基于多齿羧酸配体的Zn配位聚合物的合成及晶体结构

选用2-(3,5-二羧基苯基)-6-羧基苯并咪唑（H2cpcbi）作为配体,在溶剂热的反应条件下与锌盐反应,成功制备出了一种新的锌配位聚合物[Zn(cpcbi)]n(1)。采用X射线单晶衍射、X射线粉末衍射、热重分析和红外分析对产物的结构进行分析。结果表明：该化合物结晶于单斜晶系,p21/n空间群,具有二维层状结构。     

基于柔性羧酸配体与叠氮离子配体的配位聚合物的设计、合成与结构

为了探究配体对配位聚合物结构的影响,选用羧酸类柔性配体 1,4-双(3-羧酸吡啶基-1-亚甲基)苯二溴(H₂LBr₂)为主配,叠氮离子为辅配,Cd²⁺作为金属离子,合成了含有叠氮羧基共桥的配位聚合物测定并分析其晶体结构。分析表明其晶体拥有一个双重互穿的三维网络结构。     

配位聚合物的合成及其性质

通过对配位聚合物的合成方法、影响因素、性质应用等内容的介绍,指出了配位聚合物作为新型功能性材料得到广泛关注的原因。并对配位聚合物的发展前景作了展望。     

配位聚合物的分类以及合成方法

配位聚合物由金属离子和有机配体通过配位键自组装而形成,结构多样,文章主要通过综述配位聚合物配体的分类情况以及配位聚合物的合成方法来介绍不一样的配位聚合物。     

基于含铜簇配位聚合物的制备及晶体结构

通过席夫碱配体2-羟基-3-甲氧基-苯甲醛缩烟酰肼(IAH)和碘化亚铜在溶剂热条件下得到新型的铜(I)配位聚合物[(Cu2I2)L]n。通过元素分析、红外光谱和热重分析等方法对该配合物进行了表征,并测定了它的单晶结构。配合物属三斜晶系,空间群P-1,a=7.998 8(8)?,b=12.642 3(12)?,c=17.919 7(17)?,α=89.528(2)°,β=89.528(2)°,γ=73.688 0(10)°,V=1 738.9(3)?~3,Z=2。     

三维锌孔道配位聚合物的合成及结构

在DMF/H2O/C2H5OH混合体系中,以2-(4-吡啶)-咪唑二羧酸为有机连接体与Zn2+反应得到了一个新的含有孔道的三维锌配位聚合物,分子式为:Zn3(HL)3(DMF)2.2DMF,H3L=2-(4’-吡啶)-咪唑二甲酸,DMF=N,N-二甲基甲酰胺。单晶X射线分析显示1是带有一维矩形孔道的三维开骨架结构,孔道直径大小为18.28×6.952。     

一维梯状配位聚合物[ZnL（bbi）0.5（H2O）]n的结构及性质研究

一种新的配位聚合物[ZnL(bbi)0.5(H2O)]n(1)(L=3-羧甲基苯甲酸,bbi=1,4-二咪唑丁烷)被合成出来。结构分析表明化合物1结晶于单斜晶系,P21/n空间群,a=0.9674(3)nm,b=0.6294(2)nm,c=2.4918(7)nm,β=96.91(1)°。两种配体与金属离子连接形成一维梯状链,链间通过分子间相互作用形成二维网络结构。化合物1的元素分析,红外光谱,热重分析和荧光性质被表征。     

含羧基超支化聚酯丙烯酸酯的合成及其性能研究

以季戊四醇为"核",二羟甲基丙酸为AB2单体,利用逐步聚合方法合成了不同代数超支化聚酯。将得到的不同代数超支化聚酯用丁二酸酐和六亚甲基二异氰酸酯与丙烯酸羟乙酯的半加成产物按不同比例进行改性,得到了含羧基超支化聚酯丙烯酸酯。对得到的含羧基超支化聚酯丙烯酸酯的结构用傅里叶红外光谱、核磁共振波谱等手段进行了表征。紫外光谱表明,所有超支化低聚物在210 nm处有强紫外吸收;差示扫描结果表明,所有超支化聚酯丙烯酸酯都具有低的玻璃化转变温度;热重分析测试结果显示,随着超支化聚酯代数增加,超支化聚酯丙烯酸酯固化膜耐热性能提高。     

Synthesis, Crystal Structures and Fluorescence Properties of Two One-Dimensional Cadmium(II) Coordination Polymers Containing Flexible Bis(benzimidazole) Ligands

Two one-dimensional Cd(II) coordination polymers constructed by ribbon-like molecules, {[Cd(L₁)₂(NO₃)]·NO₃} _n (1) (L₁ = 1,3-bis(5,6-dimethylbenzimidazol-1-yl)benzene) and [Cd(L₂)₂(NO₃)₂] _n (2) (L₂ = 1,3-bis(benzimidazol-1-yl)benzene) have been obtained through assembly of the two structurally similar flexible bis(benzimidazole)-based ligands and cadmium nitrate tetrahydrate. The cadmium(II) centers display different coordination environments with trigonal-bipyramidal geometry in 1, and a octahedral geometry in 2. Weak C–H···O interactions in 1 result in a two-dimensional supramolecular layer; two π–π interactions are present in 2 forming a three-dimensional supramolecular network structure. The solid state fluorescence properties of 1 and 2 were investigated.     

Synthesis,Structures, and Catalytic Properties of Two Zinc(II) Coordination Polymers Constructed from Polycarboxylate and Bis(Benzimidazole) Ligands

Two Zn(II) coordination polymers, formulated as {[Zn(L1)_0.5(btc)_0.5(H₂O)]·H₂O} _n (1) and {[Zn(L2)(1,4-ndc)]·2H₂O} _n (2) [L1 = 1,4-bis(2-methylbenzimidazole-1-ylmethyl)benzene, L2 = 1,4-bis(2-methylbenzimidazole)butane, H₄btc = butane-1,2,3,4-tetracarboxylic acid, 1,4-H₂ndc = 1,4-naphthalenedicarboxylic acid] have been synthesized and structurally characterized by single crystal X-ray diffraction. Complex 1 features a 3D (3,4)-connected network with the topology of fsh-3,4-P2₁/c. Complex 2 is a 2D (4,4) grid with sql topology and further extends into a 3D supramolecular framework by π–π stacking interactions. In addition, the thermal stability, fluorescence, and catalytic properties of two complexes for degrading methyl orange dye in a Fenton-like process were investigated.     

Synthesis and Properties of pH-Dependent Gemini Surfactants Containing Multiple Carboxyl Groups

A series of Gemini surfactants N,N″-dialkyl-N,N′,N″-tripropionate diethylenetriamine (referred as DTPDT-n, where n is the length of the hydrocarbon chain, n = 10, 12, 14) were synthesized, which have three carboxylic head-groups and two hydrophobic alkane chains. The products were characterized by means of nuclear magnetic resonance and mass spectrometry. The physicochemical properties of DTPDT-n surfactants with different hydrocarbon chain lengths were studied such as isoelectric point, surface activities, emulsifying properties, and foam properties. It is showed that these compounds exhibit pH-dependent protonation-deprotonation behavior. The isoelectric points of DTPDT-n surfactants are between 3.40 and 10.90. The critical micellar concentration (cmc) of all three surfactants are lower than the corresponding monomeric surfactants (single head group, single-chain), especially DTPDT-14, whose cmc can reach 2.29 × 10⁻⁵ mol/L. With an increase in the length of the alkyl chain, the solubility of the surfactants decreases and the surface tension of the three surfactants at cmc increases. In consideration of pH, all of three surfactants appear better emulsifying capacity and foaming property under weak alkaline conditions. DTPDT-14 has the best performance of emulsifying capacity among the three surfactants. DTPDT-10 has excellent foaming ability and foam stability.     

含咔唑基聚合物的合成、发光性能及应用

采用封管聚合法合成了3种含咔唑基聚合物——聚乙烯基咔唑(PVK)、聚2-(9-咔唑基)乙基甲基丙烯酸酯(PCEM)和聚N-〔3-(9-乙基咔唑基)〕甲基丙烯酰胺(PECMA),考察了其紫外光谱和荧光光谱,探讨了取代基对咔唑基团发光性能的影响。结果表明,单体CEM和ECMA表现出明显的结构自猝灭效应(SSQE),而相应的聚合物未见SSQE。单体乙烯基咔唑(NVK)、CEM的荧光最大发射波长分别为440、435 nm,相对于咔唑(418nm)有明显的红移,ECMA则蓝移(410 nm),而相应的聚合物红移或蓝移都不明显。将聚合物作为空穴传输材料,通过共聚引入8-羟基喹啉铝高分子后,8-羟基喹啉铝高分子发光材料的电致发光起亮电压由14 V下降至9V,发光效率提高了3~4倍。     

含羧基水性环氧树脂的制备及其性能

以烯丙基缩水甘油醚(AGE)和甲基丙烯酸(MAA)为原料,采用一步法,即基于自由基共聚理论,合成具有良好稳定性的含羧基水性环氧树脂。探讨了加料方式、引发剂种类及用量等因素对聚合物性能的影响,对含羧基水性环氧树脂的结构进行了红外、核磁表征,并将其应用于山羊酸皮的鞣制工序中。结果表明,采用氧化还原引发体系—过硫酸铵和亚硫酸氢钠,过硫酸铵用量为单体总质量的11%,单体全部滴加的方式制得聚合物稳定性良好,转化率为98%。应用结果表明,聚合物单独鞣制后坯革的收缩温度可达71℃,增厚率达46%;配合酸皮质量3%的铬粉鞣制后坯革的收缩温度为114.1℃,增厚率为104%;与传统铬鞣法相比,该工艺方法有效降低了废液中的Cr2O3含量,减少了环境污染。     

Syntheses,Crystal Structures and Physical Properties of Four Zinc/Cadmium Coordination Polymers Based on 4-Nitrophthalic Acid and N-donor Auxiliary Ligands

Four new d¹⁰ metal coordination polymers, [Zn(4-NPA)(2,2-bipy)] _n (1), [Zn(4-NPA)(1,3-bimb)·H₂O] _n (2), [Cd(4-NPA)(2,2-bipy)] _n (3) and [Cd(4-NPA)(1,3-bimb)·H₂O] _n (4) (4-NPAH₂ = 4-nitrophthalic acid, 2,2-bipy = 2,2-bipyridine, 1,3-bimb = 1,3-bis(imidazol-1-ylmethyl)-benzene), have been hydrothermally synthesized and characterized by elemental analyses, IR spectra, and X-ray single crystal diffractions. Compounds 1?3 possess different one-dimensional (1D) chain structures. Compound 4 shows a two-dimensional (2D) layered structure. Moreover, the luminescent and thermal stabilities properties of compounds 1–4 were investigated in the solid state.     

Syntheses, Structures, and Luminescent Properties of Two Novel Coordination Polymers with Mixed Ligands

Two novel metal–organic coordination polymers {[Pb₂(MIP)₂(BDC)₂]·H₂O} _n 1 and [Cd(MIP)(NDC)] _n 2 [MIP = 2-(3-methoxyphenyl)-1H-imidazo [4,5-f] [1, 10] phenanthroline, BDC = terephthalic acid, NDC = naphthalene-1,4-dicarboxylic acid] were obtained from hydrothermal reaction and characterized by elemental analysis, thermogravimetric (TG) analysis, infrared spectrum (IR) and single-crystal X-ray diffraction. The coordination polymers crystallize in triclinic, space group P-1 with a = 1.0335(2), b = 1.4224(3), c = 1.8156(4) nm, β = 106.088(3)° for complex 1 and the complex 2 crystallizes in monoclinic, space group P2(1)/n with a = 1.2562(8), b = 1.4800(9), c = 1.3723(8) nm, β = 97.257(1)°, respectively. The metal ions Pb(II) are located in [:PbN2O4] pentagonal bipyramidal geometry in complex 1. The metal ions Cd(II) in complex 2 act as distorted octahedral geometry, being surrounded by four carboxylate oxygen atoms from three NDC ligands and two donor nitrogen atoms from one MIP molecule. Moreover, there are hydrogen bonds in the two complexes, and it is noteworthy that the existence of hydrogen bonds and π–π interactions reinforce the structural stability of the title complexes, which have been proved by TG analysis. The luminescent properties for the ligand MIP, NDC and complex 2 are also discussed in detail.     

Two 3D Coordination Polymers with New Topology Based on Mixed Ligands: Synthesis,Structure, and Photoluminescence Properties

Employing tetracarboxylate and imidazole mixed ligands to react with different transition meat salts afford two new 3D coordination polymers, {[Zn₂(BPTC)(BBI)₂]·(H₂O)₃·DMSO}_n (1) and {[Cd₂(BPTC)(BBI)₂]·H₂O}_n (2) (H₄BPTC?=?biphenyl-3,3′,4,4′-tetracarboxylic acid, BBI?=?1,1′-(1,4-butanediyl)bis(imidazole)). Both these two coordination polymers are 4-connected network topologies. Compound 1 features a unprecedented 3-nodal (4,4,4)-connected network topology with the point symbol {6⁴·8²}, and 2 displays a (4,4)-connected binodal network bearing new topology with the point symbol of {7²·8⁴}2{7³·8³}. Additionally, thermal stability and photoluminescence properties of 1 and 2 were investigated.