DMSO)₂] _n 1, and the crystal structure has been determined (C₁₈H₂₈HgI₂N₂O₄S₂), M _r=854.93, a=10.821(2), b=25.196(5), c=10.039(2)?, space group Pnma, Z=4, and V=2737.0(9)?³. In 1 the rigidity of HgI₂ and dpb make it a zigzag structure.     

A microporous coordination polymer with 1-D channels constructed from a basic reaction system

A ytterbium coordination polymer, {[Yb₂(OH)₂(atpt)₂]·0.5H₂O} _n , (atpt = 2-aminoterephthalate) was synthesized by using the reaction of YbCl₃·6H₂O with 2-aminoterephthalic acid under hydrothermal condition and structurally characterized by single-crystal X-ray diffraction method. The Yb(III) complex crystallizes in the monoclinic system P2/c with a = 13.1306(9) ?, b = 7.8049(5) ?, c = 21.5601(12) ?, β = 111.481(3)°, V = 2056.1(2) ?³, Z = 4. There are two crystallographically independent Yb³⁺ ions in the crystal, in which one is seven-coordinate, the other is eight-coordinate, and both of them are in oxygen environments. The ligand atpt adopts two coordination modes, bis(bridging bidentate) and bis(chelating and bridging tridentate). In addition, every hydroxyl group adopts μ₃-O mode linking three Yb³⁺ ions. It is through the linkage of atpt and hydroxyl group that ytterbium ions are linked together to form a 3-D structure with an open metal–organic framework.     

二维异核铜-钠配位聚合物的合成和晶体结构

合成了铜-钠混合金属配位聚合物 [(CuL)2(CH3OO)Na(H2O)4]2 (简写为1)并进行了元素分析和单晶X射线衍射分析,L为{2-(2′-酚基)- Δ 2-噻唑-4-羧酸}.晶体结构分析表明配合物形成Cu4Na2的六核混合金属大环.相邻的Cu4Na2环之间通过进一步的配位作用连结成包含更大的Cu8Na4大环的二维网状结构.该晶体属于三斜晶系Pī空间群,晶胞参数分别为:a = 1.0777(4) nm, b = 1.5221(6) nm, c = 1.6994(6) nm, α = 84.58(1)°, β = 76.31(1)°, γ = 89.97(1) °, V = 2.696 (2) nm3, Z = 2, Mr= 1447.26, dc = 1.783 g·cm-3, T = 293(2) K, μ = 1.816 mm-1, F(000) = 1472, R1 = 0.0794, wR2 = 0.1819 [I>2σ(I)].     

Synthesis and crystal structure of the two-dimensional coordination polymer catena(bis(μ3-iodo)-(μ 2-pyrazine)-di-copper(I))

The two-dimensional coordination polymer [Cu₂ i ₂(pyz)]_n (where pyz = pyrazine) has been synthesized hydrothermally and structurally characterized by single crystal X-ray diffraction analysis. [Cu₂ i ₂(pyz)]_n crystallizes in the space group P with a = 4.1759(4) Å, b = 7.1281(7) Å, c = 8.1279(8) Å, = 109.607(2), = 101.769(2), = 96.676(2), and Z = 1. The sheet-like polymer is characterized by infinite stair step [Cu₂ i ₂]_n double chains connected in two dimensions through bridging pyrazine ligands. The coordination environment about each copper is approximately tetrahedral having three Cu–I bonds and a single Cu–N bond.