两个新型锌的配位聚合物的合成与晶体结构

本文以Zn(NO3)2.6H2O分别与1,3,5-均苯三甲酸(1,3,5-H3BTC)和2,5-噻吩二羧酸(2,5-H2TDC)通过水热/溶剂热反应合成了2个锌的配位聚合物[Zn3(OH)(BTC)2(C4N2H11)(H2O)]n(1)(C4N2H11=质子化的哌嗪)和[Zn(2,5-TDC)(i-PrOH)]n(2)。并对配位聚合物1和2进行了元素分析、FTIR和X-射线单晶结构解析等表征。X-射线单晶结构解析表明配位聚合物1和2的晶体均属于正交晶系,空间群分别为Pbca和P212121。化合物1中含有Zn3O结构单元,Zn3O结构单元通过BTC的连接构成1个层状结构,层状结构再通过堆积形成1个三维结构。化合物2中含有无机的Zn-O链。无机Zn-O链通过TDC配体与相邻的6个无机Zn-O链相连形成三维开放式的框架结构。     

金属离子导向合成两个金属配位聚合物:晶体结构和荧光性质

以2,5-呋喃二羧酸和六水硝酸锌/四水硝酸镉为原料,在溶剂热条件下,合成出2个金属有机配位聚合物,[Zn（FDC）（DMF）₂]_n（1）和{（Me₂NH₂）₂[Cd₂（FDC）₃（H₂O）₂]·4H₂O}_n（2）（H₂FDC=2,5-呋喃二甲酸,DMF=N,N-二甲基甲酰胺）。通过元素分析、红外光谱、差热分析、X射线粉末衍射和X射线单晶衍射等手段对配合物进行了结构表征。结果显示,化合物1为一维链结构,通过分子间氢键作用构筑成二维结构;而2为二维（4,4）网络结构。热稳定性表明化合物1脱去DMF配体后稳定到300 ℃;而2脱去配体水、阴离子和溶剂分子后结构立即发生坍塌。常温固态下,激发波长分别为303 和350 nm时考察了配合物1和2的荧光性质,结果显示2个化合物均发射蓝色荧光（λ_max=406,470 nm）,荧光寿命分别为76.2和138.1 ns。     

原位反应合成四唑金属配位聚合物：结构与磁性

使用Demko-Sharpless方法,在溶剂热条件下可以安全、有效地获得含四唑基团的配体。基于此反应,引入叠氮短桥共配,获得了2个结构新颖的配位聚合物Co₃(3-ptz)₄(N₃)₂(H₂O)₂·4H₂O (1)与Mn₃(3-ptz)₂(N₃)₄(H<     

金属离子导向合成两个金属配位聚合物:晶体结构和荧光性质

以2,5-呋喃二羧酸和六水硝酸锌/四水硝酸镉为原料,在溶剂热条件下,合成出2个金属有机配位聚合物,[Zn (FDC)(DMF)₂]_n(1)和{(Me₂NH₂)₂[Cd₂(FDC)₃(H₂O)₂]·4H₂O}_n(2)(H₂FDC=2,5-呋喃二甲酸,DMF=N,N-二甲基甲酰胺)。通过元素分析、红外光谱、差热分析、X射线粉末衍射和X射线单晶衍射等手段对配合物进行了结构表征。结果显示,化合物1为一维链结构,通过分子间氢键作用构筑成二维结构;而2为二维(4,4)网络结构。热稳定性表明化合物1脱去DMF配体后稳定到300℃;而2脱去配体水、阴离子和溶剂分子后结构立即发生坍塌。常温固态下,激发波长分别为303和350 nm时考察了配合物1和2的荧光性质,结果显示2个化合物均发射蓝色荧光(λ_max=406,470 nm),荧光寿命分别为76.2和138.1 ns。     

两种锌卟啉聚合物自组装染料敏化太阳能电池

合成了2种新型锌卟啉并与金属Mn构建配位聚合物(CPsx,x=1,2)。2种配位聚合物与锚定卟啉(ZnPA)通过金属-配体轴向配位自组装染料敏化太阳能电池(DSSC)。测试结果表明自组装电池具有较好的光电转换效率,特别是基于CPs2的装置具有较高的短路电流和转换效率。我们还对其光学、电化学及光电性能进行了研究,并通过透射电镜(TEM)对自组装体有效敏化在TiO_2电极上进行验证。     

Hydrothermal Synthesis of Two New Transition Metal Coordination Polymers with Mixed Ligands

Hydrothermal reactions of 1, 2, 4‐benzenetricarboxylic acid, 1, 10‐phenanthroline and transition metal cations including Zn^II or Co^II, in basified aqueous solution gave rise to two complexes, [Zn₃(btrc)₂(1, 10‐phen)₂(H₂O)₂]_n ( 1 ), and [Co₃(btrc)₂(1, 10‐phen)₂(H₂O)₂]_n ( 2 ) (btrc = 1, 2, 4‐benzenetricarboxylate, and 1, 10‐phen = 1, 10‐phenanthroline). 1 2 crystalize isotypically in the triclinic space group P1¯. The btrc ligand acts as multi‐dentate bridging ligand in both compound 1 and 2 to link up transition metal atoms into lamella networks, which are further attached into three‐dimensional frameworks through complex hydrogen bonding and π‐π interactions. The photoluminescence spectrum for compound 1 has also been studied. The corresponding reaction with Cu²⁺ follows another pathway.     

Two Novel Diamagnetic-metal Coordination Polymers of Nitronyl Nitroxide Radical Incorporating Isophthalate Bridges

Two novel coordination polymers of formula [Zn(NIT4py)₂(ip)]_n (1) and [Cd(NIT4py)₂(ip)(H₂O)]_n (2) (NIT4py=2-(4′-pyridinyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide and ip=isophthalate dianion), have been synthesized and determined by X-ray diffraction. The crystal structures of the complexes are both neutral 1-D chains. The Zn(II) ion adopts a distorted tetrahedral geometry and the Cd(II) ion adopts a distorted pentagonal bipyramidal geometry. Each isophthalate dianion binds two metal ions in bis-monodentate mode for complex (1) and in bis-bidentate mode for complex (2) leading to the 1-D chains. In complex (2) the 1-D chains develop into two-dimensional network via the hydrogen bond interactions. The magnetic studies show a weak antiferromagnetic coupling between two radicals through the diamagnetic Zn(II) in complex (1).     

Linear Conjugated Coordination Polymers Containing Eight-Coordinate Metal Centers

Two linear coordination polymers are reported in which conjugated organic ligands and nonrigid eight-coordinate metal centers are linked to form macromolecules with molecular weights of greater than 10⁴ Daltons. The tungsten(IV) chelate is an inert low-spin d² species with four oxygen and four nitrogen donors per metal with two bidentate blocking ligands and one bis-bidentate bridging ligand. The zirconium(IV) chelate is rendered inert through the use of a bis-quadridentate Schiff-base ligand. Future possibilities and potential uses are also discussed.     

Solvent Dependent Assembly,Structural Diversity and Topology Analysis in Two Novel Ni Coordination Polymers

Solvent dependent assembly obtained two novel Ni coordination polymers with H_2 tbtpa and flexible 1,2-bix ligand(H_2tbtpa = tetrabromoterephthalic acid and 1,2-bix = 1,2-bis(imidazol-1-ylmethyl)benzene),formulated as [Ni_(0.5)(tbtpa)_(0.5)(1,2-bix)·(H_2O)]_n(1) and [Ni(tbtpa)(1,2-bix)(H_2O)_2]_n(2).They have been structurally characterized by single-crystal and powder X-ray diffraction,elemental analysis,FT-IR spectra and TGA.Compound 1 crystalizes in triclinic,space group P1 with a = 9.0276(4),b = 10.0012(6),c = 11.4955(5) ?,α = 69.121(5),β = 76.398(4),γ = 89.668(4)o,C_(36)H_(32)Br_4 Ni N_8O_6,Mr = 1051.04,V = 939.05(8) ?~3,Z = 1,Dc = 1.859 g·cm~(-3),μ = 6.222 mm~(-1),F(000) = 520,8.502≤2θ≤134.16°,λ(Cu Kα) = 1.54184 ?,T = 294(6) K,the final R = 0.0750,w R = 0.1988 and S = 1.033.Compound 2 crystalizes in triclinic,space group P1 with a = 11.1257(7),b = 11.5062(6),c = 12.3529(4) ?,α = 88.861(3),β = 84.572(4),γ = 64.235(6)o,C_(22)H_(18)Br_4 Ni N_4O_6,Mr = 812.75,V = 1417.36(1) ?~3,Z = 2,Dc = 1.904 g·cm~(-3),μ = 7.968 mm~(-1),F(000) = 788,7.2≤2θ≤134.1°,λ(Cu Kα) = 1.54184 ?,T = 294(6) K,the final R = 0.0414,w R = 0.0865 and S = 1.025.1 shows a two-dimensional(4,4)-sql topology and 2 manifests a three-dimensional 6~58 Cd SO_4 topology coordination polymer network.     

Two Calcium Coordination Polymers with Multi-Stimuli-Responsive Properties

Two skeleton isomers, [CaL(H₂O)(DMF)₂]•DMF ( 1 ) (H₂L=5-(1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl)isophthalic acid) with a 1 dimensional chain structure and [CaL(DMF)_1.72]• (DMF)_0.28 ( 2 ) with a 2 dimensional layer structure were synthesized. Mechanochromic luminescence studies reveal that 1 and 2 exhibit luminescent red-shift and blue-shift respectively under grinding stimuli. The different influence of grinding stimuli on the π⋅⋅⋅π interaction in the two structures are proposed to be the main reason for such different responses. In addition, 1 has a rare broad sensing ability for halogenated hydrocarbons and can distinguish seven halogenated hydrocarbons out of 17 solvents. 1 can also be used for rapid detection of trace water in DMF with a calculated detection limit of 0.0078 v/v %. The relevant recognition mechanism is the decomposition of the structure during the recognition process due to the water instability of the ionic bond. The above results reveal that both compounds have the potential to be used as multi-stimulus-responsive materials.     

Two New Main Group Metal Coordination Polymers Based on 2,5-Furandicarboxylic Acid:Syntheses and Crystal Structures

By using solvothermal method, two new main group metal coordination polymers based on 2,5-furandicarboxylic acid(H2FDA) ligand, [Sr2(FDA)2(H2O)5]n(1) and [Ba4(FDA)4(H2O)10]n(2), were produced and characterized by single-crystal X-ray diffraction analyses, elemental analyses, IR, and powder X-ray diffraction. Compound 1 crystallizes in monoclinic, space group C2/c with a = 13.454(3), b = 13.426(3), c = 20.166(4), β = 107.06(3)°, V = 3482.4(13) 3, Dc = 2.188 g/cm3, C12H14Sr2O15, Mr = 573.47, F(000) = 2256, μ(Mo Kα)= 6.21 mm–1, Z = 8, R = 0.0522 and w R = 0.1229 for 2493 observed reflections(I 2σ(I)), and R = 0.0689 and w R = 0.1324 for all data. Compound 2 crystallizes in triclinic, space group P1 with a = 6.8382(14), b = 10.932(2), c = 25.571(5), α = 94.64(3), β = 95.41(3), γ = 107.83(3)o, V = 1799.4(6) 3, Dc = 2.484 g/cm3, C24H28Ba4O30, Mr = 1345.82, F(000) = 1272, μ(Mo Kα) = 4.43 mm–1, Z = 2, R = 0.0485 and w R = 0.0906 for 5020 observed reflections(I 2σ(I)), and R = 0.0706 and w R = 0.0991 for all data. In 1, the trinuclear clusters Sr3 are connected with adjacent four clusters by a carboxylate group to produce a two-dimensional(2D) sheet, which is extended by a FDA-based pillar into a 3D framework. In 2, neighbouring trinuclear clusters Ba3 are linked through two-O–C–O- of FDA2-ligands to form one-dimensional(1D) chains, which are connected by a FDA-based pillar to construct a 2D framework. The thermal stabilities of 1 and 2 are also investigated.     

Temperature Dependent Assembly,Structural Diversity and Luminescent Property in Two Novel Cd Coordination Polymers

Temperature dependent assembly of two novel Cd coordination polymers with the phen and H2 MIP ligands(phen = 1,10-phenanthrolion and H2 MIP = 5-methyl-isophthalic acid), formulated as Cd2(MIP)2(phen)2(1) and Cd3(MIP)3(H2MIP)(phen)2(2). They have been structurally characterized by single-crystal X-ray diffraction, elemental analysis, FT-IR spectra and TGA. 1 crystallizes in the monoclinic space group P2/n, while 2 crystallizes in the triclinic space group P1. 1 shows a 2D(two-dimensional) plane and 2 shows a 1D(one-dimensional) chain. In addition, their solid-state luminescent properties have also been investigated.     

Two New Coordination Polymers Containing Metal-carboxylate Helix

Two novel compounds, {[Cd(nbdc)(bpp)(H2O)]·H2O}n 1 and {[Cd(nbdc)(dpds)-(H2O)]·H2O}n 2(H2nbdc = 4-nitro-1,2-benzenedicarboxylic acid, bpp = 1,3-bis(4-pyridyl)propane and dpds = 4,4ˊ-dipyridyldisulfide), were solvothermally synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis(TGA), fluorescent analysis and single-crystal X-ray diffraction. Complex 1 is of monoclinic system, space group P21/c with a = 14.4370(17), b = 8.4090(10), c = 19.168(2) , β = 104.5050(10)°, V = 2252.8(5) 3, Dc = 1.639 g/cm3, Mr = 555.81, Z = 4, F(000) = 1120, μ = 1.022 mm-1, the final R = 0.0269 and wR = 0.0599 for 16656 observed reflections with I 2σ(I). 2 is isostructural to 1 with a = 14.4175(11), b = 8.4737(7), c = 18.0120(14) , β = 106.7220(10)°, V = 2107.5(3)3, Dc = 1.821 g/cm3, Mr = 577.85, Z = 4, F(000) = 1152, μ = 1.287 mm-1, the final R = 0.0280 and wR = 0.0705 for 15136 observed reflections with I 2σ(I). Both complexes present intimately related structures featuring infinite Cd-carboxylate helix of [CdⅡ(nbdc)(H2O)]n connected by bpp(or dpds) molecule to produce the 2D layer frameworks.     

Novel Furochromone Derivatives: Synthesis and Anticancer Activity Studies

Medicinal plant extracts have been used for medical purposes throughout human history. In this study, khellin, having furochromone structure, which is obtained from a well‐known traditional medicinal plant, was selected. A series of furochromonyl compounds ( K1 – K14 ) were synthesized for their anticancer activities. Furochromonyl compounds ( K1 – K14 ) were synthesized by Knoevenagel reaction of substituted 2,4‐thiazolidinediones ( Ia – j )/rhodanines ( Ik – n ) with khellin‐2‐carboxaldehyde ( V ), and their cytotoxicity was investigated in 22 cancer cell lines, which were originated from tissues such as the liver, breast, colon, and cervix. As the first step, two hepatocellular carcinoma cell lines Huh7 and PLC/PRF/5 (Alexander cells) were treated with 10 μM of each compound for 72 h, and then sulforhodamine B assay was performed to analyze their anti‐growth activities. Ethyl 2‐(5‐((4,9‐dimethoxy‐5‐oxo‐5H‐furo[3,2‐g]chromen‐7‐yl)methylene)‐4‐oxo‐2‐thioxothiazolidin‐3‐yl)acetate ( K11 ) was found as the most cytotoxic compound of primary screening. Afterwards, 12 hepatocellular carcinoma, seven breast cancer, two colon cancer, and a cervical cancer cell lines were selected to test K11 for 72 h at multiple concentrations to determine 50% effective doses. Results showed that the 14 cell lines were affected by K11 quantities lower than 10 μM. The structure of K11 , which is particularly effective on breast cancers, can be used to slow down the progression of tumors. Furthermore, the discovery of more effective compounds can be carried out on the basis of this structure.     

Two Novel Coordination Polymers of Schiff Base Ligands: Synthesis,Crystal Structures and Antibacterial Properties Studies

Two novel complexes [Ag L~1(NO_3)H_2O]_n(1) and [Pb L_2(NO_3)_2]_n(2) were synthesized by the evaporation reaction with metal salts and Schiff base ligands. They were characterized by elemental analyses, IR spectra and X-ray single-crystal diffraction. 1 crystallizes in monoclinic, space group P21/c with a = 18.358(3), b = 10.0395(15), c = 13.4643(16) ?, β = 91.749(12)o, V = 2480.4(6) ?3, Dc = 1.597 g/cm~3, Mr = 596.35, F(000) = 1208, Z = 4, R = 0.0772 and w R = 0.0927. 2 crystallizes in monoclinic space group C2/c with a = 15.8549(10), b = 21.1988(17), c = 17.7198(12) ?, β = 105.829(8)o, V = 5729.9(7) ?~3, Dc = 1.645 g/cm~3, Mr = 709.63, F(000) = 2736, Z = 8, R = 0.0541 and w R = 0.1175. X-ray single-crystal diffraction experiments of 1 and 2 display that extensive π×××π stacking interactions and hydrogen bonds construct into a 2D rectangular network and a 3D supramolecular framework. The antibacterial properties of L1, L2, 1 and 2 were also studied.     

Two Coordination Polymers: Protective Activity On Nerve Injury by Increasing miR-219 and Reducing Inflammatory Response

Two novel transition metal coordination polymers (CPs) of {Cu(tdc)(Hdmea)₂ (1, Hdmea?=?N,N-dimethylethanolamine, tdc?=?2,5-thiopenedicarboxylate) and [Co₃(H₂O)₃(tdc)₃(dioxane)]·2(dioxane) (2) were prepared via the reaction of Co(NO₃)₂·6H₂O or Cu(NO₃)₂·3H₂O and H₂tdc with or without the template reagent Hdmea. The following experiments were carried out to determine the treatment activity for compounds against nerve injury. Firstly, the real time RT-PCR was carried out to determine the miR-219 relative expression in the nerve cells. Then the activation level of the AMPK signaling pathway in the nerve cells was measured with western blot. In addition to this, the ELISA detection was also used in this research, for the inflammatory cytokines’ evaluation. Finally, the inhibition of the compound 1 and compound 2 on the death of the nerve cells was determined with MTT assay.

     

Self-Assembled Multivalent Ag-SR Coordination Polymers with Phosphatase-Like Activity

We show herein the phosphatase-like catalytic activity of coordination polymers obtained after adding Ag⁺-ions to thiols bearing hydrophobic alkyl chains terminated with a 1,4,7-triazacyclononane (TACN) group. The subsequent addition of Zn²⁺ -ions to the self-assembled polymers resulted in the formation of multivalent metal coordination polymers capable of catalysing the transphosphorylation of an RNA-model compound (2-hydroxypropyl-4-nitrophenyl phosphate, HPNPP) with high reactivity. Analysis of a series of metal ions showed that the highest catalytic activity was obtained when Ag⁺-ions were used as the first metal ions to construct the backbone of the coordination polymer through interaction with the -SH group followed by Zn²⁺-ions as the second metal ions complexed by the TACN-macrocycle. Furthermore, it was demonstrated that the catalytic activity could be modulated by changing the length of the hydrophobic alkyl chain.     

Novel Inorganic Coordination Polymers Based on Cadmium Oxalates

Three new cadmium oxalate coordination polymers, I-III, with extended layered structures have been synthesized in the presence of imidazole. While I was prepared by the reaction between imidazolium oxalate and Cd, II and III were synthesized from their constituents using hydrothermal methods. [Cd(C₂O₄)(C₃N₂H₄)]_∞ (I): monoclinic, space group P2₁/c (no. 14), a=8.7093(1) Å, b=9.9477(3) Å, c=8.4352 Å, β=93.796(1)°, Z=4; [Cd(C₂O₄)₂(C₃N₂H₄)₃(H₂O)]_∞ (II): monoclinic, space group P2₁/c (no. 14), a=7.8614(2) Å, b=14.9332(3) Å, c=15.9153(4) Å β=94.587(1)°, Z=4; [Cd(C₂O₄)₂(C₃N₂H₄)₃(H₂O)]_∞ (III): monoclinic, space group P2₁/c (no. 14), a=11.844(2) Å, b=9.066(1) Å, c=18.583(2) Å, β=103.84(2)°, Z=4. While the structure of I is made from CdO₅N distorted octahedra linked with oxalate, II and III are built-up from CdO₆N, CdO₅N₂ distorted pentagonal bi-pyramids connected to oxalate units. The framework formulas of II and III are identical and their structures closely related. In all the cases, the networking between the Cd-O/N polyhedra and oxalates give rise to layered architectures with the amine molecules pointing in a direction perpendicular to the layers (in the inter-lamellar region). The difference in the linkages between the oxalates and the Cd atoms in I-III, produces unusual Cd-O-Cd one-dimensional chains, which have been observed for the first time.