稀土高分子配合物发光材料的合成

发光稀土高分子配合物是一类很有价值的功能材料,本文就其3种合成方法进行评述。以稀土离子与含配位基团的聚合物进行反应,难以获得发光强度高的高分子配合物;使稀土离子与高分子配体和小分子配体同时作用,可以得到荧光强度比较理想的产物,但反应难以定量控制;以小分子稀土配合物单体进行聚合反应,也可获得荧光强度较高的高分子配合物,但聚合反应的空间位阻较大。并针对方法3提出了改进的思路。     

水杨醛缩氨基硫脲配合物与牛血清蛋白的弱相互作用研究

本文合成了水杨醛缩氨基硫脲席夫碱配体并与锰、镉金属离子进行配位反应,合成了两种配合物。并通过红外光谱图分析,对配体及配合物的做了表征,分析了配合物可能存在的结构。选用荧光光谱法对席夫碱及其配合物和牛血清蛋白的弱相互作用进行了研究分析,结果表明该配体及其金属配合物与牛血清蛋白形成了基态复合物,引起了牛血清蛋白内源荧光猝灭现象,而具体何种荧光猝灭还有待进一步研究。     

铕高分子配合物荧光强度与铕离子浓度的关系

稀土离子发光材料性能优良,既可电致发光又可光致发光,广泛应用于生物分析化学,激光材料,防伪商标等领域。本文以邻菲哕啉为小分子配体,聚丙烯酸-甲基丙烯酸甲酯为高分子配体,制备铕的高分子荧光配合物,研究了配合物中荧光强度与铕离子浓度的关系,发现Eu^3＋的浓度在1．25×10^-5mol／L和2．0×10^-4mol／L之间配合物的荧光强度与Eu^3＋的浓度呈线性关系,其加标回收率为98．6—101．3％,在该浓度范围内可对配合物中Eu^3＋浓度进行定量测定。     

双-8-羟基喹啉高分子配合物的合成与应用

用8-羟基喹啉在有相转移催化剂存在的碱性条件下,与氯仿作用合成5-甲酰基-8-羟基喹啉,然后将5-甲酰基-8-羟基喹啉分别与对苯二胺、联苯二胺,4,4＇-二氨基二苯砜反应,得到三种双-8-羟基喹啉-席夫碱配体,然后与金属离子配位,得到了一类新型的双-8-羟基喹啉-席夫碱-金属高分子配合物,再结合双-8-羟基喹啉-席夫碱配体与其它离子的显色反应,进行对比分析.利用红外光谱、紫外光谱对配体和配合物的结构进行表征,利用荧光光谱研究了高分子配合物的光致发光性能.     

聚苯乙烯-聚4-乙烯基吡啶-稀土铕(Ⅲ)发光配合物的微观结构及荧光性能表征

含共轭结构氮杂环的非离子嵌段共聚物能与铕(Ⅲ)络合反应形成发光配合物,研究了该发光配合物的配位结构及其荧光性能。以聚苯乙烯-聚4-乙烯基吡啶(PS-b-P4VP)作为高分子配体,以邻菲罗啉(Phen)作为小分子配体,通过吡啶环的氮原子与Eu(Ⅲ)离子配位发生络合反应形成了以网状的Eu(Ⅲ)-P4VP核层以及PS链段为壳层的共聚物-稀土配合物,通过电子透射电镜(TEM)分析了其微观形态结构。用荧光分光光度计分别表征了嵌段聚合物-稀土铕(III)配合物不同链段的荧光发光强度并且进行了荧光强度的对比。此外,还研究了不同的Eu(Ⅲ)离子浓度对荧光强度的影响,得到了制备共聚物-稀土配合物荧光的最佳Eu(Ⅲ)离子浓度。     

羟基苯二磺酸金属配合物的制备及表征

以苯酚为原料磺化制得羟基苯二磺酸。通过自组装法进行羟基苯二磺酸配体与金属（K、Sr、Ba）化合物反应,并深入地研究了羟基苯二磺酸金属配合物的合成方法及其性质。利用红外光谱、荧光光谱对配体、配合物、配位情况进行表征。结果表明,配体与金属配位良好。     

含吡啶基吸附材料的研究进展

介绍了含吡啶基吸附材料对金属离子、无机阴离子及有机污染物的吸附分离研究进展。吡啶环的氮原子具有较强的配位功能,能与多种金属离子形成络合物。这类吸附材料对金属离子显示出高的吸附容量和吸附选择性,其吸附金属离子后形成金属主体高分子,然后再利用金属离子与具有配位性能的无机阴离子、有机污染物通过路易斯酸-碱在水溶液中进行配体交换,从而达到吸附分离的目的。作为高分子交换配体(PLE),这类新型吸附材料将是今后发展的重点。     

荧光材料钴配合物的合成、晶体结构及荧光传感

以5-氨基间苯二甲酸为配体,采用溶剂热法构筑了一个新型的[Co(C_8H_5NO_4)(H_2O)]_n·2H_2O配合物。通过IR、元素分析以及X-射线单晶衍射表征产物的结构。该配合物的中心离子CoII分别与来自四个不同配体的四个羧酸氧原子、一个氨基氮原子和一个水分子上的氧原子配位,形成了六配位CoO_5N的八面体构型。对配合物的荧光性质及荧光传感性能进行了研究,结果表明不同金属离子对配合物荧光强度有不同程度的影响,该配合物可作为荧光传感材料选择性的检测Mn~(2+)。     

可高分子化的小分子8-羟基喹啉金属配合物的合成与表征

通过8-羟基喹啉的氯甲基化,预先合成5-氯甲基-8-羟基喹啉,在催化剂无水醋酸钠的作用下,再使之与双官能团的化合物氯乙醇反应,合成具有反应活性点的8-羟基喹啉的衍生物(C lCH2CH2OCH2-Hq),然后与含有A l3+,Zn2+,L i+的金属化合物及8-羟基喹啉经由配位反应,合成了可溶性的具有单反应活性点的小分子8-羟基喹啉金属配合物(这些配合物含有A lQ3,ZnQ2,L iQ基团),这类化合物可以接枝到高聚物上,得到高相对分子质量的含8-羟基喹啉金属配合物的发光材料1。HNMR、FTIR、元素分析确定了小分子8-羟基喹啉金属配合物的组成;紫外吸收光谱(UV)、光致发光光谱(PL)说明小分子8-羟基喹啉金属配合物的发光来自于A lQ3,ZnQ2,L iQ基团。     

染料木素金属配合物的抗氧化活性研究

以染料木素化合物为配体与铜、锌金属离子配位,合成出染料木素过渡金属配合物。利用红外、紫外光谱、元素分析及摩尔电导等方法,对染料木素及其配合物进行了结构表征。此外,对配体及其金属配合物进行了抗氧化能力的测定。结果表明:金属离子与染料木素配体的协同作用可提高其抗氧化活性的能力。     

Fluorescence properties of ternary complexes of polymer-bond triphenylphosphine,triphenylarsine, triphenylstibine,and triphenylbismuthine,rare earth metal ions,and thenoyltrifluoroacetone

Rare earth metal ions containing polymer ternary complexes were synthesized and characterized. The functional polymers investigated were polymer-bond triphenylphosphine (PBDP), polymer-bond triphenylarsine (PBDAs), polymer-bond triphenylstibine (PBDSb), and polymer-bond triphenylbismuthine (PBDBi) as polymer ligands. Several substances, such as thenoyltrifluoroacetone (TTA), and 8-hydroxyquinoline (oxin), phenanthroline (phen) were used as low molecular weight ligands. The results show that TTA is the best low molecular weight ligand among them. The fluorescence properties of synthesized complexes were investigated; PBDAs is a better polymer ternary complex that possesses stronger fluorescence intensity coordinated with any low molecular weight ligand. The fluorescence lifetimes of Eu³⁺-containing polymer ternary complexes are between 0.350 and 0.469 MS. The reaction conditions of the formation and stability of rare earth metal ions–polymer–TTA ternary complexes are discussed. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1605–1611, 1998     

α-二亚胺后过渡金属配合物在烯烃聚合中的应用研究进展

介绍了α-二亚胺配体后过渡金属烯烃聚合催化剂的研究进展,对此类催化剂因改变配体空间位阻、改变配体取代基电子效应而对催化活性、相对分子质量、分子结构的影响进行了综述。三联苯基配体催化剂兼具高活性和高稳定性,刚性环和轴向给电子基团有机结合的α-二亚胺配体后过渡金属催化剂具有高活性、产物高相对分子质量、高线型、低支化度的特点,为新型催化剂的制备以及新型材料的合成提供了新思路。     

Nematicidal, Fungicidal and Bactericidal Activities of Manganese (II) Complexes with Heterocyclic Sulphonamide Imines

Some manganese(II) complexes derived from different sulphadrugs and heterocyclic ketones have been prepared. These complexes have been characterized on the basis of elemental analyses, molecular weight determinations, conductivity measurements, infrared, ESR and magnetic measurements. The spectral data suggest that the ligands act in a monobasic, bidentate manner coordinating through nitrogen atom. A high spin tetrahedral geometry around this metal has been proposed on the basis of magnetic and spectral studies. The isolated products are coloured solids, soluble in DMSO, DMF and MeOH. All the complexes are monomeric in nature as indicated by their molecular weight determinations and conductivity measurements in dry DMF show them to be non-electrolytes. All the ligands and their corresponding complexes have been screened for their fungicidal, bactericidal and nematicidal activities.     

Synthesis and fluorescence properties of rare earth metal ion–polymer ligand–low molecular weight ligand ternary complexes

Eu³⁺-containing polymer ternary complexes were synthesized using different kinds of functional polymers such as poly(benzylmalonic acid styrene) (PBMAS), poly(benzylacetone styrene) (PBAAS), and poly(benzyl-azo-o-hydroxybenzoic acid styrene) (PBAHBAS) as polymer ligands. The structures of the complexes were investigated by elemental analysis and IR spectroscopy. The fluorescence intensity of Eu³⁺–polymer–TTA (2-thenoyltrifuoroacetone ion) complexes was decreased in the order PBMAS(61) > PBAAS(42) > PBAHBAS(32). In system of Eu³⁺–PBMAS–low molecular weight ligand, the emission spectrum shape, the fluorescence intensity, and the wavelength of the maximum emission peak were changed when the low molecular weight ligand was varied. The fluorescence intensity of the Eu³⁺–PBMAS–TTA ternary complex was 610 times stronger than that of the Eu³⁺–PBMAS binary complex and 160 times stronger than that of Eu³⁺–PBMAS–oxine complex. The fluorescence intensity of the Eu³⁺–PBAAS–TTA complex was enhanced greatly when the proper mol ratio of HTTA/Eu³⁺ and pH in the reaction were chosen.     

Aminothiol polyalkylene sulfide oligomers

The carbonates and oxides of zinc and cadmium polymerize propylene sulfide to elastomeric materials, but with the addition of ammonia low molecular weight polymers are produced. The effect of the ammonia is to react with some of the propylene sulfide to give aminopropanethiol, which will itself polymerize monomer by a stepwise reaction or, after reaction with the metal carbonate, form a metal bis(aminopropanethiolate) which is an active initiator. Chemical and spectroscopic examination of these polymers shows them to be essentially bifunctional, with one NH₂ and one SH terminal group. There is, however, evidence to suggest that further reaction of monomer occurs with the terminal amine groupings to give polyfunctional compounds. From the relative proportions of ammonia, zinc carbonate, and monomer, the rate of polymerization, molecular weight, and degree of endgroup coordination with catalyst residue can be controlled as desired. Due to the highly reactive endgroups, the polymers are readily crosslinked with epoxy resins, aziridinyl compounds, and hexamethoxymethylene melamine to give useful products exhibiting high solvent resistance.     

π-Conjugated soluble palladium poly-ynes: Synthesis and fluorescence properties

Insertion of thiophene-2,5-diyl, or 1,4-phenylene into palladium poly-ynes by the polycondensation of dihalide complexes PdCl₂(PR₃)₂ (R = Ph o γ n-butyl) with a di-yne monomer (obtained from the reaction of equimolar quantities of p-diethynyl-benzene with 2,5-diiodothiophene or 1,4-diiodobenzene) affords a series of palladium poly-ynes 1–6. The polymers/oligomers, soluble in common organic solvents, exhibit strong fluorescence at the excitation of UV-visible light at room temperature. The emission intensity of the polymers/oligomers with thiophene-2,5-diyl is 3–17 times stronger than that of the analogous polymers without thiophene-2,5-diyl. Polymers with phenyl substituted phosphine ligands emit stronger emission than those only with n-butyl phosphine ligands. The effects of molecular weight, ligands, solvents, and concentration on the fluorescence properties are also investigated. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 1657–1665, 1997     

基于巯基三氮唑及其衍生物构筑配合物的研究进展

巯基三氮唑是一种含硫氮杂环有机化合物,由于具有多个配位点和较强的配位能力以及衍生物的多样性, 近些年在配位化合物、医药等方面受到广泛研究。本文按照取代基数目的不同将巯基三氮唑衍生物分为疏基三 氮唑、单取代巯基三氮唑、多取代巯基三氮唑、多臂巯基三氮唑衍生物,并按照分类系统地总结了近些年来这 类配体及其金属配合物的合成方法和结构特征方面的研究成果,同时介绍了其金属配合物在药物、功能材料方 面的应用。最后依据巯基三氮唑及其衍生物构筑配合物的研究现状,从配体、金属离子两方面对巯基三氮唑未 来的研究方向进行了展望。     

Supramolecular Structure,Mode of Coordination,Thermal and Potentiometric Studies of Polymer Complexes: A Review

Chelating compounds derived from acryloyl monomers are being utilized as suitable ligands. They enable the formation of rigid coordination polymers. This review gives information about preparation and structurally characterization the polymer complexes by analyses, spectral techniques like IR, NMR, ESR thermal and potentiometric methods. The ESR spectral data of the Cu(II) complexes showed that the metal–ligand bonds have considerable covalent character. The thermal stability was investigated using thermogravimetric analysis. The thermal behavior of these chelates shows that the hydrated complexes lose water molecules of hydration in the first step followed immediately by decomposition of the anions and ligand molecules in the subsequent steps. The results showed that the polymer complexes are more stable than the homopolymer. Proton ligand dissociation and metal ligand stability constants of acryloyl monomers with some transition metal ions in monomeric and polymeric forms potentiometrically were determined.