稀土(La~(3+),Eu~(3+),Tb~(3+))萘甲酸邻菲咯啉三元配合物的性质

在95%乙醇溶液中合成了3种稀土萘甲酸邻菲罗啉三元配合物,其通式为RE(Nap)3·phen(RE=La3+,Eu3+,Tb3+;Nap=萘甲酸根;phen=邻菲咯啉).并用元素分析、IR、1H NMR、XPS、XRD等分析手段对产物进行了表征,结果表明萘甲酸根以双齿方式与稀土离子配位.     

Iron(II) and Iron(III) Perchlorate Complexes of Ciprofloxacin and Norfloxacin

The reactions of ciprofloxacin (CIP) and norfloxacin (NOR) with iron(II) and iron(III) perchlorate have been investigated. The optical spectra support the formation of four complexes for each oxidation state with 1 : 1, 1 : 2, 1 : 3 and 1 : 4 metal to ligand molar ratios. The electrical conductivity and magnetic susceptibility measurements show that the isolated complexes are high spin and the Fe(ClO 4 ) 2 and Fe(ClO 4 ) 3 complexes behave as 1 : 2 and 1 : 3 electrolytes, respectively. The IR spectra indicate that CIP and NOR bind to the iron ion as bidentate ligands through the carbonyl oxygen atom and one of the oxygen atoms of the carboxylate group.     

四(对己氧苯基)卟啉稀土配合物的合成,表征和电化学性质

合成了四种乙酰丙酮-meso-四(对己氧苯基)卟啉稀土配合物,LnT(p-C6H13O)PPacac(Ln:Y,Dy,Er,Yb;Hacac:乙酰丙酮),研究了其紫外-可见光谱、红外光谱、氢核磁共振谱和荧光光谱,对各个谱带进行了归属,并用循环伏安法对其电化学性质进行了研究.     

Synthesis and spectroscopic characterization of cobalt(II) thiosemicarbazone complexes

Thiosemicarbazone derivatives are formed on reaction between acetophenone, salicylaldehyde, benzophenone and/or 2-hydroxy-4-methoxybenzophenone and thiosemicarbazide or its N⁴H substituents (ethyl-, phenyl-, and p-chlorophenyl-). The ligands were investigated by elemental analysis and spectral (IR, ¹H?NMR and MS) studies. The formulas of the prepared complexes have been suggested by elemental analyses and confirmed by mass spectra. The coordination sites of each ligand were elucidated using IR spectra revealing bidentate and tridentate coordination. Different geometries for the complexes were proposed on the basis of electronic spectra and magnetic measurements. The complexes have been analyzed thermally (TG and DTG) and the kinetic parameters for some of their degradation steps were calculated.     

稀土金属有机配合物的红外和拉曼光谱研究

利用新合成的配体N,N,N′,N′－四正丁基己二酰胺Bu2NCO(CH2)4OCNBu2(TBAA)(Bu=正丁基）与一系列稀土金属硝酸盐反应,得到了一系列配合物Ln2(TBAA)3(NO3)6(Ln=La,Nd,Sm,Eu,Gd,Tb,Dy,Tm,Lu)。研究表明,该系列配合物具有相似的红外和拉曼光谱特性,有机配体以羰基中的氧通过双龄和桥连方式与Ln^3 配位,每个Ln^3 的配位数为9。     

Synthesis and characterization of novel water-soluble zinc(II) Schiff-base complexes derived from amino acids and salicylaldehyde-5-sulfonates

New water-soluble zinc(II) Schiff-base complexes derived from amino acids (glycine, L-phenylalanine, and L-valine) and salicylaldehyde-5-sulfonates (sodium salicylaldehyde-5-sulfonate and sodium 3-methoxy-salicylaldehyde-5-sulfonate) have been synthesized. The complexes were characterized by elemental analysis, IR, electronic, ¹H?NMR, and ¹³C?NMR spectra. In the IR spectra of the complexes, the large difference between the asymmetric ν_as(COO) and symmetric ν_s(COO) carboxylate stretch, Δν(ν_as(COO)–ν_s(COO)) of 199–247?cm^?1, indicates monodentate coordination of the carboxylate group. Spectral data showed that in these complexes the ligand is a tridentate ONO moiety, coordinating to the metal through its phenolic oxygen, imine nitrogen, and carboxyl oxygen.     

1,2-邻苯二氧基二乙酸铕及掺杂L(L=La,Y,Yb,Nd)配合物的合成及荧光性质研究

在乙醇体系中,以氯化铕与1,2邻苯二氧基二乙酸和二苯甲酰甲烷反应合成了三元配合物Eu-BDDA-DBM以及弱荧光离子La3+,Y3-,Yb3-和Nd3+掺杂的铕配合物.通过红外、紫外-可见、热重、荧光光谱对配合物进行了表征.红外光谱表明,单一配合物和掺杂配合物具有相似的配位结构.荧光光谱表明,La3+和Nd3+离子掺杂可以大幅度提高的铕配合物的荧光强度,其中La3+掺杂荧光强度增强最明显.     

meso-四(烷氧基苯基)卟啉及其金属络合物的波谱研究

采用^1H NMR、MS、IR、UV、元素分析等分析测试表征手段确证了所合成的10个系列卟啉及其金属络合物的结构,研究了不同位置、不同链长烷氧基四苯基卟啉和不同金属离子卟啉络合物的结构与^1HNMR、IR和UV等波谱之间的关系,总结了卟啉配体及其金属络合物的^1H NMR、IR和UV判据,报道和解释了meso-四(烷氧基苯基)卟啉铜、锰络合物和meso-四(邻烷氧基苯基)卟啉钴络合物的^1H NMR研究结果,通过MS、^1H NMR、IR、UV、元素分析确证了我们所合成的铁卟啉为μ-氧桥联夹心二聚体结构,且存在两种典型构象,导致同系列络合物有四种类型^1H NMR谱图。     

Synthesis and spectroscopic characterization of cadmium(II) complexes of thiones and thiocyanate

Cadmium(II) complexes of thiones and thiocyanate, [(>C=S)₂Cd(SCN)₂], have been prepared and characterized by IR and NMR spectroscopy. An upfield shift in the >C=S resonance of thiones in the ¹³C NMR and downfield shift in N–H resonance in ¹H NMR are consistent with sulfur coordination to cadmium(II). The presence of ν(N–H) of thiones in IR spectra of the complexes indicates the thione forms of the ligands in the solid state; some contribution of the thiolate form was observed in one complex. The appearance of a band around 2100 cm^?1 in IR and a resonance around 132 ppm in ¹³C NMR indicates the binding of thiocyanate to cadmium(II).     

卟啉-二芳基乙烯分子及其金属配合物的合成与光致变色特性

以苯甲醛和吡咯为初始原料,经多步反应合成了5-[2,3-双(2,4,5-三甲基-3-噻吩基)马来酰亚胺-N-苯基]-10,15,20-三苯基卟啉(TPPMA)及其金属锌配合物(ZnTPPMA)与铜配合物(CuTPPMA),通过IR,MS,1H NMR和13C NMR确认了化合物的结构,并利用UV-Vis光谱探讨了化合物的光致变色性能.实验结果表明,无论在聚乙烯醇缩丁醛(PVB)膜还是在溶液中,TPPMA在254 nm紫外光照射下,没有光致变色现象,而在254和650 nm的光照下其金属配合物CuTPPMA和ZnTPPMA在溶液及PVB膜中皆可以发生可逆的光致变色反应.     

Study of fluorescence characteristics of the charge-transfer reaction of quinolone agents with bromanil

A spectrofluorimetric method was discussed for the determination of three antibacterial quinolone derivatives, ofloxacin (OFL), norfloxacin (NOR) and ciprofloxacin (CIP) through charge-transfer complexation (CTC) with 2,3,5,6-tetrabromo-1,4-benzoquinone (bromanil, TBBQ). The method was based on the reaction of these drugs as n-electron donors with the pi-acceptor TBBQ. TBBQ was found to react with these drugs to produce a kind of yellow complexes and the fluorescence intensities of the complexes were enhanced by 29-36 times more than those of the corresponding monomers. UV-vis, (1)H NMR and XPS techniques were used to study the complexes formed. The various experimental parameters affecting the fluorescence intensity were studied and optimized. Under optimal reaction conditions, the rectilinear calibration graphs were obtained in the concentration range of 0.021-2.42 microg mL(-1), 0.017-2.63 microg mL(-1) and 0.019-2.14 microg mL(-1) for OFL, NOR and CIP, respectively. The methods developed were applied successfully to the determination of the subject drugs in their pharmaceutical dosage forms with good precision and accuracy compared to official and reported methods as revealed by t- and F-tests.     

Synthesis,characterization, semi-empirical study,and biological activities of organotin(IV) complexes with cyclohexylcarbamodithioic acid as biological active ligand

Cyclohexylcarbamodithioic acid has been synthesized by the reaction of cyclohexylamine with carbon disulfide at room temperature. Its complexes have been synthesized by the reaction of cyclohexylcarbamodithioic acid with organotin(IV) chlorides in 1?:?1/1?:?2 molar ratio. The ligand and complexes have been characterized by elemental analysis, infrared (IR), and multinuclear (¹H, ¹³C, and ¹¹⁹Sn) NMR spectroscopy. Elemental data show good agreement between calculated and found values of carbon, hydrogen, nitrogen, and sulfur. IR data show that the ligand is bidentate and complexes exhibit a five-coordinate geometry in the solid state, which is also confirmed by semi-empirical studies. NMR data show that the complexes exhibit tetrahedral geometry in solution state. The ligand and its complexes were screened for their in vitro mutagenic, antimicrobial, MIC, antioxidant activities, and cytotoxicity. Biological screening data demonstrate that complexes show significant activity against various bacterial and fungal strains and are good antioxidants. The cytotoxicity data show positive lethality for complexes as compared to ligand and can play a very significant role in drug development.     

Spectroscopic studies of complex compounds derived from the tribochemistry reactions of KBr and HgX2(Cl, Br, I, CN) with crown ethers (DC18C6 and DB18C6)

Several new K and Hg(II) complexes derived from crown ethers (DC18C6, DB18C6) have been prepared by tribochemistry reactions. The isolated solid complexes have been characterized by I.R. spectral measurements. The isolated solid complexes are compared with the corresponding metal complexes prepared in solution. Also, the IR and NMR spectra of the solid complexes have been used to determine the strength of bond between Hg(II) ion and the crown ether.     

Synthesis,characterization and in vitro cytotoxicity of platinum(II) complexes of selenones [Pt(selenone)2Cl2]

Platinum(II) complexes with various selenones (L) having the general formula [PtL₂Cl₂] were prepared and characterized by elemental analysis and, IR and NMR (¹H, ¹³C, and ⁷⁷Se) spectroscopies. A decrease in the IR frequency of the >C=Se mode and an upfield shift in ¹³C NMR for the >C=Se resonance of selenones are consistent with their selenium coordination to platinum(II). The NMR data show that the complexes are stable in solution and do not undergo equilibration at 297 K. The geometrical structures of the complexes were predicted theoretically (with DFT method) using Gaussian09 program. DFT calculations predicted that the trans configurations were up to 1.7 kcal/mol more stable than the cis forms in gas phase, while in solution form the cis isomers were predicted to be more stable. The UV–vis spectra of the two complexes, 6 and 7 were also recorded at room temperature for 24 h and it was observed that the complexes were stable and did not undergo decomposition. The in vitro antitumor properties of the complexes as well as of cisplatin were evaluated on two human cancer cell lines, HeLa (cervical cancer cells) and MCF7 (breast cancer cells) using MTT assay. The results indicated that the prepared complexes exerted significant inhibition on the selected cancer cells.     

氨噻肟酸稀土配合物的合成、抗氧化性及抗菌活性的研究

合成了１２种稀土氨噻肟酸（ＨＬ）固体配合物,其通式为ＲＥＬ３（ＲＥ＝Ｌａ,Ｃａ,Ｐｒ,Ｎｄ,Ｓｍ,Ｅｕ,Ｇｄ,Ｔｂ,Ｅｒ、Ｔｍ,Ｙｂ,Ｙ）。利用元素分析、红外光谱、核磁共振氢谱、摩尔电导、热分析等测试手段对配合物进行了表征,研究了ＮｄＬ３、ＥｒＬ３配合物在ＤＭＳＯ溶液中电子吸收光谱,计算了电子云伸效应参数β,共价参数　和键合参数ｂ＾１／２,讨论了配合物的共价成键情况,并对其抗氧化及抗菌活性做了研究     

五配位锡(Ⅳ)有机化合物的合成与表征(Ⅲ)──含Fe-Sn-Fe三核金属有机配合物

5种氨基酸的Schiff碱及2种半卡巴腙分别与双-(茂基二羰基铁)二氯化锡反应制得7种新的含有Fe-Sn-Fe三核金属有机配合物,中心锡原子为五配位.合成反应产率较好,产品纯度也高.该类配合物的母体为双环氮杂锡氧烷.产物结构均经红外、核磁、质谱及元素分析确证.研究发现,氨基酸中α-碳上的取代基对铁上的茂环有影响.     

Synthesis of Cyclic Carbonates Catalysed by Aluminium Heteroscorpionate Complexes

New aluminium scorpionate based complexes have been prepared and used for the synthesis of cyclic carbonates from epoxides and carbon dioxide. Bimetallic aluminium(heteroscorpionate) complexes 9 – 14 were synthesised in very high yields. The single‐crystal X‐ray structures of 12 and 13 confirm an asymmetric κ²‐NO‐μ‐O arrangement in a dinuclear molecular disposition. These bimetallic aluminium complexes were investigated as catalysts for the synthesis of cyclic carbonates from epoxides and carbon dioxide in the presence of ammonium salts. Under the optimal reaction conditions, complex 9 in combination with tetrabutylammonium bromide acts as a very efficient catalyst system for the conversion of both monosubstituted and internal epoxides into the corresponding cyclic carbonates showing broad substrate scope. Complex 9 and tetrabutylammonium bromide is the second most efficient aluminium‐based catalyst system for the reaction of internal epoxides with carbon dioxide. A kinetic study has been carried out and showed that the reactions were first order in complex 9 and tetrabutylammonium bromide concentrations. Based on the kinetic study, a catalytic cycle is proposed.     

New cerium(III) and neodymium(III) complexes as cytotoxic agents

The cerium(III) and neodymium(III) complexes of 5‐aminoorotic acid were synthesized and characterized by means of spectral data (IR, Raman, ¹H NMR and ¹³C NMR) and elemental analysis. Significant differences in the IR spectra of the complexes were observed as compared with the spectrum of the ligand. A comparative analysis of the Raman spectra of the complexes with that of the free 5‐aminoorotic acid allowed a straightforward assignment of the vibrations of the ligand groups involved in coordination. ¹H NMR and ¹³C NMR spectra confirmed the formation of the complexes. The ligand and the complexes were tested for the cytotoxic activities on the chronic myeloid leukemia‐derived K‐562, overexpressing the BCR‐ABL fusion protein, and the non‐Hodgkin lymphoma‐derived DOHH‐2, characterized by a rexpression of the antiapoptotic protein bcl‐2 cell lines. The results obtained indicate that the tested compounds exerted a considerable cytotoxic activity upon the evaluated cell lines in a concentration‐dependent manner, which enabled the construction of dose–response curves and the calculation of the corresponding IC₅₀ values. Cytotoxicity towards tumor cells was determined for a broad concentration range. The inorganic salts exerted a very weak cytotoxic effect on these cells that is in contrast to the lanthanide complexes, which exhibited potent cytotoxic activity towards K‐562 and DOHH‐2 cell lines. Copyright © 2006 John Wiley & Sons, Ltd.     

Synthesis and characterisation of Cu(II), Ni(II), Mn(II), Zn(II) and VO(II) Schiff base complexes derived from o -phenylenediamine and acetoacetanilide

Neutral tetradentate N₂O₂ type complexes of Cu(II), Ni(II), Mn(II), Zn(II) and VO(II) have been synthesised using a Schiff base formed by the condensation of o-phenylenediamine with acetoacetanilide in alcohol medium. All the complexes were characterised on the basis of their microanalytical data, molar conductance, magnetic susceptibility, IR, UV-Vis¹H NMR and ESR spectra. IR and UV-Vis spectral data suggest that all the complexes are square-planar except the Mn(II) and VO(II) chelates, which are of octahedral and square pyramidal geometry respectively. The monomeric and neutral nature of the complexes was confirmed by their magnetic susceptibility data and low conductance values. The ESR spectra of copper and vanadyl complexes in DMSO solution at 300 K and 77 K were recorded and their salient features are reported.     

Paramagnetic NMR shift,spectroscopic and molecular modeling studies of lanthanide(III)-morin complexes

Studies on nine-coordinate lanthanide complexes of morin are described. The complexes were characterized by elemental analysis, molar conductance, UV–Vis spectra, IR spectra, thermal analysis and NMR spectra. Molecular modeling studies were also carried out. The complexes are non-electrolytes in DMSO. TGA showed anhydrous nature of the complexes. The electronic spectra of the complexes were recorded in methanol. ¹H NMR spectra of lanthanum, praseodymium, neodymium, samarium and dysprosium complexes have been studied in DMSO-d₆. The complexes do not dissociate in DMSO and retain their coordination. ¹H NMR spectra of paramagnetic and diamagnetic complexes exhibit downfield as well as upfield shifts of morin resonances that shows change in geometry during coordination.