一维链状配位聚合物{[Pb(PTCP)(2,5-pydc)]_2·H_2O}_n的水热合成、晶体结构和发光性质研究(英文)

A new metal-organic coordination compound framework formulated {[Pb(PTCP)(2,5-pydc)]2·H2O}n (1) (PTCP=2-phenyl-1H-1,3,7,8-tetraazacyclopenta[l]-phenanthrene, H2pydc=pyridine-2,5-dicarboxylic acid) has been prepared in the hydrothermal condition and characterized by single-crystal X-ray diffraction, elemental analysis, IR and TG. It crystallizes in monoclinic, space group C2/c with a=2.129 2(4) nm, b=1.111 2(2) nm, c=2.049 4(4) nm, β=105.02(3)°, V=4.683 2(16) nm3, Z=4, Pb2C52H32N10O9, Mr=1 355.26, Dc=1.922 g·cm-3, F(000)=2 600, S= 0.825, R1=0.056 2 and wR2=0.168 9. In the crystal, the Pb atom is five-coordinated by three N and two O atoms. The complex forms a one-dimensional zigzag polymeric chain along the b axis which is stacked to furnish a two- dimensional supramolecular layer structure via aromatic π-π interactions in the ab plane. In addition, hydrogen bonds are observed in the compound which play an important role in forming the final structure. Solid-state fluorescence spectrum of 1 exhibits the maximum emission peak at 621 nm.     

一维链状铁(Ⅱ)配位聚合物的合成与晶体结构

A coordination polymer, namely [Fe(DPPZ)(dipic)]_n (1) (DPPZ=dipyrido[3,2-a∶2′,3′-c]phenazine and H₂dipic=pyridine-2,6-dicarboxylic acid), has been obtained by using hydrothermal synthesis method. The crystal structure was determined by X-ray single crystal structure analysis with the following data: Monoclinic, P2₁/c, a=0.794 95(16) nm, b=3.601 1(7) nm, c=0.734 32(15) nm, β=106.07(3)°, V=2.020 0(7) nm³, Z=4, M_r=503.25, D_c=1.655 g·cm^-3, F(000)=1 024, μ(Mo Kα)=0.795 mm^-1, R=0.038 5 and wR=0.081 0. Complex 1 has octahedral coordination geometry and forms 1D zigzag coordination chains that organize into an unusual 3D supramolecular motif through noncovalent bonds, such as π-π stacking interactions and C-H…O hydrogen bonds. The result of TG analysis indicates that the title complex is stable till 290 ℃. CCDC: 716602.     

一个吡啶二甲酸镉配位聚合物的合成、晶体结构及荧光性质

通过水热方法,采用H3CAM(H3CAM=4-hydroxy-pyridine-2,6-dicarboxylic acid)与Cd(NO3)2.4H2O反应,合成了1个镉配位聚合物[Cd4(HCAM)4(H2O)8]n(1),并对其结构和荧光性质进行了研究。结构分析结果表明该配合物属于单斜晶系,C2/c空间群。四个HCAM2-配体桥联4个镉离子形成了1个四核镉单元。这些孤立的单元通过氢键作用形成了1个三维配位框架。研究表明,该配合物在室温下能发出兰色荧光。     

一维链状锌配位聚合物[Zn(Pyphen)(PZDC)(H2O)]的水热合成、结构与荧光性质

The title coordination polymer, [Zn(Pyphen)(PZDC)(H2O)] (1) (Pyphen=pyrazino [2,3-f][1,10]phen-anthroline and H2PZDC=pyrazine-2,3-dicarboxylic acid) has been obtained by using hydrothermal synthesis andcharacterized by elemental analysis, IR, TG, fluorescence spectrum and X-ray diffraction single-crystal structureanalysis. The crystal is of triclinic, space group P1 with a=0.681 8(14) nm, b=0.743 9(15) nm, c=1.759 8(35) nm,α=94.329(30)°,β=95.514(30)°,γ=97.043(3)°,V=0.878 2(3)nm3,Z=2,Mr=481.73,Dc=1.822 g·cm-2,μ=1.452 mm-1,F(000)=448, Rint=0.033 9, R=0.042 5, wR=0.090 7. In complex 1, PZDC ligands link the Zn(Ⅱ) ions to form 1Dchain structures, and further extended into a 3D supramolecular framework through π-π interactions andhydrogen bonding interactions. In addition, complex 1 exhibits strong photoluminescence at room temperature.     

新颖一维配位聚合物[Ni(3，5-pdc)(H2O)4]·(H2O)的合成与晶体结构

The hydrothermal reaction of 3,5-pyridinedicarboxylic acid and NiCl₂·6H₂O results in a novel coordination polymer， [Ni(3,5-pdc)(H₂O)₄]·(H₂O). The crystal structure of the compound was determined by X-ray single crystal diffraction. The crystal belongs to monoclinic system with space group P2₁/n, a=1.136 1(3)nm, b=0.709 8(2) nm, c=1.459 7(4) nm, β=107.538(4)°， V=1.122 4(6) nm³, D_c=1.858 g·cm^-1, Z=4, F(000)=648, R₁=0.0264, wR₂=0.0665. CCDC: 224880.     

一维梯子状配位聚合物[Na3Er(2，6-PDA)3]·11.5H2O的合成与晶体结构

A novel 1D Ladder-like coordination polymer [Na₃Er(2，6-PDA)₃]·11.5H₂O (2,6-H₂PDA is pyridine-2,6-dicarboxylic acid) has been synthesized and the crystal structure was determined by X-ray diffraction. The crystal structure of the complex belongs to Monoclinic system with space group P2₁/c, a=0.969 7(3) nm, b=1.914 6(6) nm, c=1.8031(6) nm, β=91.524(5)°, V=3.346 6(18) mm³, Z=4, D_c=1.863g·cm^-3, μ=2.645 mm^-1. The coordination geometry configuration of Er³⁺ center is tricapped trigonal prism. The structures of the title compound exhibit a novel 1D Ladder-like chain.     

新型三维配位聚合物[Fe(C_5H_4NCOO)_2]_n的可控合成、晶体结构和UV-VIS-NIR反射光谱研究

近年来，金属有机配位聚合物由于其独特的电学、磁学、催化和光学性能而受 到普遍关注。通过选择不同的多齿配体和金属离子，可以组装成具有各处新型骨架 结构和特殊物理化学性能的配位聚合物。异烟酸根可以通过吡啶环氮原子和羧基氧 原子与金属离子配位，生成配位聚合物。本文采用三氯化铁和4-氰基吡啶在水热条 件下的反应可控地合成具有三维骨架结构的配位聚合物[Fe(C_5H_4NCOO)_2]_n，并 进行元素分析、红外光谱表征，单晶结构测定和UV-VIS-NIR（紫外-可见-近红外） 反射光谱研究。     

一个新的三维超分子配位聚合物[Ni(pyridine-2-carboxylate)_2]_n·2nH_2O的水热合成及晶体结构

采用水热法合成了一个新的金属-有机配位聚合物[Ni(pyridine-2-carboxylate)2]n·2nH2O,对其进行元素分析、红外光谱和X射线单晶衍射测定.结构分析表明:该晶体属于三斜晶系,P-1空间群,晶胞参数a=5.128 4(6) nm,b=7.634 6(9) nm,c=9.229 5(11) nm,α=74.902(2)°,β=84.347(2)°,γ=71.442(2)°,V=330.70(7) nm3,化学式为C12H12NiN2O6,Mr=338.95,Dc=1.702 g/cm3,μ(Mo,Kα)=1.497 mm-1,F(000)=174,Z=1,R=0.033 3,wR=0.038 4((I＞2σ(I)).并且该配合物通过O-H...O和C-H...O氢键形成了三维超分子网状结构.     

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℃.     

镍(II)的两种配位聚合物的合成、晶体结构和性质

分别用水热法和溶液法合成了镍的两种配位聚合物[2{Ni(HO-BDC)(bpe)H₂O}]_n·n(py)·nH₂O (1) (HO-H₂BDC=5-羟基-1,3-苯二甲酸，bpe=1,2-二(4-吡啶)乙烷，py=吡啶)和[Ni(HO-BDC)(bipy)]_n·nH₂O (2) (bipy=2,2’-联吡啶)，并对它们进行了元素分析、红外光谱等表征，并用X-射线单晶衍射测定了配合物的单晶结构。配位聚合物1晶体属三斜晶系,P1空间群,晶体学数据为：a= 1.019 2(2) nm, b=1.145 5(3) nm, c=1.246 0(3) nm, α=68.377(5)°, β=67.275(12)°, γ=71.821(7)°,V=1.222 7(5) nm³, Z=1, M_r=979.26, D_c=1.330 g·cm^-3, F(000)=508, μ=0.835, R₁=0.049 4, wR₂=0.112 1；配位聚合物2晶体属单斜晶系, P2/c空间群,晶体学数据为：a= 0.861 1(2) nm, b=1.106 8(3) nm, c=1.839 4(4) nm, β=104.267(9), V=1.699 0(7) nm³, Z=4, M_r=413.00, D_c=1.615 g·cm^-3, F(000)=848, μ=1.182, R₁=0.063 5, wR₂=0.196 9。配合物1中形成了具有纳米孔的2D结构，而配合物2则是一个1D链状结构，它们分别通过氢键和π-π堆积效应形成3D结构。     

Synthesis, crystal structure, and thermal stability of 1D coordination polymer [Zn(BDOA)(Py)2(H2O)] n

A new coordination polymer, [Zn(BDOA)(Py)₂(H₂O)] _n (I) (BDOA = benzene-1,4-dioxylacetate, Py = pyridine), has been prepared via self-assembly of benzene-1,4-dioxylacetate with zinc nitrate under mild conditions and characterized by IR spectra, elemental analysis and X-ray diffraction single-crystal analysis. The complex crystallizes in the monoclinic system, space group C2/c with a = 15.5751(9), b = 6.0898(4), c = 21.7133(13) Å, V = 1991.9(2) ų, β = 104.719(1)°, Z = 4. The zinc atoms are bridged by BDOA ligand, forming a one-dimensional chain along the z axis. A two-dimensional layer structure is formed by the intermolecular hydrogen bonds. The thermal decomposition profile of the complex is reported as well.     

Dimorphism of a new CuI coordination polymer:synthesis,crystal structures and properties of catena[CuI(2-iodopyrazine-N)] and poly[CuI(mu2-2-iodopyrazine-N,N')

Two modifications of the new copper(I) iodide coordination polymer CuI(2-iodopyrazine) were obtained by the reaction of CuI and 2-iodopyrazine in acetonitrile. During this reaction, intensely yellow crystals of form I appear first which transform within several minutes to intensely red crystals of form II which is the thermodynamically most stable form at room temperature. In catena[CuI(2-iodopyrazine-N)] (form I; a = 4.1830 (6) A; b = 10.814 (1) A; c = 17.961 (4) A; V = 812.5 (2) A(3); orthorhombic; P2(1)2(1)2(1); Z = 4), corrugated CuI double chains are found in which each copper atom is coordinated by one additional 2-iodopyrazine ligand. In poly[CuI(mu-2-iodopyrazine-N,N')] (form II; a = 4.2679 (5) A; b = 13.942 (2) A; c = 13.017 (2) A; b = 92.64 (1) degrees; V = 773.76 (2) A(3); monoclinic; P2(1)/c; Z = 4), CuI single chains occur which are connected via mu-N,N' coordination by the 2-iodopyrazine ligands to layers parallel to (010). The thermal behavior of both forms was investigated using simultaneous differential thermoanalysis, thermogravimetry, and mass spectrometry as well as differential scanning calorimetry and temperature resolved X-ray powder diffraction. On heating, both forms decompose to copper(I) iodide, and the decomposition temperature of form I is significantly lower than that of form II. From all experiments, there is no indication of a phase transition of one form into the other or for the formation of a phase with lower amine content.     

Synthesis, structure and photoluminescence of [Cu(acac)(dppe)]n with novel 1D zigzag chain-like motif

A novel complex [Cu(acac)(dppe)]_n (1) [acac = acetylacetone; dppe = 1,2-bis(diphenylphosphino)ethane] was obtained by solution reactions and structurally characterized by X-ray diffraction. The crystal structure analysis indicates that the title complex is characteristic of a polymeric chain formed by the dppe ligands bridging neighboring copper centers. The copper atom is in a distorted tetrahedral geometry. Photoluminescent investigation reveals that the title complex displays a strong emission in bluelight region.     

Synthesis,crystal structure,magnetic properties and electrochemical behavior of the mixed valence compound [CuI(CN)3CuII(dipn)]

A mixed-valence cyano-bridged Cu^II/Cu^I complex, 1, has been prepared. Complex 1 was fully characterized spectroscopically (UV-Vis and IR), and its structure was determined by X-ray crystallography. The magnetic property was measured in the temperature range 2–300?K. Electrochemical studies of 1 reveal a one-electron oxidation-reduction process associated with the Cu(II)/Cu(I) couple.     

Local aromaticity of [n]acenes, [n]phenacenes, and [n]helicenes (n = 1-9)

The local aromaticity of the six-membered rings in three series of benzenoid compounds, namely, the [n]acenes, [n]phenacenes, and [n]helicenes for n = 1-9, has been assessed by means of three probes of local aromaticity based on structural, magnetic, and electron delocalization properties. For [n]acenes our analysis shows that the more reactive inner rings are more aromatic than the outer rings. For [n]phenacenes, all indicators of aromaticity show that the external rings are the most aromatic. From the external to the central ring, the local aromaticity varies in a damped alternate way. The trends for the [n]helicene series are the same as those found for [n]phenacenes. Despite the departure from planarity in [n]helicenes, only a very slight loss of aromaticity is detected in [n]helicenes as compared to the corresponding [n]phenacenes. Finally, because of magnetic couplings between superimposed six-membered rings in the higher members of the [n]helicenes series, we have demonstrated that the NICS indicator of aromaticity artificially increases the local aromaticity of their most external rings.     

The crystal and molecular structure of oxo-bis[tribenzylsilicon(IV)]

Crystals of oxo-bis[tribenzylsilicon(IV)], O[(PhCH₂)₃Si]₂, are triclinic, space group P$\text{1}$, with a = 9.780(7), b = 9.938(9), c = 10.283(6) Å, α = 93.35(1), β = overall symmetry close to $\text{3}$: the SiOSi skeleton is strictly linear with SiO = 1.613(4) Å. The conformations of molecules and ions isoelectronic with O[(PhCH₂)₃Si]₂ are compared and discussed.     

The crystal and molecular structure of oxo-bis[tribenzylgermanium(IV)]

Crystals of oxo-bis[tribenzylgermanium(IV)], O[(PhCH₂)₃Ge]₂, are rhombohedral, space group R$\text{3}$, having a = 9.621(2) Å, α = 85.48(3)°. The structure was solved by Patterson methods using diffractometer data and refined by full-matrix least squares to R = 0.0876. The structure consists of molecules lying along the 3-fold axis of the unit cell, in which the GeOGe fragments are strictly linear and centrosymmetric. The GeO distance is 1.730(1) Å and the GeC distance is 1.980(5) Å.     

DBBD及其Cu(Ⅰ)配位聚合物[CuI(DBBD)2]n的合成

In this article we report the synthesis of (R,S)-4,4'-biquinoline-6,6'-dimethyl-3,3'-dicarboxylate (DBBD)(1) and the formation of copper(Ⅰ) coordination polymer [CuI(DBBD)2]n (2) by inducing a bidentate organic ligand (DBBD). The crystal 1 belongs to monoclinic system with space group P21, and a=0.881 30(19) nm, b=1.9660(6)system with space group Fmm2, and a=2.04441 (17) nm, b=1.543 06 (13) nm, c=1.65245 (13) nm, V=5.2129(7)     

The crystal structure of bis(1,4-dithioniumdicyclo-[2,2,2]-octane) μ-oxo-bis[tetracyanooxorhenate(V)]tetrahydrate

Summary The structure of [S(CH₂CH₂)₃S]₂[Re₂O₃(CN)₈]·4H₂O has been determined from three-dimensional x-ray diffraction data. The blue crystals are monoclinic, space group P2₁/c, with cell dimensionsa=9.431(2),b=10.879(2),c=16.217(3)Å, =110.84(2)°,Z=2 andD _m=2.11 gcm^–3. Anisotropic refinement by least-squares methods of 2483 observed reflections converged toR=0.050.The centrosymmetric binuclear anion has a linear O=Re–O–Re=O grouping with an eclipsed configuration for the cyano ligands. Bond distances: Re–O (terminal)=1.69(1), Re–O (bridging)=1.921(1) and Re–C_av=2.12(2)Å. Each Re atom is displaced by 0.11(2)Å towards the terminal oxygen atom giving a slight square-pyramidal distortion of the octahedral environment. The ring-constrained cation has C–S_av=1.82(2)Å with averaged bond angles C–S–C=101(1) and S–C–C=113(1)°.