Synthesis,Crystal Structure,Luminescence and Thermal Stability of a New Coordination Polymer Constructed by Europium(III) and 2,4‐Dichlorophenoxyacetate

A new coordination polymer {[Eu₂(Cl₂C₆H₃OCH₂COO)₆(H₂O)₄]·(DMF)₄·(H₂O)₂}_n with 2,4‐dichlorophenoxy acetic acid as the ligand has been synthesized. The crystal data for this complex are as follows: monoclinic, space group P2(1)/n, a=0.86474(17) nm, b=3.2475(7) nm, c=1.3843(3) nm, β=92.81(3) °, V=3.8827(13) nm³, D_c=1.718 g/cm³, Z=2, µ(Mo Kα)=2.093 mm⁻¹, F(000) =2008, final discrepancy factors R₁=0.0454, wR₂=0.1165. The crystal structure shows that the title complex forms one‐dimensional chain structure by bridging 2,4‐dichlorophenoxy acetic acid anions. Every centric europium(III) ion is coordinated with ten oxygen atoms from five 2,4‐dichlorophenoxy acetic acid anions and two water molecules, giving a ten‐coordinated distorted bicapped square antiprism geometry. The luminescent property and thermal stability of the complex are also studied.     

一维螺旋状3，6-哒嗪二甲酸镉(Ⅱ)配位聚合物的合成与结构

Using the ligand pyridazine-3，6-dicarboxylate (H₂pzdc)， a coordination polymer [Cd₂(pzdc)₂(H₂O)₄] was synthesized and characterized by elemental analysis， thermal analysis， IR and single-crystal X-ray diffraction. The complex crystallizes in the tetragonal system with space group I4₁/a. The crystallographic data are: a=1.470 6(4) nm， c=1.489 8(6) nm， V=3.222 0(19) nm³， Z=16， μ=2.725 mm^-1， D_c=2.594 g·cm^-3， R₁=0.017 8， wR₂=0.044 6. In the complex， the cadmium(Ⅱ) ions with the eight-coordinated dodecahedral geometry are linked by the pzdc ligands to generate one-dimensional chains， which are associated into the three-dimensional architecture via O-H…O hydrogen bonding. CCDC: 658853.     

Luminescent Europium(III) Coordination Zippers Linked with Thiophene‐Based Bridges

Novel Eu^III coordination polymers [Eu(hfa)₃(dpt)]_n (dpt: 2,5‐bis(diphenylphosphoryl)thiophene) and [Eu(hfa)₃(dpedot)]_n (dpedot: 2,5‐bis(diphenylphosphoryl)ethylenedioxythiophene) with hydrogen‐bonded zipper structures are reported. The coordination polymers are composed of Eu^III ions, hexafluoroacetylacetonato ligands, and thiophene‐based phosphine oxide bridges. The zig‐zag orientation of single polymer chains induced the formation of densely packed coordination structures with multiple intermolecular interactions, resulting in thermal stability above 300 °C. They exhibit a high intrinsic emission quantum yield (ca. 80 %) due to their asymmetrical and low‐vibrational coordination structures around Eu^III ions. Furthermore, the characteristic alternative orientation of substituents also contributes to the dramatically high ligand‐to‐metal energy transfer efficiencies of up to 80 % in the solid state.     

抗菌药物柳氮磺胺镉配聚物的合成和晶体结构

0 Introduction Crystal engineering of pharmaceutical solids rep- resents a fertile and emerging research filed[1]. The im- petus for discovery of diverse crystal forms of drugs stems from the critical need to balance stability, bioavailability and other performance characteristics as well as provides valuable intellectual property pro- tection. Sulfasalazine (synonyms salazopyridine and salazosulfapyridine, abbreviated as H-SSZ) is a conju- gate of 5-aminosalicylic acid and sulfapyridine pos…     

一维链状铜(Ⅱ)配合物的合成及晶体结构表征

The 1D-chain polymer of [Cu(Ⅱ)₃L₃(H₂O)]_n, (H₂L=3-(3,5-dichloro-2-hydroxybenzylid-eneamino)propanoic acid) has been synthesized by reaction of 3,5-dichlorosalicylaldehyde, β-alamine and copper nitrate in ethanol solution. The crystal structure was determined by X-ray diffraction method. The crystal structure belongs to mono-clinic system with space group C2/c and cell parameters: a=3.853 7(3) nm, b=0.777 38(18) nm, c=2.656 36(2) nm, β=116.924(2)° and V=7.095 4(17) nm³, M_r=998.85, Z=8, D_c=1.870 g·cm^-3 and F(000)=3 992. The two Cu(Ⅱ) atoms are coordinated with four atoms from Schiff base, and another one is coordinated with five atoms. The square bridging links three metal centers through a novel μ-4,4,5 coordination model, which is further assembled into 1D chain coordination polymer. The 1D chain is further constructed a 3D network by strong O-H…O and C-H…O hydrogen bonds. The coordination polymer presents a good thermal stable property through the thermal analysis. CCDC: 679005.     

Synthesis,Crystal Structure,and Magnetic Properties of a New 2D Twofold Interpenetrated Coordination Polymer [Cu(3,4‐pybz)2]n

A new coordination polymer, [Cu(3, 4‐pybz)₂]_n ( 1 ) [3,4‐Hpybz = 3‐pyridin‐4‐yl‐benzoic acid], was synthesized by hydrothermal reaction of CuCl₂ · 2H₂O and 3,4‐Hpybz, and characterized by elemental analysis, IR spectroscopy, PXRD, and single‐crystal X‐ray diffraction. The structure determination reveals that 1 exhibits a 2D twofold interpenetrated 4‐connected (4,4) network topology, these 2D layers are further enlarged to form the final 3D supramolecular edifice via aromatic π–π stacking interactions. In addition, the magnetic behavior and thermogravimetric analysis of 1 were also studied.     

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.     

Synthesis and Crystal Structure of a Novel 2D Coordination Polymer [Cu_3（mal）_2（di-2-pyridlyktone）_2]

A novel coordination polymer of Cu II with flexible ligands,namely,[Cu 3 (mal) 2 (di2-pyridlyktone) 2 ] (1,H 2 mal=maleic acid),was synthesized and characterized by single-crystal X-ray diffraction,thermogravimetric analyses,elemental analysis and IR spectroscopy.The structure indicates that the complex crystallizes in monoclinic,space group P2 1 /c with a=10.268(2),b=17.737(3),c=8.038(1),β=98.275(2)°,V=1448.6(4) 3,Z=2,D c=1.883 Mg·m-3,μ=2.260 mm-1,F(000)=826,and the final R=0.0321 and wR=0.0820.In 1,three Cu II centers (Cu(1),Cu(2),Cu(1A)) are bridged by two uncommon μ 3-bridging H 2 mal ligands,furnishing a centrosymmetric trimetallic unit.Via further Cu-O COO coordination interactions,extention of these trimetallic units in two directions gives rise to an infinite corrugated 2D layer.In addition,thermal stability and electrochemistry of 1 were studied.     

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.     

(1‐Butyl‐4‐methyl‐pyridinium)[Cu(SCN)2]: A Coordination Polymer and Ionic Liquid

The compound (C₄C₁py)[Cu(SCN)₂], (C₄C₁py=1‐Butyl‐4‐methyl‐pyridinium), which can be obtained from CuSCN and the ionic liquid (C₄C₁py)(SCN), turns out to be a new organic–inorganic hybrid material as it qualifies both, as a coordination polymer and an ionic liquid. It features linked [Cu(SCN)₂]^? units, in which the thiocyanates bridge the copper ions in a μ_1,3‐fashion. The resulting one‐dimensional chains run along the a axis, separated by the C₄C₁py counterions. Powder X‐ray diffraction not only confirms the single‐crystal X‐ray structure solution but proves the reformation of the coordination polymer from an isotropic melt. However, the materials shows a complex thermal behavior often encountered for ionic liquids such as a strong tendency to form a supercooled melt. At a relatively high cooling rate, glass formation is observed. When heating this melt in differential scanning calorimetry (DSC) and temperature‐dependent polarizing optical microscopy (POM), investigations reveal the existence of a less thermodynamically stable crystalline polymorph. Raman measurements conducted at 10 and 100 °C point towards the formation of polyanionic chain fragments in the melt. Solid‐state UV/Vis spectroscopy shows a broad absorption band around 18 870 cm^?1 (530 nm) and another strong one below 20 000 cm^?1 (<500 nm). The latter is attributed to the d(Cu^I)→π*(SCN)‐MLCT (metal‐to‐ligand charge transfer) transition within the coordination polymer yielding an energy gap of 2.4 eV. At room temperature and upon irradiation with UV light, the material shows a weak fluorescence band at 15 870 cm^?1 (630 nm) with a quantum efficiency of 0.90(2) % and a lifetime of 131(2) ns. Upon lowering the temperature, the luminescence intensity strongly increases. Simultaneously, the band around 450 nm in the excitation spectrum decreases.     

Synthesis,Structure and Luminescent Property of an Europium(Ⅲ) Coordination Polymer

A novel europium(Ⅲ) coordination polymer, [Eu3(pydc)3(SO4)(H2O)5(ox)0.5]·3H2O(1, H2 ox = oxalic acid, H2 pydc = pyridine-2,6-dicarboxylic acid), has been synthesized hydrothermally from the self-assembly of lanthanide ions(Eu3+) with the flexible oxalic acid and the rigid pyridine-2,6-dicarboxylic acid ligands, respectively. It crystallizes in the triclinic system, space group P1 with a = 11.225(4), b = 12.390(5), c = 13.752(5)A, α = 89.228(7), β = 71.142(6), γ = 75.552(6)°, Dc = 2.317 g/cm3, μ = 5.480 mm-1, F(000) = 1150, Z = 2, the final R = 0.0351 and w R = 0.0949 for 8782 observed reflections with I 2σ(I). Structural analysis reveals that complex 1 exhibits a three-dimensional metal-organic framework via π-π stacking interactions. In addition, complex 1 displays a red fluorescence emission in the solid state at room temperature, which corresponds to the 5D0 → 7F2 transition of Eu3+ ions.     

Assembly and Crystal Structure of a Novel 1—D Coordination Polymer of Copper（Ⅱ）with Thiocyanate and 4—Cyanopyridine

A novel one‐dimensional coordination polymer, Catena‐poly [bis(4‐cyano‐pyridyl) copper(II)‐di‐thiocyanate], ¹_∞ [Cu^II‐(cypy)₂(μ_N.S‐SCN)₂] (cypy = 4‐cyano‐pyridyl), was synthesized in a solution reaction of Cu(NO₃)₂·3H₂O, 4‐cyano‐pyridine and KSCN in mole ratio of 1:2:2 at room temperature. Its crystal structure was determined by single‐crystal X‐ray diffraction. The crystal belongs to monoclinic crystal system, space group P2₁/c with cell parameters a = 1.0719(2), b = 1.8441(4), c =0.9144(2) nm, β = 110.49(3)° and Z = 4. A full‐matrix least‐squares refinement gave R₁ = 0. 0393 and wR₂= 0.0916 for 1554 reflections having 1 >2σ(I). The crystal is thermally stable up to approximately 170 °C.     

A new family of lanthanide coordination polymers based on 3,3′‐[(5‐carboxylato‐1,3‐phenylene)bis(oxy)]dibenzoate: synthesis,crystal structures and magnetic and luminescence properties

Six two‐dimensional (2D) coordination polymers (CPs), namely, poly[{μ₅‐3,3‐[(5‐carboxylato‐1,3‐phenylene)bis(oxy)]dibenzoato‐κ⁶O¹:O^1′:O³,O^3′:O⁵:O^5′}bis(N,N‐dimethylformamide‐κO)lanthanide(III)], [Ln(C₂₁H₁₁O₈)(C₃H₇NO)₂]_n, with lanthanide/Ln = cerium/Ce for CP1 , praseodymium/Pr for CP2 , neodymium/Nd for CP3 , samarium/Sm for CP4 , europium/Eu for CP5 and gadolinium/Gd for CP6 , have been prepared by solvothermal methods using the ligand 3,3′‐[(5‐carboxy‐1,3‐phenylene)bis(oxy)]dibenzoic acid (H₃cpboda) in the presence of Ln(NO₃)₃. The complexes were characterized by single‐crystal X‐ray and powder diffraction, IR spectroscopy, elemental analysis and thermogravimetric analysis (TGA). All the structures of this family of lanthanide CPs are isomorphous with the triclinic space group P and reveal that they have the same 2D network based on binuclear Ln^III units, which are further extended via interlayer C—H…π interactions into a three‐dimensional supramolecular structure. The carboxylate groups of the cpboda^3? ligands link adjacent Ln^III ions and form binuclear [Ln₂(RCOO)₄] secondary building units (SBUs), in which each binuclear Ln^III SBU contains four carboxylate groups from different cpboda^3? ligands. Moreover, with the increase of the rare‐earth Ln atomic radius, the dihedral angles between the aromatic rings gradually increase. Magnetically, CP6 shows weak antiferromagnetic coupling between the Gd^III ions. The solid‐state luminescence properties of CP2 , CP5 and CP6 were examined at ambient temperature and CP5 exhibits characteristic red emission bands derived from the Eu³⁺ ion (CIE 0.53, 0.31), with luminescence quantum yields of 22%. Therefore, CP5 should be regarded as a potential optical material.     

Synthesis and Crystal Structure of a 2D Coordination Polymer： [Nd2（PDB）2（CH3COO）2（H2O）3]

A novel coordination polymer [Nd2（PDB）2（CH3COO）2（H2O）3] （H2PDB = pyridine3,4-dicarboxylic acid） has been synthesized by the reaction of Nd（CH3COO）3 with pyridine3,4-dicarboxylic acid under hydrothermal conditions. Elemental analysis, IR spectra and X-ray crystal structure analysis were carried out to determine the composition and crystal structure of the title complex which belongs to the triclinic system, space group P^-1 with a = 6.9409（14）, b = 7.5497（15）, c = 22.530（5）A, α = 84.79（3）, β = 88.15（3）, γ= 75.55（3）^o, C18H18N2O15Nd2, Mr = 790.82, Z = 2, V = 1138.5（4） A^3, Dc = 2.307 g/cm^3,μ = 4.593 mm^-1, -6≤h≤8, -5≤k ≤8, -26≤l≤ 26, F（000） = 760, Rint = 0.0298, R= 0.0314 and wR= 0.0695 （I〉 2σ（I））. Nd（1） and Nd（2） are linked into zigzag chains by carboxylate groups of acetate with interesting μ3-η^2：η^2 fashion. The zigzag chains are bridged by PDB to form a 2D framework, and a 3D supramolecular network is further constructed via π-π stacking.     

Crystal Structure and Luminescence of a Europium Coordination Polymer {[Eu(p-MOBA)_3·2H_2O]·0.5H_2O· 0.5(4,4′-bipy)}_∞

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新型镉(Ⅱ)配位聚合物的合成与性能

以1,3,5-三(咪唑基)苯(tib),4,4-二苯醚二甲酸(H2L)和Cd(NO3)2·6H2O为原料,在水热条件下合成了一个新的Cd(Ⅱ)配合物[Cd2(L)4(tib)2DMF]n·DMF(Cd-2 MOF)(1,CCDC:1901161),其结构经IR,元素分析和X-射线单晶衍射表征。结果表明:配合物1属三斜晶系,P 21/n空间群,晶胞参数a=10.0363(9)A,b=14.1842(13)A,c=20.2842(18)A,α=97.754(3)°,β=98.410(3)°,γ=104.960(3)°。室温固态荧光测试结果显示配合物1具有很强的发射峰,并研究其变温荧光性质,通过后功能化修饰掺杂稀土元素实现了Ln^3+封装的MOF(Ln=Eu,Tb,Eu/Tb)材料发射的细调。     

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.     

铕与2，4-二氯苯甲酸一维链状配位聚合物的合成，晶体结构和发光性质

溶液法合成了一个新的铕配位聚合物[Eu(2,4-DClBA)₃(CH₃CH₂OH)₂]_n(2,4-DClBA=2,4-二氯苯甲酸根),并用X-射线单晶衍射分析确定了其晶体结构。配合物晶体属于三斜晶系,P1空间群。标题配合物是无限一维链状聚合物,中心Eu³⁺离子通过桥联双齿2,4-二氯苯甲酸根氧原子连接。Eu³⁺离子的配位数为8     

三维银配位聚合物[Ag3(IN)2(CF3COO)]的水热合成与晶体结构

本文在水热条件下, 通过4-氰基吡啶发生原位水解得到异烟酸, 将其与AgCF3CO2作用合成了新型银配位聚合物, 并通过元素分析和X射线单晶衍射分析等手段对其结构进行了表征.     

Synthesis and Characterization of a Novel 3D Coordination Polymer Based on Cu（II） Cations and Mellitic Acid

A new mellitate complex [Cu3（μ2-mellitate）（μ2-H2O）（H2O）2·H2O]n 1 has been synthesized by the reaction of mellitic acid and Cu（CH3COO）2·H2O in the presence of base. Crystallographic data for 1： C12H8O16Cu3, Mr = 598.80, orthorhombic, Pbcn, a = 8.4378（6）, b = 10.0396（7）, c = 17.6799（12）A, V = 1497.70（18）A^3, Z = 4, De = 2.656 g/cm^3, μ = 4.327 mm^-1, F（000） = 1180, R = 0.0431 and wR = 0.0964 for 1075 observed reflections （I 〉 2σ（I））. X-ray crystal structural analysis revealed that the mellitate anions behave as the bridging ligands and link eight copper atoms repeatedly to form a novel three-dimensional metal-organic coordination polymer with two different rhombic tunnels in the solid-state structure.