邻乙酰氨基苯甲酸及1,10-邻菲咯啉双核锰配合物的水热合成、晶体结构及热稳定性

<正>近年来,人们对锰配合物的研究引起极大兴趣,这主要归因于锰的配合物有其生物功能。生物体内的过氧氢化酶、过氧歧化酶和放氧复合物,这三种酶的作用都涉及锰离子,锰离子参与了生物体内的氧     

钆-邻氟苯甲酸-邻菲咯啉配合物的合成、晶体结构

由于有机羧酸化合物具有多种配位方式,以此为配体的稀土羧酸配合物具有多种多样的晶体结构。这类配合物有单核分子、双核分子和高聚物,可形成1D、2D、3D等多种结构。而且由于这类配合物在萃取分离、催化和发光材料等方面的潜在应用一直受到学者们的广泛研究。稀土与苯甲酸及其衍生物和1,10-邻菲咯啉的混合配体配合物已有很多报道[1￣6]。文献[1,2]报道了在同一个配合物的结构单元中存在两个晶体学不等同的双核分子,是由于羧基桥联方式不同而导致的。其中一个分子的两个中心离子通过4个苯甲酸的羧基桥联,另一个只有2个羧基桥联。我们合成了…     

3,4-二甲氧基苯乙酸邻菲哕啉镱(Ⅲ)配合物的合成、晶体结构及荧光光谱

合成了 3,4-二甲氧基苯乙酸邻菲啰啉镱(Ⅲ)配合物(C84H82Yb2N4O24):[Yb2(DMPA)6(phen)2](HDMPA=3,4-二甲氧基苯乙酸(C12H12O4),phen=1,10-邻菲哕啉)(CCDC:757541),并通过元素分析、红外(IR)光谱、热重分析(TG-DTG)对其进行了表征,用单晶X射线衍射测定了配合物的晶体结构.配合物C84H82Yb2N4O24属三斜晶系,空间群P(-1),品胞参数:a=1.22877(14)nm,b=1.23235(16)nm,c=1.45234(19)nm,α=91.726(7)°,β=103.321(7)°,γ=113.885(6)°,品胞体积:V=1.9379(4)nm3,品胞内分子数Z=1,相对分子质量M,=1877.62,电子数F(000)=946,密度Dc=1.609 g·cm-3,吸收系数μ(Mo Kα)=2.481 mm-1.测定了铕和铽掺杂(2.5%,5.0%,10.0%,摩尔分数)的配合物的荧光光谱,结果表明,单独的配体没有荧光,在形成配合物后,依然显示铕(Ⅲ)离子和铽(Ⅲ)离子的特征发射峰,这表明配体将吸收的能量有效地转移给了中心离子,配体起到了很好的敏化作用.     

α,β不饱和酸铜与1,10-邻菲绕啉三元配合物的合成、表征及晶体结构

合成了丙烯酸铜和α-甲基丙烯酸铜与1，10-邻菲绕啉形成的三元配合物，通过元素分析、红外光谱、热谱等数据对配合物进行了表征．测定了Cu（C4H5O2）2（phen）·H2O的晶体结构．配合物的组成为CuL2（phen）·H2O（L=CH2＝HC-COO-,CH2=C(CH3)-COO-），结构为畸变的四方锥形，属单斜晶系，P21/n群，晶胞参数：a=0.7322nm，b=1.7948nmc=1，6014nm，β＝97．12（2）°;Z＝4．     

3,4-二甲氧基苯乙酸邻菲啰啉镱(III)配合物的合成、晶体结构及荧光光谱

合成了3,4-二甲氧基苯乙酸邻菲啰啉镱(III)配合物(C84H82Yb2N4O24): [Yb2(DMPA)6(phen)2](HDMPA=3,4-二甲氧基苯乙酸(C12H12O4), phen=1,10-邻菲啰啉)(CCDC: 757541), 并通过元素分析、红外(IR)光谱、热重分析(TG-DTG)对其进行了表征, 用单晶X射线衍射测定了配合物的晶体结构. 配合物C84H82Yb2N4O24属三斜晶系, 空间群P1, 晶胞参数: a = 1.22877(14) nm, b=1.23235(16) nm, c=1.45234(19) nm, α=91.726(7)°, β=103.321(7)°, γ=113.885(6)°, 晶胞体积: V=1.9379(4) nm3, 晶胞内分子数Z=1, 相对分子质量Mr=1877.62, 电子数F(000)=946, 密度Dc=1.609 g·cm-3, 吸收系数μ(Mo Kα)=2.481 mm-1. 测定了铕和铽掺杂(2.5%, 5.0%, 10.0%, 摩尔分数)的配合物的荧光光谱, 结果表明, 单独的配体没有荧光, 在形成配合物后, 依然显示铕(III)离子和铽(III)离子的特征发射峰, 这表明配体将吸收的能量有效地转移给了中心离子, 配体起到了很好的敏化作用.     

2,6-二羟基苯甲酸邻菲啰啉镧配合物的合成与表征

在体积比为1∶1乙醇水溶液中,采用常规溶液法合成了一种镧的配合物[La(NO3)(phen)2(DHB)2],其中,HDHB=2,6-二羟基苯甲酸。利用元素分析、IR、PL、TG和X射线单晶衍射分析进行了表征。结果表明:晶体属单斜晶系,P21/n空间群,a=1.12404(2)nm,b=2.66197(5)nm,c=1.14734(2)nm,β=101.8482(18)°,V=3.3599(1)nm3,Z=4,R1=0.0224,wR2=0.0556。十配位的La(Ⅲ)处于四帽反三棱柱的多面体环境,配合物通过π-π堆积作用扩展为三维的超分子体系。配合物与配体HDHB具有类似的荧光性能。     

稀土N-苯基邻氨基苯甲酸-1,10-邻菲咯啉二元、三元配合物的合成、表征及其光物理性质

合成了几种新型的稀土(钆,铕,铽)的N-苯基邻氨基苯甲酸-1,10-邻菲咯啉的二元、三元配合物.以元素分析、红外光谱和紫外光谱进行了表征,确定了组成.同时以低温磷光光谱确定了配体的三重态能级为24330cm^-1,研究了配体与稀土离子的能级匹配.详细讨论了配合物的光物理性质如发光性能和配体与稀土离子之间以及有机配体之间的分子内能量传递机制,结果发现,铽的N-苯基邻氨基苯甲酸-1,10-邻菲咯啉配合物的发光性能良好.     

邻菲咯啉镉配合物的合成、晶体结构及抑菌活性

合成了以邻菲咯啉为配体的金属镉的配合物,利用红外光谱、元素分析、单晶衍射和热重分析等手段对其结构及性质进行了表征和分析,并研究了金属配合物对金黄色葡萄球菌、大肠杆菌、酵母菌的抑菌活性.结果表明,此类配合物对三类菌种均有不同程度的抑制作用.     

1,10-邻菲咯啉衍生物的合成及其晶体结构

以1,10-邻菲咯啉为原料,经氧化反应合成了1,10-邻菲咯啉-5,6-二酮(1);1与对氟苯甲醛反应合成了2-苯基(4-氟)-咪唑[4,5]-1,10-邻啡咯啉(2).1和2的结构经1H NMR,MS和X-射线单晶衍射表征.1为正交晶系,Pna21空间群,晶胞参数为:a=14.329 0(4)(A),b=12.370 0(3)(A),c=6.395 6(16)(A),α=90°,β=90°,γ=90°,V=1 133.5(5)(A)~3,Z=14,Dc=2.521 g·cm~(-3),μ=12.430 mm~(-1),F(000)=789,最终偏离因子R=0.039 8,wR=0.114 7.2为单斜晶系,P21/n,空间群晶胞参数为:a=9.810 0(4)(A),b=10.951 0(4)(A),c=17.3670(7)(A),α=90.000°,β=99.042(5)°,γ=90.000°,V=1 842.5(12)(A)~3,Z=4,Dc=1.292 g·cm~(-3),μ=0.095mm~(-1),F(000)=732,最终偏离因子R=0.091 2,wR=0.334 9.     

高氯酸二水邻菲咯啉合铜配合物的合成和晶体结构

Crystal structure of the title compound， Cu(phen)(H₂O)₂·ClO₄(phen=1，10-phenanthroline)， was deter-mined by X-ray crystallography. It crystallizes in the monoclinic system， space group C2/c with lattice parameters a=1.49071(4)nm， b=1.38594(4)nm， c=0.70292(1)nm， β=108.509(1)° and Z=4; The Cu(Ⅰ) ion is chelated by a phen ligand and two aqua ligands in cis arrangement and assumes a C2 symmetric square-planar geometry with the CuN₂O₂ core. Eight Cu(phen)(H₂O)₂·ClO₄ molecules are interconnected by strong hydrogen bonds between coordinated water molecules and uncoordinated perchlorate anions to form a molecular scale cavities along c axis. The bond distances of Cu-N and Cu-O are 0.2003(4)nm and 0.1973(3)nm， respectively. CCDC： 197600.     

N-对甲苯磺酰-5-氨基间苯二甲酸构筑的一维配位聚合物的合成、晶体结构和荧光性质

采用普通溶液法和水热法分别合成了2个金属-有机配位聚合物：{[Cu（Ts-5-AIPA）（phen）（H₂O）]·H₂O}_n（1）和[Cd（Ts-5-AIPA）（phen）]_n（2）（Ts-5-AIPA=N-对甲苯磺酰-5-氨基间苯二甲酸根,phen=菲咯啉）,并用红外光谱、热重和X射线单晶衍射对配合物的结构进行了表征。结果表明：2个配合物均为单斜晶系,配合物1为P2₁/c空间群,配合物2为C2/c空间群;2个配合物均为一维链状结构,再通过氢键和π-π堆积作用形成三维超分子结构。另外,还研究了2个配位聚合物的荧光性质。     

N-对甲苯磺酰-5-氨基间苯二甲酸构筑的一维配位聚合物的合成、晶体结构和荧光性质

采用普通溶液法和水热法分别合成了2个金属-有机配位聚合物:{[Cu(Ts-5-AIPA)(phen)(H_2O)]·H_2O}n(1)和[Cd(Ts-5-AIPA)(phen)]n(2)(Ts-5-AIPA=N-对甲苯磺酰-5-氨基间苯二甲酸根,phen=菲咯啉),并用红外光谱、热重和X射线单晶衍射对配合物的结构进行了表征。结果表明:2个配合物均为单斜晶系,配合物1为P21/c空间群,配合物2为C2/c空间群;2个配合物均为一维链状结构,再通过氢键和π-π堆积作用形成三维超分子结构。另外,还研究了2个配位聚合物的荧光性质。     

A Zn(II) 5-Aminoisophthalate Coordination Polymer

The title compound, [Zn(AIP)(4,4-bipy)0.5(H2O)]n·0.75nH2O 1, was synthesized via the hydrothermal reaction of Zn(OAc)2 with 5-aminoisophthalic acid (H2AIP) and characterized by elemental analysis and infrared spectra. The complex crystallizes in monoclinic system, space group P21/c with a = 12.672(1), b = 7.6557(4), c = 16.181(1) , β = 109.187(2)o, V = 1482.6(2) 3, Z = 1, C52H52N8O23Zn4, Mr = 1418.58, Dc = 1.589 g/cm3, F(000) = 724 and μ(MoKα) = 1.685mm-1. The final R = 0.0702 and wR = 0.1524 for 1847 observed reflections with I > 2σ(I), and R = 0.0873 and wR = 0.1664 for all data. X-ray diffraction studies reveal that the title compound has an interesting 2D microporous architecture with guest water molecules inside the channel.     

Syntheses,Crystal Structures and Thermal Stabilities of Two New Mixed Ligated Coordination Polymers with Rigid Dicarboxylate and Flexile N-donor Ligands

Two new coordination polymers,[Co(BIPA)(bpp)](1) and [Zn(BIPA)(bpp)(H2O)](2)(H2BIPA = 5-bromoisophthalic acid,bpp = 1,3-di(4-pyridyl)propane) have been synthesized via hydrothermal reactions.The two compounds were characterized by elemental analysis,IR spectra,TG analysis and single-crystal X-ray determination.Compound 1 crystallizes in triclinic,space group P1 with a = 9.0316(13),b = 10.1179(14),c = 11.8884(17) ,α = 68.022(2),β = 84.749(2),γ = 77.791(2)°,V = 984.5(2) 3,Z = 2,C21H17BrN2O4Co,Mr = 500.21,Dc = 1.687 g.cm-3,μ = 2.932 mm-1,S = 0.981,F(000) = 502,R = 0.0440 and wR = 0.1357 for 3773 observed reflections with I > 2σ(I).Compound 2 crystallizes in the monoclinic system,space group P21/c with a = 7.8466(10),b = 27.483(4),c = 9.6583(13) ,β = 96.663(3)°,V = 2068.8(5) 3,Z = 4,C21H19BrN2O5Zn,Mr = 524.66,Dc = 1.685 g.cm-3,μ = 3.155 mm-1,S = 0.969,F(000) = 1056,R = 0.0441 and wR = 0.0517 for 4058 observed reflections with I > 2σ(I).The two compounds are constructed from the BIPA2-and bpp ligands but they exhibit different kinds of one-dimensional chain structures.In 1,the chains are composed of the Co(Ⅱ) ions and BIPA2-ligands,and the chains are further extended into a 2D framework structure by π...π interactions of the benzene rings from the BIPA2-ligands between the adjacent chains.In 2,the chains are made up of Zn(Ⅱ) ions and BIPA2-ligands through another fashion,and the chains are further linked via hydrogen bonding interactions to yield a two-dimensional supramolecular layer structure.Furthermore,the bpp ligand features two kinds of different coordination modes in the two compounds.     

网络骨架组装工程：5-硝基间苯二甲酸形成的配位聚合物网络多样性

Two novel coordination polymers, [Cu(nip)(phen)]_n (1) and [Co₂(nip)₂(phen)₂]_n (2), have been synthesized by hydrothermal synthesis using 5-nitroisophthalic acid (H₂nip), 1,10-phenanthroline (phen) and metal salts and structurally characterized by X-ray single-crystal structure analysis. The results indicated that the nip ligand in compound 1 has a μ₃ mono-atomic bridging-monodentate coordination mode and the structure is a two-dimensional network, while the nip ligand in compound 2 has a chelating-bridging coordination mode and the structure is a one-dimensional network. CCDC: 222202, 1; 222203, 2.     

基于N-乙酸基-5-氧烟酸的两个Pb(II)配位聚合物的合成、晶体结构与荧光性质

采用水热法合成了2个以N-乙酸基-5-氧烟酸（H₂L）为配体的铅金属-有机配位聚合物：[Pb₄（μ₃-O）₂L₂]_n（1）和[Pb₃（μ₄-O）₂L]_n（2）。通过元素分析、红外光谱和X射线单晶衍射进行了结构表征。结构分析表明,聚合物₁属单斜晶系,C2/c空间群,其由[Pb₄（μ₃-O）₂]_n构成的刚性无机链通过配体L^2-连接成三维网络结构。聚合物₂属正交晶系,P2₁2₁2₁空间群,其三维结构由[Pb₃（μ₄-O）₂]_n构成的无机金属链与配体L^2-相互连接形成。研究了2的热稳定性及其在室温下的固体荧光性质。     

一维链状铜配位聚合物的合成、结构及热稳定性研究

A copper coordination polymer, {[Cu₃( μ-3-CPOA)₂( μ-3-PyO)₂(3-PyOH)₂(H₂O)₄]·4H₂O}_n (3-CPOA^2-=3-carboxylphenoxyacetate dianion, 3-PyOH=3-hydroxypyridine, 3-PyO^-=pyridin-3-onato) was synthesized and char-acterized by the element analysis, IR, TG and single crystal X-ray diffraction. The title complex crystallizes in triclinic system with space group P1, a=0.906 53(18) nm, b=1.155 9(2) nm, c=1.208 0(2) nm, α=93.25(3)°, β=111.05(3)°, γ=105.62(3)° and V=1.121 0(5) nm³, Z=1, R=0.052 6, wR=0.154 8. Each copper(Ⅱ) atom displays octahedron coordination geometry incorporating 3-carboxylphenoxyacetate and pyridin-3-onato ligands, except for the Cu1 atom also involving 3-hydroxypyridine and water molecules. Two adjacent copper(Ⅱ) atoms are bridged by the tridentate 3-CPOA^2- group and the tridentate pyridin-3-onato ligand, constructing a one-dimensional chain structure along b axis, with the adjacent Cu…Cu distances being 0.309 3(3) nm and 0.626 5(3) nm. CCDC: 287383.     

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。     

一维链状配位聚合物[Cd{5-(NO2)sal}2(2,2'-bipy)]n的合成与晶体结构

A coordination polymer of [Cd{5-(NO2)sal}2(2,2'-bipy)]n (5-(NO2)sal=5-nitrosalicylate, 2,2'-bipy=2,2'-bipyridine) was synthesized by hydrothermal reaction and characterized by elemental analysis, IR and X-raydiffraction single crystal structure analysis. The title complex crystallizes in monoelinic with space group C2/c, a=2.730 8(16) nm, b=1.272 3(5) nm, c=0.674 5(3) nm,β=96.73(2)°, V=2.327(2) nm3, Z=4, R=0.022 2, wR=0.057.The 5-nitrosalicylate anions doubly bridge the Cd(Ⅱ) atoms to form one-dimensional polymeric chain with therepeated eight-membered ring units (Cd-O-C-O)2. The crystal structure is stabilized by intra- and interchainhydrogen bonds interactions.     

Ytterbium Coordination Polymer with Four Different Coordination Numbers：The First Structural Characterization of Lanthanide Phthalate Complex

The novel ytterbium coordination polymer is a t4wo-dimensional framework in which the central metal ions have four different coordination numbers and form four kinds of coordination poly-hedra,The four kinds of coordination polyhedra connect into infinite chains by sharing oxygen atoms.