Complexes of Lanthanide Nitrates with Alkyl Esters of Bromomethylenediphosphonic Acid

Complexes of lanthanide nitrates (La, Ce, Sm, Gd, Er, and Yb) with tetraethyl and tetraisopropyl esters of bromomethylenediphosphonic acid were prepared. The complexes were characterized by elemental analysis, IR spectroscopy, and, in some cases, NMR. The data confirm that diphosphonates coordinate with two P[dbnd]O groups, and there are no indications for the existence of noncoordinated P[dbnd]O groups. The structure of the complexes depends only on the ionic radius of the central metal atom and not on changes in the electronic or steric behavior of the ester groups. For the complexes of La, Ce, Sm, and Gd nitrates, the formula is LnL₂(NO₃)₃, and for Er and Yb nitrates it is Ln₂L₃(NO₃)₆ (Ln[dbnd]La, Ce, Sm, Gd, Er, Yb; L = diphosphonate).     

Synthesis and Spectroscopic Characterization of Silver(I) Complexes of Selenones

Silver(I) complexes of selenones, [LAgNO₃] and [AgL₂]NO₃ (where L is imidazolidine-2-selenone or diazinane-2-selenone and their derivatives) have been prepared and characterized by elemental analysis, IR and NMR (¹H, ¹³C and ¹⁰⁷Ag) spectroscopy. An upfield shift in the C=Se resonance of selenones in ¹³C NMR and a downfield shift in N-H resonance in ¹H NMR are consistent with selenium coordination to silver(I). In ¹⁰⁷Ag NMR, the AgNO₃signal is deshielded by 450-650 ppm on coordination to selenones. Greater upfield shifts in ¹³C NMR were observed for [LAgNO₃] compared to [AgL₂]NO₃complexes, whereas the opposite trend was observed for ¹H and¹⁰⁷Ag NMR chemical shifts.     

稀土硝酸盐与Cyclam离子缔合物的合成,性质及结构

在弱酸性介质中,以硝酸稀土与Cyclam在甲醇-水溶液中反应合成了La-Tb、Y9种离子缔合物。通过元素分析和IR、~1H NMR及DTA-TG研究,推测该类化合物的通式为;L~+L_(0.7)~(2+)·[Ln(NO_3)_6]_(0.8)[Ln(NO_3)_3·3H_2O]_(0.2)·nH_2O(La,Ce:n=3;Pr-Tb,Y:n=2.5,L为Cyclam)。经单晶四圆衍射结构分析,确定了化合物的晶体结构,晶胞参数为:a=1.7000(1)nm,b=1.7000(1)nm,c=1.9862(4)nm,α=β=90°,γ=120°,R3空间群,D_c=1.703g/cm~3,μ(K_a)=132.9cm~(-1)。     

Synthesis and Characterization of Heteropolytungstosilicate Complexes with the Lanthanide Elements

Lanthanide heteropoly compounds K15[Ln(HSiW9O34)2]·28H2O(Ln = La, Ce, Nd), denoted as Ln(SiW9)2, were synthesized and characterized by element analysis, TG-DTA, IR, UV, XPS and XRD. The results show that partial oxygen in Ln(SiW9)2 was coordinated with Ln3- , where Ln-3 was in the inner side of the heteropoly anions, while the fundamental structure of SiW9 had little change. The result was supported by ion exchange experiment.     

N,N-二(2-羟乙基)氨甲基膦酸二乙酯的合成

改进了非卤反应型阻燃剂N,N-二(2-羟基乙基)氨甲基膦酸二乙酯(BHAPE)的合成方法.在35℃左右将二乙醇胺滴入37%~40%的甲醛水溶液中,加毕,于40~45℃继续保温反应2 h,然后于80~82℃,小于0.094 MPa,减压蒸馏直到没有馏分为止,得到中间体3-(2-羟基乙基)-1,3-氧氮杂环戊烷(HENH).向HENH中加入阳离子交换树脂催化剂,于55~62℃滴入亚磷酸二乙酯,加毕,于60~62℃保温反应2 h,降到室温,过滤回收催化剂,得黄色透明液体产品,收率98.5%.用元素分析、红外光谱和核磁共振谱表征了中间体和标题化合物.     

Keggin结构的磷钨钒稀土四元杂多配合物对过氧化氢分解的催化作用

在磷钨钒稀土四元杂多配合物中，由于Ｖ原子的使用，使其对Ｈ２Ｏ２分解的催化活性显著增加。因配合物中心原子稀土元素不同。催化活性也随之变化，其活化能与三阶稀土离子的电离能有密切关系。动力学曲线为Ｓ型。实验证明，在反应过程中有反应活性中间体生成。     

N－乙酸基取代四氮杂大环及其镧系配合物的热力学研究

用ｐＨ电位滴定法分别在２５±０．１℃，４０±０．１℃和８０±０．１℃，０．５ｍｏｌ／ＬＫＮＯ３水溶液中测定了Ｈ_４Ｌ（５，７，１２，１４－四甲基－１，４，８，１１－四氮杂环十四烷－Ｎ＇，ｎ＂，Ｎ＂＇，Ｎ＂＂－四乙酸）的逐级质子化常数和焓值。又在４０±０．１℃和８０±０．１℃条件下测定了Ｈ４Ｌ与镧系金属离子（Ｌａ~（３＋），Ｎｄ~（３＋），ｐｒ~（３＋），Ｓｍ~（３＋），Ｅｕ~（３＋），Ｇｄ~（３＋），Ｄｙ~（３＋），Ｙｂ~（３＋））配合物的稳定常数。结果表明：配合物稳定性高。     

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,Structure and Thermal Decomposition of Cu(II) Complexes with 2-Chloro- and 2,3-Dichlorobenzoic Acids and Imidazole

The reaction products of Cu(II) 2-chlorobenzoate and imidazole (1), and of Cu(II) 2,3-dichlorobenzoate and imidazole (2) formulated as CuL'₂·3imd and CuL"·3imd (L' = C₇H₄ClO₂, L" = C₇H₄Cl₂O₂ ^?, imd = imidazole), were prepared and characterized by means of structural and spectroscopic measurements and thermochemical properties. The blue (1) and green (2) compounds crystallize in the monoclinic system with space group C2/c, cell parameters a = 20.753(4), b = 8.414(2), c = 14.429(3) Å, β = 90.15(3)°, V = 2519.5(9) &Aringsup3;, Z = 4 for (1) and a = 21.335(4), b = 8.417(2), c = 15.030(3) Å, β = 94.11(3)°, V = 2692.1(10) &Aringsup3;, Z = 4 for (2). The complexes decompose at 483 K.     

镧系1：10系列钼钒杂多配合物的合成与性质

报道用一步酸化法制得四种未见报道的１：１０系列镧系钼钒杂多配合物Ｋ７Ｈ８ＬｎＭｏ４Ｖ６Ｐ３６．ｘＨ２Ｏ（Ｌｎ＝Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ）。提示元素分析，红外光谱，紫外光谱，Ｘ射线粉末衍射及差热－热重分析结果讨论了它们的结构及性质。     

Synthesis and Crystal Structure of Two Lanthanide Complexes with Benzenecarboxylic Derivatives

Two novel lanthanide coordination polymers, [La(tpaa)₃(H₂O)₂] ( 1 ) and [Eu₂(BDC)₃(DMF)₂(H₂O)₂] ( 2 ) (Htpaa = terephthalamic acid, H₂BDC = 1,4‐benzenedicarboxylic acid, DMF = N,N‐dimethylformamide), were hydro(solvo)thermally synthesized by reactions of the corresponding lanthanide nitrate salts with 1,3,5‐triazine‐2,4,6‐tri(4‐benzenecarboxylate) ( L ), in which a simultaneous hydrolysis of the ligand L occurred. Single‐crystal X‐ray analysis revealed that complex 1 comprises one‐dimensional chains that are further interlinked via hydrogen bonds, resulting in a two‐dimensional network; while complex 2 is a three‐dimensional interpenetrated coordination architecture.     

The Crystal and Molecular Structures of Pb(II) Complexes with Furan-2-Carboxylate and Furan-3-Carboxylate Ligands

The crystals of Pb(II) 2-furancarboxylate (title compound I) contain tetrameric structural units Pb₄(2-FCA)₈(H₂O₂) in which four Pb(II) ions are bridged by carboxylate oxygen atoms forming a circular moiety. In addition, pairs of Pb(II) ions are bridged by carboxylate oxygen atoms inside this moiety. The molecular pattern observed in Pb(II) 3-furancarboxylate (title compound II) is polymeric. It consists of Pb(3-FCA)₂(H₂O) structural units bridged by carboxylate oxygen atoms donated by the furan-3-carboxylate (3-FCA) ligands which are bidentate, using both their carboxylate oxygen atoms for chelation. The coordination around Pb(II) ions is eightfold and ninefold including, apart from carboxylate oxygen atoms, a water oxygen atom and oxygen atoms donated by the furan rings of the ligand molecules. Hydrogen bonds with the water molecule as the donor operate between adjacent ligand molecules. The stereochemical activity of the lone 6s ² electron pair on the Pb(II) is observed in title compound II.     

模板分子诱导的微孔镧系-2-羧基肉桂酸超分子配合物的合成与结构

由水热法合成了2个微孔镧系超分子配合物[Ln(CCA)(OH)(phen)(H2O)]n·n(phen)·nH2O(Ln=Yb,1;Er,2;H2CCA=2-羧基肉桂酸;phen=1,10-菲啰啉),并用元素分析、IR及X-射线单晶衍射对其进行了表征。晶体结构研究表明,2个配合物都是由配体2-羧基肉桂酸连接而形成的一维双链结构,该链状结构通过氢键和π-π堆积作用扩展为具有微孔结构的超分子。1,10-菲啰啉在微孔结构的形成过程中起到了模板剂的作用。     

Synthesis and Characterization of Binuclear Lanthanide Complexes with Macrocyclic Schiff Base Derived From 2,6-Diacetylpyridine and 1,3-Diamino-2-hydroxypropane

Nine homobinuclear lanthanide complexes with macrocyclic Schiff base were prepared by condensing 2, 6-diacetylpyridine and 1, 3-diamino-2-hydroxypropane in the presence of template lanthanide metal ions. These complexes were characterized by elemental analysis, IR, molar conductance and magnetic susceptibility. The variable-temperature magnetic susceptibility (4-300 K) of complexes of Gd( Ⅲ ) and Dy( Ⅲ ) was determined. A satisfactory fit to theoretical curve derived from spin Hamiltonian operator was obtained using least-squares method. The exchange interaction parameters are J=-0.26 cm-1, g=1.98 and △=0.06 cm-1, Z.J'=-0. 21 cm-1,g'=1.33 for Gd( Ⅲ ) and Dy( Ⅲ ), respectively. The results indicate a very week antiferromagnetic interaction between Gd( Ⅲ )-Gd( Ⅲ ) and Dy( Ⅲ )-Dy( Ⅲ ) ions.     

模板分子诱导的微孔镧系-2-羧基肉桂酸超分子配合物的合成与结构

由水热法合成了2个微孔镧系超分子配合物[Ln(CCA)(OH)(phen)(H₂O)]_n·n(phen)·nH₂O(Ln=Yb, 1;Er, 2;H₂CCA=2-羧基肉桂酸;phen=1, 10-菲啰啉), 并用元素分析、IR及X-射线单晶衍射对其进行了表征。晶体结构研究表明, 2个配合物都是由配体2-羧基肉桂酸连接而形成的一维双链结构, 该链状结构通过氢键和π-π堆积作用扩展为具有微孔结构的超分子。1, 10-菲啰啉在微孔结构的形成过程中起到了模板剂的作用。     

N-硬脂酰-L-谷氨酸及其乙酯衍生物的合成与成胶性质研究

研究了N-硬脂酰-L-谷氨酸(C18-GIu)——一个具有多个氢键位点的有机胶凝剂分子及其乙酯(C18-GIu-2ES)衍生物的合成与成胶性质．文献报道的合成方法是将硬脂酰氯滴加到L-谷氨酸钠的丙酮与水的混合溶液中,但我们的多次实验结果表明该合成方法的可操作性比较差,究其原因主要在于：反应的副产物之一盐酸的强酸性容易导致反应液的局部强酸性环境,而使反应产生的C18-GIu分子继续与L-谷氨酸反应,这大大增加了产物的后处理难度,很难得到高纯度的产物．因此,我们改用L-谷氨酸二乙酯为原料,在二环己基碳酰亚胺催化下或通过硬脂酰氯得到所需的高纯度产物．在此基础上,研究了．合成的C18-GIu及C18-GIu-2ES的成胶性质,结果表明C18-GIu-2ES具有比C18-GIu更广的成胶范围和更小的成胶浓度．     

镧系与直链醚-2,4-二羟基苯甲醛席夫碱新配合物的合成及波谱研究

Vogtle等发现,直链醚除具有类似冠醚配位各种金属离子的能力外,还弥补了冠醚的不足之处,如易合成、产率高、价廉等.我们曾报道过有关EPR工作.本文合成了2,4-二羟基苯甲醛缩二甘醇二胺(DHYDA)与镧系的新配合物.     

2, 4, 6-三甲基苯甲酸与5, 5'-二甲基-2, 2'-联吡啶构筑的系列镧系超分子配合物的晶体结构、热分解机理和性能

Six ternary lanthanide complexes formulated as [Ln(2, 4, 6-TMBA)₃(5, 5'-DM-2, 2'-bipy)]₂ (Ln = Pr 1, Nd 2, Sm 3, Eu 4, Gd 5, Dy 6; 2, 4, 6-TMBA = 2, 4, 6-trimethylbenzoate; 5, 5'-DM-2, 2'-bipy = 5, 5'-dimethyl-2, 2'-bipyridine) have been synthesized under solvothermal conditions and characterized by single-crystal X-ray diffraction, elemental analysis, thermogravimetric analysis, etc. The results of crystal diffraction analysis show that complexes 1–6 are binuclear units, crystallizing in the triclinic Pī space group. Complexes 1–5 are isostructural, and each of the central metal ions has a coordination number of 9. The asymmetric unit of complexes 1–5 consists of one Ln³⁺, one 5, 5'-DM-2, 2'-bipy ligand, and three 2, 4, 6-TMBA^- moieties with three coordination modes: chelation bidentate, bridging bidentate, and bridging tridentate. The coordination geometry of Ln³⁺ is distorted monocapped square antiprismatic. The binuclear units of complexes 1–5 form a one-dimensional (1D) supramolecular chain along the c-axis via π–π stacking interactions between the 2, 4, 6-trimethylbenzoic acid rings. The 1D chains are linked to form a supramolecular two-dimensional (2D) sheet in the bc plane via π–π stacking interactions between the pyridine rings. Although the molecular formulae of complex 6 and complexes 1–5 are similar, the coordination environment of the lanthanide ions is different in the two cases. The asymmetric unit of complex 6 contains a Dy³⁺ ion coordinated by a bidentate 5, 5'-DM-2, 2'-bipy and three 2, 4, 6-TMBA^- ligands adopting bidentate and bridging bidentate coordination modes. The Dy³⁺ metal center has a coordination number of 8, with distorted square antiprismatic molecular geometry. The binuclear molecule of 6 is assembled into a six-nuclear unit by π–π weak staking interactions between two 5, 5'-DM-2, 2'-bipy ligands; then, adjacent six-nuclear units form a 1D chain via offset π–π interactions between 5, 5'-DM-2, 2'-bipy ligands on different adjacent units. The adjacent 1D chains are linked by C―H···O hydrogen bonding interactions to form a 2D supramolecular structure. The thermal stability and thermal decomposition mechanism of all the complexes are investigated by the combination of thermogravimetry and infrared spectroscopy (TG/FTIR) techniques under a simulated air atmosphere in the temperature range of 298–973 K at a heating rate of 10 K·min^-1. Thermogravimetric studies show that this series of complexes have excellent thermal stability. During the thermal decomposition of the complex, the neutral ligand is lost first, followed by the acid ligand, and finally, the complex is decomposed into rare earth oxides. The three-dimensional infrared results are consistent with the thermogravimetric results. The photoluminescence spectra of complex 4 show the strong characteristic luminescence of Eu³⁺. The five typical emission peaks at 581, 591, 621, 651, and 701 nm correspond to the ⁵D₀ → ⁷F₀, ⁵D₀ → ⁷F₁, ⁵D₀ → ⁷F₂, ⁵D₀ → ⁷F₃, and ⁵D₀ → ⁷F₄ electronic transitions of Eu³⁺, respectively. The emission at 621 nm is due to the electric dipole transition ⁵D₀ → ⁷F₂, while that at 591 nm is assigned to the ⁵D₀ → ⁷F₁ the magnetic dipole transition. The lifetime (τ) of complex 4 is calculated as 1.15 ms based on the equation τ = (B₁τ₁² + B₂τ₂²))/(B₁τ₁ + B₂τ₂), and the intrinsic quantum yield is calculated to be 45.1%. Further, the magnetic properties of complex 6 in the temperature range of 2–300 K are studied under an applied magnetic field of 1000 Oe.     

镧系元素钨钒杂多配合物的合成与表征

报道了镧系元素钨钒杂多配合物的合成方法。元素分析和热重分析确定其通式为：Ｋ７Ｈ６「Ｌｎ（ＶＷ１０ＶＯ３９）２」．ｘＨ２Ｏ（Ｌｎ＝Ｌａ＾３＋、Ｃｅ＾３＋、Ｐｒ＾３＋、Ｎｄ＾３＋、Ｓｍ＾３＋、Ｅｕ＾３＋、Ｇｄ＾３＋、ｄＹ＾３＋、Ｙｂ＾３＋）。利用红外，喇曼，电子自旋共振，紫外和Ｘ射线衍射谱对其进行了表征。配合物的热解性质研究表明，其分解温度范围为４００－４５０℃，还研究了的氧化还原性质。     

二茂基镧系8—羟基喹啉化合物的合成及其热稳定性研究

通过三茂基镧系化合物Cp_3Ln(Cp=C_5H_5;Ln=Sm,Dy,Ho)与8-羟基喹啉反应(HL),合成了3种新的镧系金属有机化合物,通式为Cp_2LnL(Ln=Sm,Dy,Ho)。经元素分析、红外光谱、X光电子能谱、质谱及分子量测定,推断化合物具有二聚体结构,分子内存在通过喹啉氮原子和氧原子与金属配位而形成的五元螯合环。对化合物的热稳定性进行了研究和比较,发现化合物Cp_2SmL对热不稳定,在180℃以上分解为Cp_3Sm和SmL_3。