Coordination chain polymeric assemblies of trivalent lanthanides with multidentate Schiff base synthetic, spectral investigation and thermal aspects

The coordination chain polymers of La(III), Ce(III), Pr(III), Nd(III) and Sm(III) with N,N’-di(o-thiophenyl)terephthalaldehydediimine have been prepared and characterized by elemental analysis, ¹H NMR, ¹³C NMR, magnetic measurements, infrared spectra, reflectance spectra and thermogravimetric analysis. A coordination number of seven around the metal ion is suggested. The thermal decompositions of the coordination polymers have been studied. The kinetic parameters have been calculated using Freeman-Carroll method. The thermodynamic activation parameters such as entropy (S*), preexponential factor (A), enthalpy (H*) and free energy of the decomposition (G*) have been evaluated.     

对苯二胺缩对苯二甲醛席夫碱及其配合物的制备和电化学性能

以对苯二胺和对苯二甲醛为原料缩合制备出对苯二胺缩对苯二甲醛席夫碱聚合物（PT）,研究了采用不同物质的量之比的单体所制备的聚合物的电化学性能。利用席夫碱聚合物中N原子上的孤对电子与不同金属离子配位形成席夫碱配位聚合物（PT-M）,并对所形成聚合物的电化学性能进行了研究。采用X射线衍射（XRD）、红外（IR）、热重-差示扫描量热法（TG-DSC）、扫描电子显微镜（SEM）和能谱（EDS）对产物进行了表征,PT-M的XRD峰强度相比于PT明显降低,表明金属离子配位进入分子链骨架中引起的空间位阻减少了分子链排列的有序性。采用循环伏安、恒电流充放电和交流阻抗评价了所制备的配位聚合物材料的电化学性能。研究发现,聚席夫碱铝配合物（PT-Al）表现出较优的电化学性能,在0.5 A·g^-1的电流密度下其电容值为649.6 F·g^-1,并且具有较好的循环稳定性,在8 A·g^-1的电流密度下循环1 000次后仍有80.9%的电容保持率。     

两种含硫Schiff碱及其配合物的合成与光谱性质

合成了2-氨基噻唑缩5-溴水杨醛(HBrsatz)和2-乙酰噻吩缩4-羟基苯甲酰腙(Hetphz)两种含硫Schiff碱及其配合物[Cu(Brsatz)2](Ⅰ)和[Cd(H2O)(Hetphz)(phen)](NO3)2(Ⅱ),通过元素分析、红外光谱和紫外光谱对它们的结构进行了表征,并研究了它们在DMF溶液中的发光性质,结果表明HBrsatz和Hetphz及配合物Ⅱ具有较强的荧光发射.     

基于ZnTMPP一维线性配位聚合物的合成及其光、电性能

以四(对甲基苯基)卟啉锌(ZnTMPP)配合物为核心配体,选择联吡啶、联苯胺和新合成的Schiff碱-双(4-吡啶甲醛)缩联苯胺为桥联配体合成了3种新型π-π共轭的一维线性配位聚合物。通过FT-IR、1 H-NMR、UV-Vis-NIR和XRD衍射谱图等对配体及配位聚合物结构进行了表征。考察了桥联配体的长度及结构对配位聚合物光学性能、电性能和结晶态的影响。结果表明,以Schiff碱-双(4-吡啶甲醛)缩联苯胺为桥联配体合成的配位聚合物在300~1 100nm有宽吸收带,并且可在低电位发生氧化还原反应,其满带和空带之间的能隙为0.19eV;以联吡啶和联苯胺为桥联配体的配位聚合物结晶度较好。     

取代芳基席夫碱类化合物的室温研磨合成及其紫外可见吸收光谱的研究

研究了取代芳基单席夫碱及双席夫碱的室温研磨固态缩合反应,测定了其在环己烷和甲醇中的紫外可见吸收光谱,并探讨了其电子吸收光谱与分子结构的关系,以及溶剂对电子吸收光谱的影响.     

Synthesis and Crystal Structure of 1D Cd-amine Coordination Polymer and Its Luminescent Properties

A novel one dimension（1D） cadmium coordination polymer {[Cd（mpda）3]·2（NO3）}n（1） was synthesized via refluxing a mixture of tetradentate Schiff base ligand N,N＇-bis（2-pyridinylethylidene）phenylene-1,3-diamine（L） and Cd（NO3）2 in acetonitrile, whose structure was characterized by means of single crystal X-ray diffraction, FTIR spectroscopy, elemental analysis and proton nuclear magnetic resonance（1H NMR）. Center metal Cd（II） ion is six-coordinated by six nitrogen atoms from six different m-phenylenediamine（mpda）, giving rise to a [CdN6] octahe- dral coordination environment. The two adjacent cadmium centers are linked by three mpda molecules leading to the construction of 1D chain structure. The crystal structure is stabilized by N-H…O hydrogen bonds to form three-dimension supramolecule. Compound 1 exhibits intense yellow luminescence in solid state at 298 K（λem=554 nm）, which shows a blue shift at 77 K（ca. 147 nm）. Additionally, fluorescence characteristics of compound 1 were investigated in different solvents（polarity： DMSO〉CH3CN〉CH3OH〉CHC13〉toluene） at 298 and 77 K. The results show that the emission peak of compound 1 in solvent exhibits a slight bathochromic shift. However, the emission peaks of compound 1 in CH3OH and CHC13 are red shift compared with that in CH3CN. It is revealed that the lumi- nescence behavior of compound 1 depends on not only the polarity of solvent but also the hydrogen bonding proper- ties between solvent and solute. In addition, the emission peak of compound 1 in solution shows a red shift obviously at 77 K than that at 298 K（ca. 144-159 nm）, with the fluorescence lifetime increased at 77 K. The lifetime in DMSO at 77 K（r=12.470μs） was the longest one. The quantum yield of compoud 1 increases with increasing the polarity of solvent within a range of 1.8%-8.3 %.     

Expanded Porphyrins: The Synthesis and Metal Binding Properties of Novel Tripyrrane-Containing Macrocycles

Abstract

Novel tripyrrane macrocycles have been prepared by the Schiff base condensation of 2,5-bis-(3-ethyl-5-formyl-4-methyl-pyrrol-2-ylmethyl)-3,4-diethylpyrrole and simple diamines. The structurally characterized macrocycle 1 forms 1:1 complexes with both Rh(I) and Zn(II) cations in which the metal is coordinated only to the imine nitrogens. In the presence of Cd(II) and oxygen, however, compound 1 is oxidized to the aromatic pentadentate ‘expanded porphyrin’ macrocycle 5, into which the metal cation is fully complexed.     

联邻甲苯胺缩PMBP及其配合物的合成

以联邻甲苯胺和1-苯基-3-甲基-4-苯甲酰基吡唑啉酮(PMBP)为原料,采用固相法合成了两种新型Schiff碱——联邻甲苯胺单缩PMBP(L’)和联邻甲苯胺双缩PMBP(L);L分别与Cu(Ⅱ),Ni(Ⅱ)和Co(Ⅱ)配合制得三个对应的Schiff碱配合物,其结构经UV,1H NMR,IR和元素分析表征。     

Antibacterial Properties of a Kind of Schiff Base and Its Neodymium(III) and Zn(II) Complex (ZnNdL) on Escherichia coli

The microcalorimetric and electronic microscopy methods were used to study the antibacterial activity of a Schiff base and its complex ZnNdL on Escherichia coli. The metabolic power‐time curves of the bacteria treated with the compounds were obtained, and the thermokinetic parameters were analyzed. The results show that the compounds (H₂L, ZnNdL) have good activity on aerobic multiplying metabolism of E. coli, with the values of IC₅₀ 57.0 and 54.4 mg·L^?1, respectively. In order to further investigate their mechanism on E. coli, transmission electronic microscopy and scanning electronic micrography were used to study the cell membrane change induced by the dibasic quadridentate Schiff base and its neodymium(III) complex. At a low concentration of the compound, the flagellum was inhibited and the cell did not show distinct changes. However, the flagella around the cell membrane were exfoliated, the morphology of E. coli was changed from a rod shape into a spherical shape or a short rod, and the flagella disappeared completely at a high concentration. The drug permeability into cell membrane was investigated by fluorescence quenching of probe dis‐C₃‐(5), which suggested that H₂L and ZnNdL could influence on the intra and extra cell membrane.     

席夫碱类混价七核锰金属配合物的合成、表征及磁性

以3-乙氧基水杨醛缩乙醇胺席夫碱(H2L)为配体合成了2个新的七核锰配合物[Na2MnⅡMnⅢ6O2(L)6(N3)4(CH3COO)2]·4DMF(1)和[Na2MnⅡMnⅢ6O2(L)6(SCN)4(CH3COO)2]·2DMF (2),并对它们进行红外分析、元素分析、热重分析和单晶结构分析。单晶衍射结果表明,配合物1和2均为混价七核锰配合物,包含1个Mn2+和6个Mn3+。此外还研究了配合物1和2的磁学性质,磁性研究表明配合物1和2都表现出反铁磁作用。     

三种酰腙类Schiff碱的锌配合物的合成、晶体结构与表征

采用不同的方法合成了3种酰腙的锌配合物[Zn(Lss)(phen)(DMF)](1)、{[Zn(HLdis)]_2·2CH_3OH}_n(2)和[Zn(Baf)_2]·CH_3OH (3),通过元素分析、红外光谱、紫外光谱和热重分析进行了表征,并经X射线单晶衍射分析它们晶体结构。1和3的晶体属于三斜晶系P1空间群,Zn(Ⅱ)的配位数为6;2属于单斜晶系P2_1/n空间群,Zn(Ⅱ)的配位数为5。3的前驱体是一种吡唑啉类化合物(C_(15)H_(14)N_2O_3,Pzl),它的晶体属于单斜晶系P2_1/c空间群;Pzl与锌离子配位时发生分子重排,开环产物HBaf以酰腙结构与Zn(Ⅱ)配位形成3。     

三种水杨醛类席夫碱的合成与性质研究

以取代水杨醛和3-氨基噻吩为原料合成了三种水杨醛类席夫碱,探讨了水杨醛结构中酚羟基对位取代基结构变化对于该席夫碱探针的激发态内质子转移过程、pH响应和金属离子响应的影响。研究结果表明,改变取代基团的推、吸电子能力,可调节酚氧负离子对活泼氢的束缚能力,进而影响这些席夫碱分子的激发态内质子转移性能。同时,酚氧负离子的电荷密度也决定了其与阳离子的配位能力,从而表现出不同结构的席夫碱对金属离子的选择性和灵敏性差异。     

两个2,4-二羟基苯甲醛缩甘氨酸配合物的合成、结构及其对醇的选择性氧化催化

合成和表征了两个2,4-二羟基苯甲醛缩甘氨酸(H₃L)席夫碱配合物[Cu(Py)₂(HL)] (1)和[Zn(Py)₃(HL)]·2Py(Py=吡啶) (2),并通过X射线单晶衍射分析确定了其结构。配合物1通过分子间的O-H…O氢键形成了一维链状结构,配合物2通过分子间的O-H…O和C-H…O氢键形成了二维网状结构。重要的是,配合物1在醇的选择性氧化反应中显示出了良好的催化效率(转化率高达94.8%,选择性高达98.3%)。     

两个2,4-二羟基苯甲醛缩甘氨酸配合物的合成、结构及其对醇的选择性氧化催化

合成和表征了2个2,4-二羟基苯甲醛缩甘氨酸(H₃L)席夫碱配合物[Cu(Py)₂(HL)] (1)和[Zn(Py)₃(HL)]·2Py(Py=吡啶) (2),并通过X射线单晶衍射分析确定了其结构.配合物1通过分子间的O-H…O氢键形成了一维链状结构,配合物2通过分子间的O-H…O和C-H…O氢键形成了二维网状结构.重要的是,配合物1在醇的选择性氧化反应中显示出了良好的催化效率(转化率高达94.8%,选择性高达98.3%).     

杯[6]-1,4-冠-4酰胺型聚合物的合成与吸附性能

杯[6]-1;4-冠-4酰胺型聚合物的合成与吸附性能;芳烃聚合物;构象固定     

席夫碱型环磷腈类化合物的合成及光谱性质

通过亲核取代反应, 在2,2'-联苯二酚氧基环氯磷腈母体N₃P₃(O₂C₁₂H₈)₂Cl₂ (1)和N₃P₃(O₂C₁₂H₈)Cl₄ (2)上引入2-醛基吡啶与对胺基苯酚形成的席夫碱侧基, 合成了两种新型环磷腈化合物N₃P₃(O₂C₁₂H₈)₂(p-O-Ph-N＝C-Py)₂ (3)和N₃P₃(O₂C₁₂H₈)(p-O-Ph-N＝C-Py)₄ (4), 这些化合物是一类能形成配合物的多齿配体. 通过元素分析, IR, ¹H NMR, ³¹P NMR和TOFMS确定其结构, 研究了它们的吸收光谱和荧光光谱. H^＋和Cu^＋离子对其光谱性质的影响研究表明两种化合物的吸收和荧光光谱对H^＋和Cu^＋离子异常敏感, 因而在作为这些阳离子的荧光探针方面具有应用前景.     

含席夫碱基的螺吡喃双功能光致变色材料的合成及性质

设计合成了一系列含席夫碱基的螺吡喃双功能光致变色材料4a~4n. 通过1H NMR, IR和HRMS对其结构进行了表征. 研究了化合物在几种溶剂和PMMA膜中的光致变色性质, 研究了化合物4a在甲醇中, 以及化合物4a和4f在高分子介质聚甲基丙烯酸甲酯(PMMA)中的消色过程. 结果表明, 化合物4e在PMMA膜中光照后呈现出与其它化合物不同的颜色, 为罕见的绿色. 化合物4a在二氯甲烷溶液中有良好的荧光性能. 所合成的新型含席夫碱基的螺吡喃双功能光致变色材料在甲醇、二氯甲烷和环己烷溶液中及在PMMA膜中均表现出良好的光致变色性质.     

Synthesis,Characterization and Antimicrobial Activity of a New Aromatic Sulfonyl Hydrazone Derivative and Its Transition Metal Complexes

In this study, benzenesulfonicacid‐1‐methylhydrazide (bsmh) derivatives such as 2‐hydroxy‐1‐naphtaldehydebenzenesulfonylhydrazone (Hnafbsmh) and its Ni(II), Pd(II), Pt(II), Cu(II), Co(II) complexes were synthesized. The structures of these complexes were investigated using elemental analyses (FT‐IR, LC‐MS, UV‐VIS), magnetic susceptibility and conductivity measurement techniques. The complexes were found to have general compositions [ML₂]. All the synthesized complexes were evaluated in vitro as antimicrobial agents against representative strains of six gram‐positive and four gram‐negative bacteria and as an antifungal agent by disc diffusion methods. All the bacteria and fungi studied were screened against some commercial antibiotics to compare them with our chemical's zone diameters.     

Polymeric complexed membranes used as oxygen carrier: Axial and in-plane ligand effects

The complex formation reaction of modified styrene–butadiene–styrene block copolymer (SBS-g-VP and ESBS) with cobalt Schiff base (CoS) in chloroform solution is studied. The coordination number and formation constant are determined by the Miller method. The polymeric complexed membranes (SBS-g-VP–CoS and ESBS–CoS and ESBS–CoS) are made by solution casting method. The kinetics of oxygen binding to polymeric complexed membranes (SBS-g-VP–CoS and ESBS–CoS) is studied and the equilibrium, association, and dissociation constants are determined. The effects of polymeric axial ligand and of the equatorial chelate group are discussed. © 1993 John Wiley & Sons, Inc.     

新型双二元席夫碱的合成与谱学性质

新型双二元席夫碱的合成与谱学性质;双二元席夫碱化合物