二维配位聚合物[Cu(μ-I)(μ-4,4-bipy)]_n的溶液合成与晶体结构(英文)

碘化亚铜和4,4′-二联吡啶在溶液中反应的二种方法可制备出标题化合物的2个不同红色晶体,结构表征出两种晶体分别是单斜C2/c(1)和四方I41/acd(2)空间群。在[Cu(μ-I)(μ-4,4-bipy)]n结构中,铜原子是处于与2个碘原子和2个相互扭曲4,4′-二联吡啶中的氮原子的扭曲四面体配位环境中,2个[Cu(μ-I)]2单元和2个桥式4,4′-二联吡啶配体形成1个[Cu2(μ-I)2(μ-4,4-bipy)]2直角单元,4个直角单元经4个4,4′-二联吡啶侧式桥联而形成1个大的八角环,并由此与直角单元相互垂直而形成1个二维框架结构。     

二维配位聚合物[Cu(μ-Ⅰ)(μ-4,4-bipy)]n的溶液合成与晶体结构

碘化亚铜和4,4'-二联吡啶在溶液中反应的二种方法可制备出标题化合物的2个不同红色晶体,结构表征出两种晶体分别是单斜C2/c(1)和四方I41/acd(2)空间群.在[Cu(μ-Ⅰ)(μ-4,4-bipy)]n结构中,铜原子是处于与2个碘原子和2个相互扭曲4,4'-二联吡啶中的氮原子的扭曲四面体配位环境中,2个[Cu(μ-Ⅰ)]2单元和2个桥式4,4'-二联吡啶配体形成1个[Cu2(μ-Ⅰ)2(μ-4,4-bipy)]2直角单元,4个直角单元经4个4,4'-二联吡啶侧式桥联而形成1个大的八角环,并由此与直角单元相互垂直而形成1个二维框架结构.     

层状Cu(Ⅰ)配位聚合物[Cu(μ-CN)(μ-INH)]n的合成、晶体结构及热稳定性研究

0 引言 在过去的十几年里,金属基治疗再次引起人们的兴趣,有人已提出:金属离子可协调生物活性配体以改善其生物活性,使无生物活性的配体有可能获得有效的药理性能[1,2].桥联多核配合物广泛存在于生物体内的金属酶中.研究该类物质,有助于探索酶的结构及其活性中心的本质、获取生物体系中电子转移机理等信息.因此,合成、研究新型的桥联多核配合物的工作,已日益受到研究者们的关注[3-7].     

一维链状配位聚合物[Ag(bix)(NO3)(H2O)]n的合成和晶体结构

A one-dimensional (1D) Z conformation coordination polymer, [Ag(bix)(NO₃)(H₂O)]_n was obtained by the reaction between AgNO₃ and flexible ligand of 1,4-bis(imidazol-1-ylmethyl)-benzene under hydrothermal conditions. It crystallizes in triclinic with space group P1. The crystallographic data of the compound are: a=0.777 1(2) nm, b=1.043 4(3) nm, c=1.082 7(3) nm, α=71.403(4)°, β=80.946(5)°, γ=88.794(4)°. The 1D chainlike structure was connected by π-π interaction between phenyl rings, leading to a 2D layered network. The lattice water and the NO₃^- anions were involved between the layers, therefore the 2D layered structure further extended to an intricate 3D framework. CCDC: 257100.     

二维配位聚合物[Cu(anol)(μ1,3-N3)]n的合成、晶体结构及磁性

合成了一个结构新颖的二维Cu(Ⅱ)配位聚合物[Cu2(anol)2(μ1,3-N3)2]n(anol=2-氨基乙醇),通过X-射线单晶衍射确定了其晶体结构.晶体属单斜晶系,P21/n空间群,晶胞参数a=0.83806(17)nm,b=0.77355(15)nm,c=0.85349(17)nm,β=113.26(3)°.配体2-氨基乙醇以双齿模式配位,其配位原于包括醇羟基氧原子和氨基氮原子.在[Cu2(anol)2(μ1,3-N3)2]单元中,Cu(Ⅱ)离子通过2个μ1,1桥联方式配位的醇羟基氧原子相连,形成一个双核单元;单元之间以叠氮根离子EE桥联方式连接Cu(Ⅱ)离子形成二维网格状结构.变温磁化率测定结果表明,在配合物中,Cu(Ⅱ)离子之间存在反铁磁相互作用.     

一维链状的3-羧基苯氧乙酸铜配位聚合物[Cu(3-cpoa)(phen)(H2O)]n的合成与晶体结构

A novel coordination polymer [Cu(3-cpoa)(phen)(H₂O)]_n(3-cpoa^2-=3-carboxylphenoxyacetate, phen=1,10-phenanthroline) was synthesized and characterized by elemental analysis, IR spectra and single crystal X-ray diffraction. Crystallographic facts are as follows: monoclinic crystal system, space group P2₁/n， a=0.688 96(14) nm， b=1.652 3(3) nm， c=1.651 1(3) nm， β=95.20(3)°, V=1.871 9(6) nm³, Z=4, D_c=1.618 g·cm^-3， F(000)=932， μ=1.211 mm^-1，R=0.048 2 and wR=0.062 2. The copper atom exhibits a distorted square pyramidal coordination geometry, involving two oxygen atoms of different 3-cpoa^2- ligands, two nitrogen atoms of 1,10-phen ligand and one coordinated water molecule. The copper atoms are bridged by 3-cpoa^2- ligand, forming a one-dimensional chain along c axis. The distance of adjacent Cu…Cu is 0.916 6(4) nm. A three-dimensional network structure is constructed by the intermolecular hydrogen bond and π-stacking interactions. CCDC: 219724.     

阶梯状配位聚合物[Cu(μ3-I)INH]n的合成、晶体结构及其热稳定性研究

The complex [Cu(μ₃-I)INH]_n has been synthesized in DMF solution with INH, CuI, where INH=isoniazid. The crystal structure of the complex has been determined by X-ray diffraction single crystal structure analysis. The crystal belong to monoclinic system, space group P2₁/c. The cell parameters are: a=1.009 48(10) nm, b=0.467 51(5) nm, c=1.992 62(19) nm, β=101.413 0(10)°, and V= 0.921 81(16) nm³, Z=4, μ(Mo Kα)=5.674 mm^-1, F(000)=616.0, R₁=0.031 6, wR₂=0.082 5 [I>2σ(I)]. The copper(Ⅰ) atom locates in a distorted coordination tetrahedron. The copper(Ⅰ) atoms bridged by μ₃-I to form a band stair-like chain, and INH occupying the remaining coordination site of the approximately tetrahedral. The stair-like chains extend along b axis. The results of TG analysis show the title complex was stable under 200℃. CCDC: 705346.     

二维配位聚合物[Mn(2，4-DAA)2(4，4′-bipy)]n的合成、晶体结构及荧光性质研究

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3种酶的作用都涉及锰(Ⅱ)离子,锰离子参与了生物体内的氧化还原反应,是绿色植物的第二类光合系统的活性中心[1].     

配位聚合物[Ni(cpna)(bpy)(H2O)]n的合成、晶体结构及磁性质

通过水热方法,采用H₂cpna(H₂cpna=5-(2′-carboxylphenyl))和bpy(bpy=2,2′-bipyridine)与Ni(OAc)₂·4H₂O反应,合成了一个具有二维结构的配位聚合物[Ni(cpna)(bpy)(H₂O)]_n (1),并对其结构和磁性质进行了研究。结构分析结果表明该聚合物的晶体属于单斜晶系,P2₁/c空间群。3个镍(Ⅱ)离子、3个cpna配体、3个2,2′-bpy配体和3个配位水分子形成了一个[Ni₃(cpna)₃(bpy)₃(H₂O)₃]环,这些环通过镍(Ⅱ)离子与cpna配体的配位作用形成了一个二维层状结构。层与层之间又通过π-π堆积作用形成了一个三维的配位框架。研究表明,该聚合物中相邻镍(Ⅱ)离子之间存在很弱的反铁磁相互作用。     

配位聚合物[Fe(HL)(H2O)]n的合成、晶体结构及磁性质

通过水热方法,采用H₃L(H₃L=2-(4-carboxypyridin-3-yl)terephthalic acid)与FeSO₄·7H₂O反应,合成了一个具有二维结构的配位聚合物[Fe(HL)(H₂O)]_n (1),并对其结构和磁性质进行了研究。结构分析结果表明该聚合物的晶体属于正交晶系,Pnna空间群,a=1.45465(11) nm,b=2.47423(15) nm,c=0.73565(4) nm,V=2.6477(3) nm³,D_c=1.802 g·cm^-3,Z=8,R=0.0468,wR=0.1256(I>2σ(I))。HL^2-配体交替连接相邻的铁(Ⅱ)离子形成了一维链结构单元,这些链又通过配体与铁(Ⅱ)离子的配位作用形成了二维层。最后这些层通过氢键作用形成了一个复杂的三维超分子框架。拓扑分析表明,配合物1具有一个双节4,4-连接的拓扑网络结构,其拓扑符号为(4³.6².8)。研究表明,该聚合物中相邻铁(Ⅱ)离子之间存在反铁磁相互作用。     

氨基酸配位聚合物[Co(L-trp)(D-trp)]n

The coordination polymer [Co(L-trp)(D-trp)]_n (where L-trp is L-tryptophan or (S)-2-Amino-3-(3-indolyl)propionic acid and D-trp is D-tryptophan or (R)-2-Amino-3-(3-indolyl)propionic acid) was prepared by hydro-thermal method. The structure and physicochemical properties were characterized by single-crystal X-ray diffraction structure determination, infrared spectroscopy, elemental analysis and cyclic vohammogram. The crystal data for the title compound: Monoclinic, P2₁/c, β=98.024(2)°, a=1.959 5(3) nm, b=0.546 45(7) nm, c=0.905 54(17) nm, Z=2, μ=0.934 mm^-1, R₁=0.063 2, wR₂=0.155 3. The crystal structure shows a two-dimensional double chain plane structure feature. The cyrstallized coordination polymer has a centrosymmetric space group. Each Co²⁺ is coordinated with a pair of racemes, and the complex is a mesomer. CCDC: 651088.     

阶梯状配位聚合物[Cu(μ_3-I)INH]_n的合成、晶体结构及其热稳定性研究

The complex [Cu( μ3-I)INH]n has been synthesized in DMF solution with INH, CuI, where INH=isoniazid. The crystal structure of the complex has been determined by X-ray diffraction single crystal structure analysis. The crystal belong to monoclinic system, space group P21/c. The cell parameters are: a=1.009 48(10) nm, b=0.467 51(5) nm, c=1.992 62(19) nm, β=101.413 0(10)°, and V= 0.921 81(16) nm3, Z=4, μ(Mo Kα)=5.674 mm-1, F(000)=616.0, R1=0.031 6, wR2=0.082 5 [I2σ(I)]. The copper(Ⅰ) atom locates in a distorted coordination tetrahedron. The copper(Ⅰ) atoms bridged by μ3-I to form a band stair-like chain, and INH occupying the remaining coordination site of the approximately tetrahedral. The stair-like chains extend along b axis. The results of TG analysis show the title complex was stable under 200℃.     

二维配位聚合物[Mn(FA)2(4，4′-bipy)]n的合成、晶体结构及量子化学研究

A novel manganese coordination polymer [Mn(FA)₂(4，4′-bipy)]_n(HFA=2-furancarboxylic acid, 4,4′-bipy=4,4′-bipyridine) has been synthesized by hydrothermal methods. The crystal structure was determined by single-crystal X-ray diffraction. The crystal is of monoclinic, space group C2/c with a=1.698 4(3) nm, b=1.168 6(2) nm, c=1.009 5(17) nm, β=109.455(11)°, V=1.889 2(6) nm³, Z=4, D_c=1.523 g·cm^-3, M_r=433.27, F(000)=884, μ=0.740 mm^-1, R₁=0.028 2 and wR₂=0.071 0. In the crystal, the manganese atom is six-coordinated by two nitrogen atoms from 4,4′-bipyridine and four oxygen atoms from furancarboxylic acid molecules, completing an octahedral geometry. The 4,4′-bipyridine molecules are connected to the infinite chain [Mn(FA)₂]_n to form a two-dimensional layer. The quantum chemistry calculation on the title complex has been performed by means of G98W package and taking Lanl2dz basis set. CCDC: 296763.     

聚合物[Zn(pht)(pzH)2]n的合成，晶体结构与荧光性质

A Zn(Ⅱ) coordination polymer [Zn(pht)(pzH)₂]_n (where pht^2-=dianion of o-phthalic acid, pzH=pyrazole) has been synthesized and the structure was determined by X-ray diffraction. The complex crystallizes in the monoclinic space group P2₁/c, a=0.821 39(10) nm, b=1.662 2(2) nm, c=1.156 42(14) nm, β=100.349(2)°, V=1.5532(3) nm³, Z=4. Both carboxylate groups of the phthalate dianion coordinated in a monodentate mode bridged two Zn(Ⅱ) atoms forming the structure of 1-D chain. The pyrazole ligands play two different roles: one only coordinates the metal atom and the other joins the coordination polymer into a 2-D sheet via N-H…O and C-H…O hydrogen bonds besides the coordination property. A blue photoluminescence peak at 435 nm was observed in solid state at room temperature. CCDC: 227946.     

一维链状配位聚合物[M(H2bpb)(H2O)4](SO4)2·6H2O[M=Zn(Ⅱ)，Cu(Ⅱ)]的合成及晶体结构表征

设计并合成了一个含吡啶基团的柔性配体：N，N′-Bis(3-pyridylmethyl)-1，4-benzenedimethylamine(bpb)。通过bpb与硫酸锌及硫酸铜反应得到了两个新型具有一维链状结构的配位聚合物：[M(H₂bpb)(H₂O)₄](SO₄)₂·6H₂O[M=Zn(Ⅱ) 1，Cu(Ⅱ) 2]。X-射线晶体结构测定表明，这两个     

二维层状铜配位聚合物[Cu2(3-PyOH)2(EDTA)]n的合成与结构研究

A 2D copper coordination polymer of [Cu₂(3-PyOH)₂(EDTA)]_n (EDTA^4-=ethylenediaminetetraacetate quadrivalent anion C₁₀H₁₂N₂O₈, 3-PyOH=3-hydroxypyridine) was synthesized and characterized by the element analysis, IR and single crystal X-ray diffraction. The title complex crystallizes in monoclinic system with space group P2₁/c, a=1.327 5(3) nm, b=0.930 39(19) nm, c=0.948 44(19) nm, β=108.21(3)°, and V=1.112 8(4) nm³, Z=2, R=0.025 2, wR=0.066 1. Each copper(Ⅱ) atom is five-coordinated by three O atoms and one N atom from two different EDTA^4- groups and one N atom from 3-PyOH ligand, forming a distorted square-pyramidal coordination geometry. Two adjacent copper(Ⅱ) atoms are bridged by the bis-tetradentate EDTA^4- groups, constructing a two-dimensional layer structure along bc plane. The adjacent Cu…Cu distances are 0.502 5(3) and 0.611 3(3) nm. CCDC: 618806.     

配位聚合物{[Co(4,4′-bpy)(H2O)4](Fum)·4H2O}n的合成和晶体结构

The complex {[Co(4,4′-bpy)(H₂O)₄](Fum)·4H₂O}_n(where 4,4′-bpy = 4,4′-bipyridine and Fum = fumarate) was synthesized and characterized by X-ray diffraction. The complex consists of one-dimensional chains containing cobalt(Ⅱ) ions bridged by 4,4′-bpy molecules. The six-coordination of Co²⁺ is achieved by means of four water molecules. The fumarate is not coordinated to cobalt ion while it forms hydrogen bonds with coordinated and non-coordinated water molecules and extends the structure into three-dimensional hydrogen bonding network. CCDC: 190488.     

一维链状铜配位聚合物[Cu(m-BDOA)(bipy)·H2O]n的合成与晶体结构

A novel coordination polymer, [Cu(m-BDOA)(bipy)·H₂O]_n (m-BDOA^2-=benzene-1,3-dioxyacetate), was synthesized and characterized by elemental analysis, IR spectra, X-ray single crystal structure analysis. Crystallographic data are as follows: orthorhombic, space group Pna2₁, a=1.606 9(3) nm, b=1.685 9(3) nm, c=0.699 7(1) nm, V=1.8955(7) nm³, Z=4, D_c=1.619 g·cm^-3, μ=1.200 mm^-1, F(000)=948，R=0.038 1, wR=0.038 6. The copper atom is five-coordinated involving two oxygen atoms of different m-BDOA^2- ligand, two nitrogen atoms of 2,2′-bipy ligand and one coordinated water, there is a distorted square pyramidal environment. Two copper atoms are bridged by m-BDOA^2- ligand, forming a one-dimensional chain along a axis. The adjacent distance of Cu…Cu atoms is 0.877 3nm. The crystal network was formed by the intermolecular hydrogen bond and π-packing interactions.     

二维层状铜(Ⅱ)配位聚合物[Cu(PAc)2(μ-3-PyOH)2]n的合成、晶体结构及热稳定性研究

A two-dimensional coordination polymer, [Cu(PAc)₂(μ-3-PyOH)₂]_n(HPAc=phenyl acetic acid, 3-PyOH=3-hydroxypyridine) was synthesized and characterized by the element analysis, IR, TG and X-ray diffraction single crystal structure determination. The title complex crystallizes in the monoclinic system with space group P2₁/c, a=1.228 7(3) nm, b=0.967 05(19) nm, c=1.076 4(2) nm, β=109.93(3)° and V=1.202 4(5) nm³, Z=2, M_r=524.01, F(000)=542, μ=0.953 mm^-1, R=0.030 9, wR=0.080 7. Each copper(Ⅱ) ion displays an elongated octahedron with two nitrogen atoms from two different 3-PyOH ligands and two oxygen atoms from two different terminal phenyl acetate groups occupying the basal positions and two oxygen atoms of two different 3-PyOH ligands from the neighbouring molecules occupying the axial positions. Each four identical mononuclear Cu(Ⅱ) unit in the two-dimensional layer is joined by four 3-PyOH ligands, related by inversion centers with a Cu…Cu separation of 0.723 5(10) nm across the 3-PyOH-N,O bridge in bc plane. CCDC: 664483.     

铜(Ⅰ)配位聚合物[Cu3Hpt3]n的水热合成、晶体结构及荧光光谱

Three-dimensional framework copper(Ⅰ) coordination polymer with cuprous chloride, and 3-(pyridin-2-yl)-1,2,4-triazole, has been hydrothermally synthesized. Crystal data for this complex: Monoclinic, space group P2₁/n, a=1.203 3(2) nm, b=1.289 1(3) nm, c=1.582 3(3) nm, V=2.338(8) nm³, D_c=1.779 g·cm^-3, Z=4, F(000)=1 248. GooF =1.060, R₁=0.026 6, wR₂=0.064 0. The asymmetric structural unit contains three copper atoms and three ligands. Copper ion is coordinated with four nitrogen atoms, forming a distorted tetrahedron. The result of fluorescence spectrum analysis shows that the title complex at room temperature exhibits an intense photoluminescence with maximum emission at 414 nm. CCDC: 759692.