直链醚型Schiff碱与钴(Ⅱ)、镍(Ⅱ)配合物的合成、表征及其活性的研究

合成了双水杨醛缩二甘醇二胺(SALDA)及双水杨醛缩四甘醇二胺(SALTTA)两类直链醚型Schiff碱,并用于合成钴、镍的四种Schiff碱配合物,经分析,其组成为[M(SALDA)](NO₃)₂·H₂O和[M(SALTTA)](NO₃)₂·nH₂O,并以热重-差热分析、紫外、红外光谱以及核磁共振谱等方法研究了它们的配位作用.此类配合物能有效清除超氧阴离子自由基,具有明显的生物活性,并对甲基丙烯酸甲酯(MMA)聚合有催化效果,转化率~70%,分子量峰值可达100万.     

Ln(Ⅲ)-Ni(Ⅱ)与双水杨醛缩乙二胺席夫碱异核配合物的合成与波谱

合成了双水杨醛缩乙二胺席夫碱(SALEN)与镍的配合物Ni₃(SALEN)₂(NO₃)₆·H₂O及镧系镍的异核配合物Ln₂Ni₃(SALEN)₆(NO₃)₁₂·H₂O(Ln=La,Nd,Sm,Gd,Yb,Y).以紫外、红外光谱、磁化率,特别是¹H NMR及EPR波谱等方法研究了它们在组成、结构和配位等方面的异同.Gd-Ni-SALEN配合物的EPR谱表明其在低温THF中呈"单峰效应".文中讨论了配合物在不同溶剂中峰宽的相对关系、配合物晶体场强度及Gd³⁺周围局部对称性问题.     

SYNTHESIS AND CATALYTIC ACTIVITY OF NONCYCLIC POLYETHER SCHIFF BASE COMPLEXES OF COBALT(

合成了双水杨醛缩二甘醇二胺(SALDA)及双水杨醛缩四甘醇二胺(SALTTA)两类直链醚型Schiff碱,并用于合成钴、镍的四种Schiff碱配合物,经分析,其组成为(NO     

[Co(H2O)4(NCS)2](18-C-6)配合物的NMR研究

该文测定了最近合成的[Co(H₂O)₄(NCS)₂](18-C-6)的¹H、¹³C、¹⁴N核磁共振谱,验证了其配合物的结构,并用红外光谱(IR)作了进一步的确定.     

DTPA双酯Gd (Ⅲ)配合物的合成及其弛豫率

二乙三胺五乙酸双酐与甘醇单醚反应,得到含多氨基多羧基双酯配体,配体与GdCl₃·6H₂O反应生成非离子配合物.配体及配合物用IR、¹H NMR和元素分析进行了表征,并测试了配合物的驰豫率,其中3种配合物的弛豫率比已用于临床诊断的Gd (DTPA)强,     

邻啡啰啉─吡啶2,6二甲酸铕二、三元配合物的NMR研究

报道了稀上铕(Eu³⁺)与吡啶-2,6-二甲酸(H₂DPC)及邻啡啉(Phen)形成的二元和三元固体配合物的制备.对它们进行了元素分析,确定该配合物的组成为二元Na₃[Eu(DPC)₃]·2H₂O和三元NaEu(DPC)₂·4H₂O,对上述配合物的结构作了核磁共振氢谱(¹H NMR)、碳谱(¹³CNMR)和氮谱(¹⁴N NMR)及红外光谱(IR)的研究.吡啶-2,6-二甲酸中的羧基以单齿配位(整个分子为三齿配位),二、三元配合物中铕的配位数分别为9和8.     

Spectroscopic Characterizations of Metal-Complexes of 4-Hydroxybenzoic Acid With the Ni(Ⅱ), Mn(Ⅱ), and Cu(Ⅱ) Ions

One of the phenolic acids is 4-hydroxybenzoic acid (HBA) which takes the form of a white crystalline solid with a molecular formula of C₇H₆O₃, a melting point of 214.5 ℃ and a molecular weight of 138.12 g·mol-1. It soluble in polar organic solvents like acetone and alcohols, and slightly soluble in chloroform and water. The reactions between the metal ions and the HBA were carried out under specific conditions like (molar reaction was 2∶2 (ligand to metal), reaction temperature was 60 ℃, media was neutral (pH 7), and solvent was H₂O ∶MeOH (1∶1). Under these conditions, the HBA was deprotonated to form (HOC₆H₄CO-₂; L-). The ligand L- was coordinated to the metal ions forming the metal complexation. The reaction of 4-hydroxybenzoic acid (HOC₆H₄CO₂H; HL) with the Ni(Ⅱ), Mn(Ⅱ) and Cu(Ⅱ) ions afford metal-complexes with gross formula of [Ni₂L₂(NO₃)₂(H₂O)₄], [Mn₂L₂(NO₃)₂(H₂O)₄] and [Cu₂L₂(NO₃)₂(H₂O)₄], respectively. These complexes were characterized by elemental analysis (CHN), magnetic susceptibility, UV-Vis spectra, infrared (IR), and X-ray powder diffraction (XRD) techniques. The complexes of HBA are insoluble in common solvents and hence molar conductance could not be measured, but this very insolubility indicates that the complexes are neutral. Data has demonstrated that the ligand (L-) was coordinated to the metal ion by bidentate bridging carboxylate group (COO-), with an octahedral geometry. Thus, HBA is expected to act as bidentate uninegative ions and the coordination number of the metal ions is six. XRD results showed that the complexes possess uniform and organized microstructures in the nanometer range with a main diameter in the range of 11～28 nm.     

用多核固体核磁共振研究CsH2PO4 和CsH5(PO4)2的制备

探讨可能用作燃料电池固体酸电解质的化合物CsH₂PO₄ (CDP)和CsH₅(PO₄)₂(CPDP)的制备. CDP和CPDP混合物由摩尔比1∶4的Cs₂CO₃∶H₃PO₄水溶液结晶而成,而CDP和Cs₂HPO₄·1.5H₂O (H-DCHP)混合物依其摩尔比1∶2的水溶液制备. 甲醇清洗能最有效地将CDP从其混合物中分离出来. CDP、CPDP以及H-DCHP的¹³³Cs 和³¹P 魔角旋转谱以及CPDP和H-DCHP的¹H魔角旋转谱均为首次报道,对各化合物的谱峰做了指认. 说明,透过确认合成的电解质以及合成过程所产生的副产物,多核固体核磁共振对于控制固体酸电解质合成的品质是一个非常有用的工具.     

[1ChCl∶2EG]/CrCl3·6H2O离子液体中Cr(Ⅲ)配合物的研究

利用电喷雾质谱(ESI-MS)和紫外-可见吸收光谱(UV-Vis)分析,研究了CrCl₃·6H₂O 浓度为0.1～0.6 mol·L-1的水溶液和[1ChCl∶2EG]/CrCl₃·6H₂O ILs中,Cr(Ⅲ)配合物的存在形式。研究结果表明,在含有CrCl₃·6H₂O的溶液中,Cr(Ⅲ)与Cl-和H₂O形成[Cr(H₂O)_nCl_6-n]n-3配合物,其配合物的优势物种受CrCl₃·6H₂O浓度的影响。水溶液中Cr(Ⅲ) 的优势配合物为[Cr(H₂O)₆]3+与[Cr(H₂O)₅Cl]2+,并随CrCl₃·6H₂O浓度增加,水溶液的UV-Vis吸收光谱峰红移,[Cr(H₂O)₅Cl]2+的相对含量增加。而[1ChCl∶2EG]/CrCl₃·6H₂O ILs中的优势配合物为[Cr(H₂O)₂Cl₄]-和[Cr(H₂O)₃Cl₃],且随CrCl₃·6H₂O 浓度增加,溶液的颜色从浅橙红色逐渐变为深绿色,溶液的UV-Vis吸收光谱峰蓝移,[Cr(H₂O)₃Cl₃]的相对量增加。说明CrCl₃·6H₂O的浓度变化,将影响配体Cl-和H₂O与Cr(Ⅲ)配位结合的配位数,从而影响配合物优势物种的相对量。     

1-(2-羧基苯基甲酰基)氨基硫脲及其Cu+配合物的NMR研究

利用¹H-¹H COSY,¹H-¹³C HMQC,HMBC等2D NMR技术对一种新的配体1-(2-羧基苯基甲酰基)氨基硫脲(H₃L)进行¹H、¹³C NMR谱数据分析与归属,对于它与Cu⁺离子配位的化合物[Cu₂(H₃L)₂Cl₂](H₂O)₃也作了¹H、¹³C NMR的测定,简单讨论了它的配位行为,粗略确定了它的结构.     

两种以Znq2为基体的新型电致发光材料的合成与性能

以8-羟基喹啉为配体的金属配合物是一种性能优良的有机电致发光材料,其中有关8-羟基喹啉铝(Alq₃)研究已有大量报道,8-羟基喹啉锌(Znq₂)研究还有待发展。介绍了两种以Znq₂为基体的新型有机电致发光材料Znq₂(H₂O)₂和(Znq₂)₄的合成方法。用IR、XRD、TG、DTA和荧光测试方法进行表征与分析表明:Znq₂(H₂O)₂和(Znq₂)₄的玻璃化温度(T_g)分别为104.2℃和204.9℃;在161℃下Znq₂(H₂O)₂脱去水分子成为Znq₂,在361℃高温下四聚体(Znq₂)₄裂解为单体Znq₂;Znq₂(H₂O)₂和(Znq₂)₄具有很好的发光性能,在光致发光谱中λ_max分别是505,550nm。     

基于二缺位钨多酸化合物的二维相关红外光谱研究

通过水热法合成了一例新颖的稀土钨多酸化合物H₂₆(C₂H₈N₂H₂)K(H₂O)[K(H₂O)Nd₈(H₂O)₂(W₃O₁₂)(SiW₁₀O₃₈)₄]·18H₂O 1。该化合物的不对称单元由两个[SiW₁₀O₃₈]^12-通过一个{Nd₄(H₂O)¹²⁺}结构单元和W₃O₁₂连接而成。化合物1簇阴离子通过K离子连接成一维无限链,再通过氢键连接成二维平面结构。针对该化合物,做了一系列表征,测试了其二维相关红外光谱,并对其作了详细分析,结果说明化合物1簇阴离子振动偶极矩对磁...     

二正丁基锡(IV)基羧酸酯的谱学表征

合成了10个二正丁基锡(IV)基羧酸酯化合物{[ⁿBu₂Sn (O₂CR)]₂O}₂(A1~A5)和ⁿBu₂Sn (O₂CR)₂(B1~B5)(R=1:CCl₃;2:CHCl₂;3:CH₂Cl;4:PhCH=CH;5:2,2,3,3-四甲基环丙基),其中A4、A5和B5为新化合物,对它们进行了元素分析和IR及、¹H、¹³C、¹¹⁹Sn NMR谱表征,重点讨论了¹³C和¹¹⁹Sn NMR谱的谱学特征及化学位移值与母体酸的PKa值大小的关系,并在此基础上推测了它们分子结构。     

Synthesis,Structural,Spectroscopic Characterization and Biological Properties of the Zn(Ⅱ),Cu(Ⅱ),Ni(Ⅱ),Co(Ⅱ),and Mn(Ⅱ) Complexes With the Widely Used Herbicide 2,4-Dichlorophenoxyacetic Acid

2,4-Dichlorophenoxyacetic acid (2,4-D) is a board-leaf selective herbicide and globally used in agricultural activities. Complexation mode, spectroscopic investigations and biological properties of complexes formed between 2,4-D (C₆H₃Cl₂OCH₂·COOH; HL) with Zn(Ⅱ), Cu(Ⅱ), Ni(Ⅱ), Co(Ⅱ), and Mn(Ⅱ) metal ions were investigated. To characterize the binding mode between 2,4-D and the metal ions, many physicochemical approaches were employed. The complexes obtained are characterized quantitatively and qualitatively by using micro elemental analysis, FTIR spectroscopy, UV-Vis spectroscopy, 1H-NMR, and magnetic susceptibility measurements. Results of these approaches suggested that the gross formula of the complexes obtained with the metal ions were [ZnL₂](2H₂O (1), [CuL₂(H₂O)₂] (2), [NiL₂](3H₂O (3), [CoL₂(H₂O)₂] (4), and [MnL₂(H₂O)₂] (5). In all complexes, two L- anion were coordinated the metal ion by their bidentate carboxylate groups. From the spectral study, all the complexes obtained as monomeric structure and the metals center moieties are six-coordinated with octahedral geometry except Ni(Ⅱ) and Zn(Ⅱ) complexes which existed as a tetrahedral and square pyramidal geometry respectively. The complexes were screened in vitro against several microbes (fungi and bacteria) using Kirby-Bauer disc diffusion method, and data has demonstrated that complex 3 showed excellent antifungal activity.     

磷掺杂硼钒氧簇化合物的二维相关红外光谱研究

一个新颖的磷掺杂硼钒氧簇化合物[Li(H₂O)₂]₂[Cu(en)₂]₃[H₂en]₂[V₁₂P₁₂B₆O₆₈(OH)₄(H₂O)]·3(H₂O)1通过水热法合成,通过Li⁺连接成一维无限结构,再通过氢键连成三维立体结构。针对该化合物,通过二维红外相关光谱并作了详细分析,化合物1簇阴离子振动偶极矩对磁场和温度的变化均有响应峰,2D-IR COS提供了一种结构表征新方法。     

水杨醛甘氨酸席夫碱-含氮杂环稀土配合物的合成及其与DNA作用的光谱研究

合成了以水杨醛甘氨酸席夫碱（Sal-GlyK）、邻菲罗啉（Phen）和2,2’-联吡啶（Bipy）为配体、Eu³⁺、La³⁺为中心的配合物。对其进行了元素分析和摩尔电导、红外光谱及紫外吸收光谱测定,推测配合物的组成分别为RE（Sal-Gly）（NO₃）·2H₂O和RE（Sal-Gly）（Phen）（NO₃）·H₂O、RE（Sal-Gly）（Bipy）（NO₃）·H₂O（RE³⁺=Eu³⁺,La³⁺）。通过紫外吸收光谱及荧光光谱研究了稀土配合物与小牛胸腺DNA的作用方式及其结合常数。结果表明,本文合成的配合物与DNA的结合能力的顺序为RE（Sal-Gly）（Phen）（NO₃）·H₂O>RE（Sal-Gly）（Bipy）（NO₃）·H₂O >RE（Sal-Gly）（NO₃）·2H₂O,表明配合物是以插入方式与DNA结合,含有良好平面性和较大表面积配体的配合物可以更好地插入到DNA的碱基对中。     

Spectroscopic and Fluorescence Studies on the Trivalent Ce,Eu,Nd and La Metal Ions Rhodamine C Florescent Dye Complexes

The four isolates solid complexes: [La(RHC)(NO₃)₂]·3H₂O, [Nd(RHC)(NO₃)₂]·4H₂O, [Eu(RHC)(NO₃)₂]·2H₂O, and [Ce(RHC)(NO₃)₂]·5H₂O that obtained by the reaction of the nitrate salts of the Ce(Ⅲ), Eu(Ⅲ), Nd(Ⅲ) and La(Ⅲ) ions and rhodamie C (RHC) ligand were interpretative using elemental analysis (C, H and N), molar conductivity, infrared, electronic, fluorescence and 1H-NMR spectra to achieve the speculated suitable formula. The low molar conductance values of the synthesized RHC complexes concluded the non-electrolytic behavior. The infrared spectra recorded the absence of stretching vibration ν(OH) of the -COOH and presence of two new vibration bands at 1 597～1 601 and 1 383～1 399 cm-1 which were assigned to ν_as(COO-) and ν_s(COO-). The difference between them revealed that the carboxylate group acts as a bidentate ligand. 1HNMR spectra of Europium and lanthanum(Ⅲ) complexes were supported the FTIR results based on the absent of proton of the carboxylic group. Therefore, the microanalytical and spectroscopic results deduced that RHC acts as a monobasic bidentate ligand, and coordinated to the central metal(Ⅲ) ions via the two oxygen atoms of deprotonated carboxylic group. Fluorescence studies were performed on the metal complexes of Ce3+, Tb3+, Th4+, Gd3+ and La3+, that referred a quenching in the fluorescene intensity of rhodamine C in the aqueous state after complexation. The antimicrobial assessment against some kind of bacteria and fungi were also checked and recorded enhancement in case of their complexes.     

硝酸铕二甲亚砜配合物的光谱与磁性

本文合成了硝酸铕二甲亚砜配合物Eu(NO₃)₃·4(CH₃)₂SO的晶体,测定了它的组成、结构、荧光光谱和摩尔磁化率.从光谱求得Eu³⁺在此晶体中的能级.根据所得的能级数据,计算了此晶体的摩尔磁化率的倒数,与实验值基本相符.     

化合物(Et4N)2[Pd2(mp)2(μ-mpH)2]的NMR研究

采用¹H-¹H COSY,HMQC、HMBC等2D NMR技术对化合物(Et₄N)₂[Pd₂(mp)₂(μ-mpH)₂]进行¹H、¹³C NMR谱数据分析与归属,表明它在DMSO溶液中仍保持原有固体状态的分子结构.     

一个镍(Ⅱ)配合物的合成、晶体结构及其与鲱鱼精DNA/BSA作用的光谱学研究

合成了配合物[Ni(2,2′-biby)(H₂O)₄]·(Htba)₂·5H₂O单晶,分子式中2,2′-biby为2,2′-联吡啶,H₂tba为2-硫代巴比妥酸。通过红外光谱、元素分析和单晶X-射线衍射表征其结构,单晶X-射线衍射结果表明,该配合物单晶属于正交晶系,Pbca 空间群,晶胞参数为a=13.662(2) Å,b=19.470(4)Å,c=21.590(4) Å。应用紫外光谱和荧光光谱研究了其与鲱鱼精DNA/牛血清白蛋白(BSA)的相互作用,研究结果表明,标题化合物与DNA为静电结合,对牛血清白蛋白发生静态猝灭作用。