壳寡糖铕、铽配合物的合成、表征及抗·O2^-活性

用壳寡糖分别与硝酸铕和硝酸铽反应,制备了壳寡糖-铕、壳寡糖-铽两种配合物。用红外光谱、紫外光谱、荧光和X射线光电子能谱（XPS）等分析测试手段对配合物进行了表征。以吩嗪硫酸甲酯（PMS）-还原型辅酶Ⅰ烟酰胺腺嘌呤二核苷酸（NADH）-硝基四氮唑蓝（NBT）产生超氧阴离子自由基（·O2^-）来研究壳寡糖和壳寡糖稀土金属配合物对·O2^-自由基的清除作用。结果表明：壳寡糖与Eu^3＋或Tb^3＋形成了配合物,壳寡糖-铕、壳寡糖-铽配合物中不仅壳寡糖氨基上的N原子参与了配位,同时仲羟基的O原子也参与了配位。壳寡糖和壳寡糖稀土金属配合物对·O2^-均具有明显的清除作用,配合物与壳寡糖相比对·O2^-具有更高的清除活性。     

壳寡糖铕、铽配合物的合成、表征及抗·O-2活性

用壳寡糖分别与硝酸铕和硝酸铽反应, 制备了壳寡糖-铕、壳寡糖-铽两种配合物. 用红外光谱、紫外光谱、 荧光和X射线光电子能谱(XPS)等分析测试手段对配合物进行了表征. 以吩嗪硫酸甲酯(PMS)-还原型辅酶Ⅰ烟酰胺腺嘌呤二核苷酸(NADH)-硝基四氮唑蓝(NBT)产生超氧阴离子自由基(·O-2)来研究壳寡糖和壳寡糖稀土金属配合物对·O-2自由基的清除作用. 结果表明: 壳寡糖与Eu3 或Tb3 形成了配合物, 壳寡糖-铕、壳寡糖-铽配合物中不仅壳寡糖氨基上的N原子参与了配位, 同时仲羟基的O原子也参与了配位. 壳寡糖和壳寡糖稀土金属配合物对·O-2均具有明显的清除作用, 配合物与壳寡糖相比对·O-2具有更高的清除活性.     

壳聚糖镍和壳聚糖镧配位聚合物的配位数研究

从ＩＲ、ＥＳＲ和ＸＰＳ的测试结果可知,Ｎｉ＾２＋或Ｌａ＾３＋与壳聚糖（ＣＳ）键节单元上的氨基Ｎ和仲羟基Ｏ发生配位反应,形成ＣＳ－Ｎｉ＾２＋或ＣＳ－Ｌａ＾３＋配位聚合物膜。通过电导率研究其配位数,发现Ｎｉ＾２＋或Ｌａ＾３＋可与壳聚糖的３个或５个键节单元配位。根据以上的实验可推定中心离子Ｎｉ＾２＋与壳聚糖３个键节单元上的氨基Ｎ和仲羟基Ｏ结合,形成六配位的ＣＳ－Ｎｉ配位聚合物Ｌａ＾３＋与壳聚糖５个键节单     

稀土（La^3＋和Nd^3＋）氨基葡萄糖配合物的合成、表征和抗O2^-·活性

用D-氨基葡萄糖盐酸盐（D-Glu.HCl）与LaCl3或NdCl3反应制备了Glu-La（Ⅲ）和Glu-Nd（Ⅲ）配合物。用元素分析、电导率、红外光谱、紫外光谱和X射线光电子能谱（XPS）等分析测试手段对配合物进行表征。研究了Glu及稀土配合物对O2^-·自由基的清除作用。结果表明,Glu与La^3＋、Nd^3＋形成的配合物中Glu氨基上的N原子和仲羟基的O原子参与了配位,同时Cl^-也参与了配位。Glu和稀土氨基葡萄糖配合物对O2^-·均具有明显的清除作用,配合物比Glu对O2^-·具有更强的清除活性。     

羧甲基壳寡糖与钆配合物的制备

用羧甲基壳寡糖(CM-COS)与硝酸钆反应,制备了羧甲基壳寡糖与钆的配合物(CM-COS-Gd).用红外光谱、热重分析等测试手段对配合物进行了表征.讨论了溶液的酸碱度、反应时间和物料比对配合物形成的影响,对CM-COS-Gd的配位机理进行了初步研究.结果表明,不仅CM-COS中的羧基参与了配位,氨基上的氮原子和羟基氧原子也参与了配位.CM-COS-Gd和CM-COS相比,热稳定性有所增加.     

两个含三唑环有机配体的Hg（Ⅱ）配聚物的合成、晶体结构及其荧光性质

以碘化汞为原料,分别与3,5-二(4-吡啶基)-1,2,4-三唑(L1),4-氨基-3,5-二(4-吡啶基)-1,2,4-三唑(L2)在N,N-二甲基甲酰胺(DMF)溶液中反应,合成了2个一维链状Hg(Ⅱ)配聚物{[Hg2I4(4-bpt)2]·3DMF}n(1),{[Hg2I4(L2)]·DMF}n(2)。用红外光谱、元素分析、X-射线单晶衍射对配合物进行了表征。X-射线单晶衍射表明,配聚物1中汞离子位于扭曲的配位四面体中心,相邻汞离子通过分别与L1的2个端基N原子配位,桥连形成了一维zig-zag链结构,碘离子占据配位四面体的剩余两配位点,配聚物1的一维链平行于bc平面。配合物2中汞离子位于扭曲的配位四面体中心,分别与L2的一个吡啶N原子和3个碘离子配位,其中2个碘离子充当桥联配体将相邻汞离子连接,形成了一维-Hg-I-Hg-I-的zig-zag链,相邻的-Hg-I-Hg-I-链进一步通过作为双齿配体的L2连接,形成一独特的一维双链梯状聚合物,配聚物2一维链平行于a方向。室温固态荧光测试显示,配聚物1在383.7nm处具有强的荧光发射,而配聚物2在299.7 nm和376.5 nm处具有强的荧光发射。     

两个含三唑环有机配体的Hg(Ⅱ)配聚物的合成、晶体结构及其荧光性质（英文）

以碘化汞为原料,分别与3,5-二(4-吡啶基)-1,2,4-三唑(L1),4-氨基-3,5-二(4-吡啶基)-1,2,4-三唑(L2)在N,N-二甲基甲酰胺(DMF)溶液中反应,合成了2个一维链状Hg(Ⅱ)配聚物{[Hg2I4(4-bpt)2]·3DMF}n(1),{[Hg2I4(L2)]·DMF}n(2)。用红外光谱、元素分析、X-射线单晶衍射对配合物进行了表征。X-射线单晶衍射表明,配聚物1中汞离子位于扭曲的配位四面体中心,相邻汞离子通过分别与L1的2个端基N原子配位,桥连形成了一维zig-zag链结构,碘离子占据配位四面体的剩余两配位点,配聚物1的一维链平行于bc平面。配合物2中汞离子位于扭曲的配位四面体中心,分别与L2的一个吡啶N原子和3个碘离子配位,其中2个碘离子充当桥联配体将相邻汞离子连接,形成了一维-Hg-I-Hg-I-的zig-zag链,相邻的-Hg-I-Hg-I-链进一步通过作为双齿配体的L2连接,形成一独特的一维双链梯状聚合物,配聚物2一维链平行于a方向。室温固态荧光测试显示,配聚物1在383.7nm处具有强的荧光发射,而配聚物2在299.7 nm和376.5 nm处具有强的荧光发射。     

壳寡糖与镧、铈配合物的合成、表征及应用

合成了壳寡糖，镧和壳寡糖，铈配合物，用红外光谱和紫外光谱进行了表征，并证实了氮，金属(N-M)键的形成，元素分析证实配合物中各元素C：H：N：La或Ce的原子个数比分别接近于24：44：4：1，即相当于配位数为4。壳寡糖一镧和壳寡糖一铈较未配位的镧或铈具有更强的催化氧化能力。配合物除去废液中磷[(PO)^3-4]的效果比未配位的镧和铈提高10％。配合物可提高蔬菜、水稻种子的发芽率，促进作物的营养生长，提高水稻产量3，3％，提高黄瓜产量12％～15％，对十字花科蔬菜的病毒有一定的抑制作用。     

新型一维链状配位聚合物{[Cu2(dhbd)(bipy)2]·10H2O}n的研究

采用水热法合成了标题配位聚合物{[Cu2(dhbd)(bipy)2]·10H2O}n(H4dhbd=2,3-二羟基丁二酸,bipy=2,2'-联吡啶),通过元素分析、红外光谱、热分析、X射线单晶衍射等技术对其进行了表征.配合物属单斜晶系,空间群C2/c,a=2.1965(4)nm,b=1.0671(2)nm,c=1.3662(3)nm,β=93.50(3)°,Z=4,R=0.0388.晶体的基本构建基元包含10个结晶H2O分子和由两个Cu(Ⅱ)原子、一个采用双二齿螯合配位的2,3-二羟基丁二酸根、两个2,2'-联吡啶形成具有C2旋转轴的U形双核单元,相邻的两个方向相反的U形双核单元通过双羧基O桥联形成沿c轴延伸的一维链;链间籍C-H…O和O-H…O氢键扩展为三维结构.配合物中呈现了一种2,3-二羟基丁二酸与过渡金属配位的新方式.     

Al(Ⅲ)-槲皮素配合物的光谱分析

采用UV和IR分析手段,研究在甲醇溶剂酸性和中性条件下,槲皮素(3,3,′4,′5,7-五羟基黄酮)与A l(Ⅲ)形成配合物的构型、反应配比及在配位反应过程中配体分子中各个配位点的配位能力大小及优先配位的顺序。实验结果表明:在酸性介质中,槲皮素与A l(Ⅲ)所形成配合物的反应配比为A l(Ⅲ)∶Q=1∶1,其配位点为3-羟基-4-酮,配位构型中心为A l(Ⅲ)与一个槲皮素分子形成五元环四配位的配合物。在中性介质中发生两步配位反应,第一步配位反应发生在3-羟基-4-酮配位点其反应配比为1∶2,配位构型为中心A l(Ⅲ)与两个槲皮素分子形成两个五元环之间四配位的配合物;第二步配位反应发生在3,′4′-二羟基配位点其反应配比为2∶1,两个A l(Ⅲ)离子分别在上述两个配位点与一个槲皮素分子形成五元环四配位构型的配合物。     

Phosphine-based coordination cages and nanoporous coordination polymers

Recent findings in the use of multidentate phosphines to synthesise porous coordination polymers (metal-organic frameworks) and their possible precursor cages are reviewed. Additional recent investigations into using large adamantoid Age cages as polymer vertices in giant diamandoid structures are also presented. The results are discussed in terms of possible strategies for the controled synthesis of porous coordination polymers.     

Silver coordination compounds with antimicrobial properties

Silver and its compounds have long been known to possess antimicrobial properties. We report here on our observations in this field of research, namely on silver coordination compounds, and in particular polymers, which can be used in the medical field. An overview of the structural diversity of coordination compounds with a particular class of organic ligands is given, together with their properties, with a special focus on antimicrobial activity, solubility and light stability. Copyright © 2013 John Wiley & Sons, Ltd.     

Ring-opening polymerisation of coordination rings and cages

Despite the great interest in crystalline coordination polymers (sometimes called metal organic frameworks) surprisingly little is known about how they form. However, there has recently been some attention given to characterising their solution-based precursors. Of particular interest is the formal ring-opening polymerisation (ROP) relationship between the structures of some precursors and polymers, and the actual observation of ring-opened oligomers by solution state NMR spectroscopy. These points are highlighted and discussed along with related aspects of isomerism in discrete and polymeric coordination structures, and polymer-polymer interconversion.     

Some applications of thermal analysis to the coordination chemistry

The behaviour of complexes of the type MeD2I2 (Me=Co,D = acetylacetone or benzoylacetone,I = imidazole and derivatives in the course of the stepwise thermal degradation is different. In the case ofD = acetylacetone in the first step acetylacetone is split off. At D = benzoylacetone the decomposition starts with the partial elimination of the heterocyclic ligands.In-position unsubstituted nickelacyclic complexes from type (bipy)Ni(CH₂CH₂CH₂COO) decompose by a reductive elimination and separating of CO₂ forming a (bipy)Ni-intermediate. A single reductive decoupling is hindered by blocking up the-position.Opposite to the high thermal stability of the trimesityl aluminium the intermediates Almes₂Cl and AlmesCl₂ show with decreasing amounts of mesityl groups and increasing content of halogene, respectively, a significant decreasing thermal stability.The thermal degradation of nickelchelates of alkylsubstituted chinolin-8-ol starts with the dehydration followed by a different separation of the ligands as a function of the chain-length and the position of the substituents of the ligands.

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Zusammenfassung Das Zersetzung Verhalten der Komplexverbindungen vom Typ C0D2I2 (P = acetylaceton, Benzoylaceton;I = Imidazol oder Derivate) erfolgt stufenweise. Im Falle vonD = Acetylaceton erfolgt zuerst eine Eliminierung von Acetylaceton wärend beiD = Benzoylaceton zuerst ein Heteroligand eine Abspaltung erfährt.Bei einer unsubstituierten-Position von Nickelacyclen des Typs (bipy)Ni(CH₂CH₂CH₂COO) erfolgt eine thermisch induzierte-Hydrideliminierung unter Ringspaltung und Freisetzung von CO₂.Im Gegensatz zur hohen thermischen Stabilität des Trimesityl Aluminium erfahren die Zwischenverbindungen Almes₂Cl und AlmesCl₂ mit abnehmenden Mesityl- bzw. zunehmenden Chlorgehalt einen wessentlich früheren thermischen Zerfall. Bei zunehmenden Kovalenzgrad ist hier ein Einfluss der veränderten Polarisation anzunehmen.Der thermische Abbau der prinzipiell wasserhaltig kristallisierenden Nickelchelate von alkylsubstituierten Chinolin-8-ol beginnt jeweils mit der Dehydratisierung. In Abhängigkeit von der Kettenlänge und der Position der Substitution am Chinolin schliesst sich der thermische Abbau der Chelatliganden ein- bzw. mehrstufig an.

     

Assembling tetrapyrrole derivatives through axial coordination

Bis(4-pyridinolato) silicon(IV) phthalocyanine (1) binds with a series of zinc(II) tetrapyrrole derivatives with the two pyridyl ligands forming the corresponding 1:2 or 1:1 molecular assemblies. The molecular structure of the first axially linked trinuclear phthalocyanine-porphyrin array has also been determined.     

Self-assembly of a cavitand-based heteronuclear coordination cage

A new self-assembly protocol leading to the formation of heteronuclear coordination cage 10 is reported. Reaction of tetradentate cavitand ligand 1, bearing one ethynylpyridine and three benzonitriles at the apical positions, with Pt(dppp)OTf₂ and Pd(dppp)OTf₂ in a 1:3 ratio yields 10 as the thermodynamic product. Under the same conditions, the self-assembly of 1 with either Pt or Pd metal precursors gives a mixture of isomeric homonuclear cages 8a-c or 9a-c, respectively.     

Reactive blending via metal-ligand coordination

d-Block transition-metal-containing polymer blends which form coordination complexes are described in this treatise. The model compounds are zinc acetate dihydrate, copper acetate dihydrate, nickel acetate tetrahydrate, cobalt chloride hexahydrate, palladium chloride bis (acetonitrile), and the dimer of dichlorotricarbonylruthenium (II). Two classes of ligands are of interest. Poly (4-vinylpyridine), P4VP, and copolymers that contain 4-vinylpyridine repeat units form complexes with zinc, copper, nickel, cobalt, and ruthenium salts. Atactic 1,2-polybutadiene contains olefinic sidegroups that displace weakly bound acetonitrile ligands and coordinate to palladium chloride. Thermal analysis via differential scanning calorimetry suggests that the glass transition temperature of the polymeric ligand is enhanced by these low-molecular-weight transition-metal salts in binary and ternary blends. In some cases, d-block salts function as transition-metal compatibilizers for copolymers that would otherwise be immiscible. The isothermal ternary phase diagram for polybutadiene with palladium chloride highlights regions of gelation, precipitation, and transparent solutions during blend preparation in tetrahydrofuran. Fourier transform infrared spectroscopy provides molecular-level data that support the concept of polymeric coordination complexes. High-resolution carbon-13 solid-state NMR spectroscopy identifies (1) near-neighbor interactions between polymeric pyridine ligands and the ruthenium salt, and (2) a considerable reduction in the molecular mobility of the polybutadiene chain backbone when it forms a coordination complex with palladium chloride. The elastic modulus of polybutadiene increases by three orders of magnitude when the palladium salt concentration is 4 mol % in a solid-state glassy film. A thermodynamic interpretation of ligand field stabilization energies appropriate to tetrahedral cobalt and octahedral nickel complexes is employed to estimate the synergistic enhancement of the glass transition temperature, particularly when coordination crosslinks are present. ©1995 John Wiley & Sons, Inc.     

功能配位聚合物研究进展

主要就配位聚合物在气体吸附、手性拆分和催化、分子磁体方面的研究进展进行了综述,指出配位聚合物作为潜在的新型功能材料近年来得到了科学家的普遍关注;列举了近年来这类配位聚合物的研究成果和开发进展,并对其发展前景作了展望.     

Thermal analysis of some polynuclear coordination compounds

The thermal behaviour of five polynuclear coordination compounds containing tartaric anion as ligand, namely (NH₄)₃[LnFe(C₄O₆H₄)₃(OH)₃] (Ln=La and Eu), (NH₄)₂[PrFe(C₄O₆H₄)₃(OH)₂] and (NH₄)[LnFe(C₄O₆H₄)₃(OH)]·3H₂O (Ln=Nd and Gd) was investigated. The reaction progress was studied by TG/DTA and FTIR measurements. Oxalates and oxocarbonates were identified as intermediates. In the case of Ln=La, Nd, Pr, Eu and Gd, pure LnFeO₃ was obtained as final decomposition product. The thermal decomposition of Eu-Fe compound, leads to a mixture of mixed (ortho-ferrite (EuFeO₃) and garnet (Eu₃Fe₅O₁₂)) and simple oxides (Eu₂O₃ and α-Fe₂O₃).     

Self-assembly of metal-organometallic coordination networks

A range of neutral metal-organometallic coordination networks (MOMNs) containing both backbone and pendant metal sites have been synthesized and characterized. These materials consist of metal ions or metal ion clusters as nodes that are linked by the bifunctional “organometalloligand” (η⁴-benzoquinone)Mn(CO)₃⁻, which binds through the quinone oxygen atoms. The resulting MOMNs can be rationally designed to a significant extent based upon a knowledge of the electronic and geometrical requirements of the metal ion nodes, the solvent, organometalloligand substituents, and the presence or absence of organic spacers. An impressive range of architectures have been accessed in this manner, suggesting that the use of π-organometallics in coordination directed self-assembly holds much promise.