Synthesis, Characterization and Crystal Structures of Lanthanide Phenoxyacetate Complexes with 1,10-Phenanthroline

IntroductionTherehasbeenconsiderableinterestinthecoordinationchemistryoflanthanidecomplexeswithcarboxylateligandsduetotheirpotentialapplicationinmolecularassembliesandluminescentprobesinsystemsofbiologicalrelevance .1 4 Ofthenumerouslanthanidecomplexesthathavebeenwidelystudied,5 9mostofthemarefoundtoexhibitavarietyofdimericorinfinitechainstructure.RecentlywehavereportedpolymericLu(POA) 3(phen)compoundinwhichlutetiumionsforminfinitechainalongtheb axisdirectionthroughthecoordinationofbridgingc…     

Synthesis,Spectroscopic, Thermochemical Properties of Lanthanide Complexes with 3,4-Diethoxybenzoic Acid and 1,10-Phenanthroline

Three novel lanthanide complexes [Ln(3,4-DEOBA)₃phen]₂[Ln=Eu(1), Tb(2), Dy(3); 3,4-DEOBA=3,4- diethoxybenzoate; phen=1,10-phenanthroline] were synthesized and characterized by elemental analysis, molar conductance, X-ray diffraction and infrared spectrometry. The luminescence spectra of complexes 1 and 2 show the characteristic emission of Eu³⁺ ion(⁵D₀→⁷F_0-3) and Tb³⁺ ion(⁵D₄→⁷F_6-3). The thermal decomposition mechanism of the title complexes and the analysis of the evolved gases were investigated by thermogravimetry/differential scanning calorimetry-Fourier transform infrared(TG/DSC-FTIR) technology. The results indicate the complexes are thermally stable. In the thermal decomposition of the complexes, phen molecules lost firstly, and then 3,4-DEOBA ligand decomposed into H₂O, CO₂ and other gaseous molecules. Besides, several gaseous organic fragments were also detected. The heat capacities of complexes 1―3 were measured by DSC in a temperature range of 263.15―340.15 K. Based on the fitted polynomial and thermodynamic equations, the smoothed heat capacities and thermodynamic functions of the three complexes were calculated. The study on biological activity showed that the complexes exhibited good antibacterial activity against Candida albicans, Staphylococcus aureus and Escherichia coli.     

PREPARATION AND MAGNETIC PROPERTIES OF POLYMERIC COMPLEXES CONTAINING 1,10-PHENANTHROLINE

A series of polymeric complexes were prepared from Fe~(2 ),Co~(2 ) or Ni~(2 ) and poly(Schiff base)(DAPcIPA), which was obtained by polycondensation of 5,6-diamino-1,10-phenanthroline(DAP)with isophthalaldehyde(IPA).The structures of the polymer and the polymeric complexes were characterized by IR,~1H-NMR and elemental analysis.The magnetic behavior of these complexes was measured as a function of magnetic field strength(0-3.98×10~6 A/m)at 5 K and as a function of temperature(5-300 K)at a magnetic field strength of 2.39×10~6 A/m.Experimental results show that DAPcIPA-Ni~(2 ),DAPcIPA-Co~(2 ) are soft ferromagnets while DAPcIPA-Fe~(2 ) exhibits features of an antiferromagnet.     

7，7，8，8－四氰基对苯醌二甲烷与邻菲咯啉稀土配合物的合成和表征

７，７，８，８－四氰基对苯醌二甲烷与邻菲咯啉稀土配合物的合成和表征张明杰，聂玉敏，史志勤，张文胜，梁惠来（天津大学化学系天津３０００７２）（天津大学电子工程系天津）关键词四氰基对苯酮二甲烷，邻菲咯啉，镧配合物，钕配合物，合成７，７，８，８－四氰基对苯...     

Synthesis and Luminescence Study of Europium Complexes with Carboxylic Acid and 1,10-Phenanthroline Ligands

A series of euroPium(Ⅱ)eomPlexes with earboxylie aeids andl,10-Phenantl飞ro-line:Eu(L):·pllen·jHoO,wl:ereL-formate,3-hydroxy-4-metlloxybenzoate,4一metl、oxybenzoate,4一ehloroPhenoxyaeetate,and diPI、enylaeetate,were synthesizedand el、araeterized by elemental analysis,UV sPeetrum,IR speetrum and melting point.IR da亡a eonfirmed tllat euroPium 15 eoordinated wirh 0 donor atoms in earboxy!ie aeidand N donor atoms inl,10一phenanthroline.A strong ligand一loealized absorption at270 nm!ed to a series of meta!一eentered emission bands between 580 and 710 nm as-signedto ~5D_0-7F_(0.1.2.3.)     

四硫富瓦烯四硫纶桥联金属邻菲哕啉配合物的合成与性质

以2,3,6,7-四(2'-氰乙硫基)四硫富瓦烯为桥配体的前驱物,合成了标题配合物μ-(trftt)-[M(phert)]2(M=MnⅡ,FeⅡ,CoⅡ,NiⅡ,CuⅡ,ZnⅡ).配合物的结构和性质经由元素分析、核磁共振波谱、红外光谱、紫外-可见光谱、荧光光谱、摩尔电导率和量子化学计算表征,研究了电氧化还原和对Li/SOCl2电池的催化特性.发现铁和钴配合物具有较高的催化活性且有利于电池的大电流和低温放电,在25℃和电流密度25 mA/cm2条件下铁配合物使电池的电压和容量分别提高了133mV和218mAh.     

两种含有四硫富瓦烯羧酸基和1,10-菲啰啉配体的金属配合物的合成、结构及光学性质研究

本文用一种水溶性的TTF羧酸盐PropylTTFK2 (1)合成了两种金属配合物,Zn(L1)(Phen)2 (化合物3) 和Cd(L1)(Phen)2?(化合物4) (L1=PropylTTF2-; Phen=1,10-phenanthroline)。用元素分析对二者进行了测试,并解析了二者的晶体结构,具有明显的分子间S???S及H键作用。同时也测定了二者的紫外、荧光和电化学性质,滴定显示两种化合物均是很好的TCNQ电子接受体。     

La/Dy掺杂-L-苏氨酸-邻菲啰啉三元配合物的合成与性质

在乙醇-水溶液中,合成了一系列不同配比的稀土掺杂(La/Dy)-L-苏氨酸(L-Thr)-邻菲罗啉(Phen)三元固体配合物。对其进行了元素分析、摩尔电导、紫外光谱、红外光谱、热重分析等表征及分析,推测配合物的组成为[LaxDy1-x(L-Thr)3Phen]Cl3.2H2O。通过荧光光谱讨论配合物的发光特性,当La和Dy掺杂比为4∶6时,配合物的荧光强度达到最大。通过抑菌实验对配合物的生物活性进行了比较研究,当La和Dy掺杂比为6∶4时,对大肠杆菌的抑菌效果最强。     

四硫富瓦烯四硫纶桥联金属邻菲啰啉配合物的合成与性质

以2,3,6,7-四(2’-氰乙硫基)四硫富瓦烯为桥配体的前驱物, 合成了标题配合物μ-(ttftt)-[M(phen)]2 (M＝MnII, FeII, CoII, NiII, CuII, ZnII). 配合物的结构和性质经由元素分析、核磁共振波谱、红外光谱、紫外-可见光谱、荧光光谱、摩尔电导率和量子化学计算表征, 研究了电氧化还原和对Li/SOCl2电池的催化特性. 发现铁和钴配合物具有较高的催化活性且有利于电池的大电流和低温放电, 在25 ℃和电流密度25 mA/cm2条件下铁配合物使电池的电压和容量分别提高了133 mV和218 mAh.     

稀土与N-对甲基苯磺酰甘氨酸和邻菲咯啉配合物的合成与晶体结构

Three new lanthanide complexes with the formulae [Eu2（TsGly）6（phen）2（H2O）2] （1）, [Ln（TsGly）2（phen）2-（H2O）2]C1·2H2O [Ln=Er（2a） and Yb （2b）, TsGly=N-p-tolylsulfonylglycinate, phen= 1,10-phenanthroline] were synthesized. Crystallographic data for 1： monoclinic, P21/n, a= 1.29791（16） nm, b= 1.9034（2） nm, c= 1.7596（2） nm,β=93.410（3）°, V=4.3394（9） nm^3, Z=4, R1 =0.0326, wR2=0.0771; and for 2b： triclinic, P1, a= 1.2674（2） nm, b= 1.4405（2） nm, c= 1.4809（3） nm, a= 113.256（3）°, β= 108.253（3）°, γ=94.739（3）°, V=2.2922（7） nm°3, Z=2, R1=0.0292, wR2=0.0669. X-ray diffractional analysis reveals that compound 1 adopts dinuclear structure with fourfold bridging TsGly ligands between the Eu（Ⅲ） centers, while compound 2b features an unusual mononuclear structure.     

Formation Thermodynamics of Binary and Ternary Lanthanide(III) Complexes with 1,10-Phenanthroline and Chloride in N,N-Dimethylformamide

Formation thermodynamics of binary and ternary lanthanide(III) (Ln = La, Ce, Nd, Eu, Gd, Dy, Tm, Lu) complexes with 1,10-phenanthroline (phen) and the chloride ion have been studied by titration calorimetry and spectrophotometry in N,N-dimethyl-formamide (DMF) containing 0.2 mol-dm^–3 (C₂H₅)₄NClO₄ as a constant ionic medium at 25°C. In the binary system with 1,10-phenanthroline, the Ln(phen)³⁺ complex is formed for all the lanthanide(III) ions examined. The reaction enthalpy and entropy values for the formation of Ln(phen)³⁺ decrease in the order La > Ce > Nd, then increase in the order Nd < Eu < Gd < Dy, and again decrease in the order Dy > Tm > Lu. The variation is explained in terms of the coordination structure of Ln(phen)³⁺ that changes from eight to seven coordination with decreasing ionic radius of the metal ion. In the ternary Ln³⁺-Cl^–-phen system, the formation of LnCl(phen)²⁺, LnCl₂(phen)⁺, and LnCl₃(phen) was established for cerium(III), neodymium(III), and thulium(III), and their formation constants, enthalpies, and entropies were obtained. The enthalpy and entropy values are also discussed from the structural point of view.     

Electrochemical Studies of Eight New Divalent Transition Metal Benzenesulphonate Ternary Complexes with 1,10-Phenanthroline

The electrochemical properties of eight new divalent transition metal benzenesulphonate complexes with 1, 10-phenanthroline in different solvents and supporting electrolytes were investigated by means of cyclic voltammetry(CV). Based on the CV data the influences of various coordination modes on the electrochemical behavior of the complexes were discussed. The diffusion coefficient Dc and rate constant k, of those complexes in DMF systems were estimated according to CV and the results show that these processes were all quasi-reversible.     

Syntheses, Structures and Photoluminescence of Two New Layered Lanthanide Coordination Polymers with Thiophenedicarboxylic Acid and 1,10-Phenanthroline

Two isostructural layered coordination polymers constructed from mixed ligands, [Ln2（tdc）3（phen）2（H2O）2] （Ln = Sm 1, Eu 2, H2tdc = thiophene-2,5-dicarboxylic acid, phen = 1,10-phenanthroline）, have been hydrothermally synthesized and characterized by elemental analysis, IR and single-crystal X-ray diffraction. Crystal data for 1： triclinic, space group P1 with a = 10.546（2）, b = 11.201（2）, c = 18.644（4）A, α = 106.69（3）, β = 91.27（3）, γ = 94.43（3）°, Dc = 1.909 g·cm-3, F（000） = 1180, μ = 2.992 mm^-1, Z = 2, the final R = 0.0300 and wR = 0.0656 for 6968 observed reflections with I 〉 2σ（I）. And those for 2： triclinic, space group P1^- with a = 10.557（2）, b = 11.159（2）, c = 18.588（2） A, α = 106.945（6）, β = 91.255（6）, γ = 94.359（6）°, Dc = 1.927 g·cm^-3, F（000） = 1184, μ = 3.204 mm^-1, Z = 2, the final R = 0.0221 and wR = 0.0459 for 6328 observed reflections with I 〉 2σ（I）. The title complexes show a two-dimensional （2D） square grid structure constructed from paddle-wheel-like [Ln2（CO2）4] dimers and tdc ligands. The 2D layers were further assembled into a 3D supramolecular assembly via O-H…O hydrogen bond. The photoluminescence properties of complexes 1 and 2 were investigated.     

Synthesis, Crystal Structure and Optical Properties of Europium Trifluoroacetate Complexes with 1,10-Phenanthroline and 2,2-Bipyridine

Two europium trifluoroacetate complexes, Eu(CF₃COO)₃·phen ( 1 ) and Eu(CF₃COO)₃·bpy ( 2 ) (where phen=1,10‐phenanthroline, bpy=2,2′‐bipyridine), were synthesized and characterized by elemental analysis, Fourier transform infrared spectroscopy (FT‐IR), photoluminescence (PL) spectroscopy and thermogravimetric analysis (TA). Single‐crystal X‐ray structure has been determined for the complex [Eu₂(CF₃COO)₆·(phen)₃·(H₂O)₂]·EtOH. The crystal structure of [Eu₂(CF₃COO)₆·(phen)₃·(H₂O)₂]·EtOH shows that two different coordination styles with europium ions coexist in the same crystal and have entirely different coordination geometries and numbers. This crystal can be considered as an 1:1 adduct of [Eu(CF₃COO)₃·(Phen)₂·H₂O]·EtOH (9‐coordination part) and Eu(CF₃COO)₃·phen·H₂O (8‐coordination part). The excitation spectra of the two complexes demonstrate that the energy collected by "antenna ligands" is transferred to Eu³⁺ ions efficiently. The room‐temperature PL spectra of the complexes are composed of the typical Eu³⁺ ions red emission, due to transitions between ⁵D₀→⁷F_J(J=0→4). The lifetimes of ⁵D₀ of Eu³⁺ in the complexes were examined using time‐resolved spectroscopic analysis, and the lifetime values of Eu(CF₃COO)₃·phen and Eu(CF₃COO)₃·bpy were fitting with bi‐exponential (2987 and 353 µs) and monoexponential (3191 µs) curves, respectively. In order to elucidate the energy transfer process of the europium complexes, the energy levels of the relevant electronic states had been estimated. The thermal analyses indicate that they are all quite stable to heat.     

新型手性稀土配合物的合成、表征及其在不对称催化反应中的应用

作为符合绿色化学标准的稀土三氟甲磺酸盐Ln(OTf)3化合物打破了传统路易斯酸催化的模式，以其在水中稳定、催化用量少(一般少于10 mol％)和可回收再用的独特性质而受到广泛关注。Ln(OTf)3化合物可以催化许多有机合成反应，得到多种多样重要的合成中间体。但是，到目前为止，手性     

两个新型的1，10-菲罗啉桥联多胺配体及其配合物的合成与热力学性质

合成了2个新型的多齿配体：2，9-二-[1′-（2″-苯并咪唑基）-2′-氮杂-正丙基]-1，10-菲罗啉(L₁)和2，9-二-[2′-（2″-苯并咪唑基）-3′-氮杂-正丁基]-1，10-菲罗啉(L₂)并且用元素分析和 ¹H NMR谱作了表征。在25 ± 0.1 ℃，运用pH电位滴定法对这2个新的配体及其与过渡金属离子M(Ⅱ)(M=Co，Ni，Cu，Zn)和稀土金属离子Ln(Ⅲ)(Ln=La，Nd，Sm，Eu，Gd)的配合物进行了热力学稳定性研究。结果表明配体和金属离子的配位比为1∶1，但是，这2个系列的配合物在稳定性方面存在很大差异。     

2,5-噻吩二甲酸与菲咯啉构筑的稀土配合物:晶体结构,荧光性质和对Cu2+离子的荧光传感

稀土硝酸盐和2,5-噻吩二甲酸与菲咯啉在水热反应条件下合成了3个新的配合物,[Ln(2,5-tdc)1.5(phen)(H2O)]n(Ln=Gd(1),Tb(2),Dy(3);2,5-tdc=2,5-噻吩二甲酸根,phen=菲咯啉)。通过X射线单晶衍射确定了它们的晶体结构。配合物1~3为同构的2D网络结构。配合物1在340 nm激发下出现最大发射中心位于366和387 nm的宽峰,可归属于配体的π*-π跃迁发射。配合物2在365 nm紫外灯照射下发绿光,其荧光发射光谱中出现了4个尖峰,位于491、545、588和620 nm处,对应于Tb3+的5D4→7FJ(J=6~3)跃迁。配合物2的荧光寿命显示为单指数衰减,其值为(0.123±0.005)ms。配合物3的发射光谱中出现了2个尖峰,位于482和575 nm处,分别对应于Dy3+的4F5/2→6H15/2和4F5/2→6H13/2跃迁。另外,研究了配合物2的荧光传感能力,该配合物可作为荧光探针检测水溶液中的Cu2+离子。     

Synthesis,Charactarization and Crystal Structures of Lanthanide Phenoxyacetate Complexes with1,10—Phenanthroline

Three new lanthanide phenoxyacetate complexes with 1,10‐phenanthroline. [Nd(POA)₃ (phen)]₂ · 2C₂H₅OH (1), [Eu(POA)₃‐ (phen)]₂ · 2C₂H₅OH (2) and [Sm(POA)₂(DMSO)(phen)]₂‐ (ClO₄)₂ (3) (POA= phenoxyacetate, phen = 1,10‐phenanthroline, DMSO = dimethyl sulfoxide), were synthesized and characterized by elemental analyses, IR, UV‐vis and FAB‐MS spectra. Their structures were determined by single crystal X‐ray diffraction analysis. In complexes 1 and 2, the carboxylate groups are bonded to Ln³⁺ ion in three modes: the chelating bidentate, the bridging bidentate and the bridging tridentate. In complex 3, the carboxylate groups are bonded to Sm³⁺ ion only involved in one mode: the bridging bidentate. The luminescence behavior of complex 2 was also studied by means of emission spectra.     

1,10-菲咯啉及其衍生物铜配合物的抗癌活性研究进展

作为一种微量生命元素,铜在生物进程中扮演着重要角色,很多铜配合物呈现抑制癌细胞增殖的活性。本文论述了以1,10-菲咯啉及其衍生物为配体的铜配合物的抗癌活性研究进展,分析了其对DNA裂解的可能机理。对比顺铂类抗癌药物,展望了铜配合物作为抗癌药物的应用前景。