二氯合铜(Ⅰ)酸四(三苯基氧膦)二氯合希土(Ⅲ)配合物的合成和红外光谱研究

合成了通式为[(Ph_3P=O)_4LnCl_2][CuCl_2](Ln=La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、He、Er、Y)的新配合物共12个,测定了它们的红外光谱(100～4600m~(-1))和部分配合物的~(31)P NMR.比较了[(Ph_3P=O)_4LnCl_3]、[(Ph_3P=O)_4LnCl_2]~+和[(Ph_3P=O)_5LnCl]~(2+)的P=O伸缩振动频率.结果表明希土配合物的正电荷越高,P=O基对希土离子配合能力越强,P=O伸缩振动频率更多地移向低波数,ν_(P=O)的顺序为:[(Ph_3P=O)_4LnCl_3]>[(Ph_3P=O)_4LnCl_2]~+≥[(Ph_3P=O)_5LnCl]~(2+).讨论了希土配位键的共价性。     

稀土噻吩甲酰三氟丙酮喹啉螯合物的振动光谱

本文测定了系列稀土螯合物(TTA)_4LnQH的振动光谱, 讨论了螯合物的结构, 低波数谱带和Ln-O振动。     

季铵盐萃取稀土分配比的变化趋势及其萃合物的远红外光谱研究

本文研究了以仲辛醇为添加剂,煤油为稀释剂的硝酸甲基三烷基铵和硫氰酸甲基三烷基铵萃取稀土的分配比随镧系元素原子序数的变化趋势及其萃合物的远红外光谱。在硝酸体系中萃合物(R_3CH_3N)_3[Ln(NO_3)_6]的Ln-O键的振动频率:从La到Nd为191～192cm~(-1),近于常数;由Nd到Sm突然上升到221cm~(-1);而由Sm到Lu又趋于常数。在硫氰酸体系中萃合物(R_3~((?))CH_3N)_3[Ln(CNS)_6]的Ln-N键的振动频率:从La到Er为189～201cm~(-1),变化缓慢;由Er到Tm突然上升到220cm~(-1);从Tm到Lu又变化缓慢。在硝酸体系中Y-O键和硫氰酸体系中Y-N键的振动频率均高于镧系元素。硫氰酸体系中Ln-N键的振动峰积分强度及吸收度均比硝酸体系中对应元素的Ln-O键的大。     

希土离子单硫代二苯甲酰甲烷配合物的合成及性质研究

本文合成了单硫代二苯甲酰甲烷(HTDBM)和三价希土离子及路易斯碱(Q)的Ln(TDBM)_4QH型配合物(Ln=除Ce外的La～Lu,Q=二乙基胺)。测定了它们的摩尔电导值、红外光谱,可见—紫外光谱,核磁共振谱.观察到配合物是通过硫原子、氧原子同时与Ln~(3+)离子配位.Ln-O键强于Ln-S键。在Nd~(3+)、Pr~(3+)、Ho~(3+)、Er~(3+)离子的该类配合物的可见吸收光谱中发现超灵敏跃迁现象。讨论了题述配合物作为核磁共振化学位移试剂的可能性.     

稀土HEH[EHP]固体配合物的红外光谱

本文制备了La,Ce,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb,Lu,Y等十五种稀土与2-乙基己基膦酸单(2-乙基己基)酯的固体配合物,测定了4000-100cm~(-1)的FT-IR光谱,对其主要红外光谱吸收带进行了归属。指认150cm~(-1)为Ln-O键的伸缩振动带,250cm~(-1)附近的谱带为COPO,CCPO骨架扭曲振动与Ln-O键的耦合振动带。结果表明配合物为多聚体系,PO_2与稀土离子可能为桥式配位形式。Ln-O键基本上为离子键。     

几种分子间氢键络合物体系的振动光谱研究

本文对X·C_2H_2[X=(CH_3)_3N、NH_3、(CH_3)_2O和CH_3(N)及(NH_3)_2·C_2H_2]五种分子间氢键络合物体系进行了振动光谱研究。用MNDO方法对这五种体系进行了几何构型优化,获得了直角坐标力常数;通过力常数变换将其转换成内坐标表达的力常数,用GF矩阵方法作全振动分析,计算了上述体系的振动光谱频率,并对频率作了理论归属,从而得到了分子间氢键的伸缩振动力常数和振动频率。     

阴离子对水的羟基伸缩振动拉曼光谱的影响

通过比较纯水、NaX(X=F, Cl, Br, I)、Na2S、NaOH、NaNO3、Na2CO3、Na2SO4溶液的羟基伸缩振动拉曼光谱, 发现所研究的阴离子对水的结构都有破坏作用. 通过比较阴离子对水的羟基伸缩振动拉曼光谱的影响, 可将所研究的阴离子分为两类, 一类阴离子有F−、OH−、S2−、CO32−, 另一类阴离子有Cl−、Br−、I−、NO3−和SO42−. 它们的主要区别在于对羟基伸缩振动拉曼光谱3600 cm−1、2900−3100 cm−1处影响不同, 产生这些区别的原因在于阴离子与水分子之间氢键的强弱. 阴离子对水的羟基伸缩振动拉曼光谱的影响因素有离子半径、离子电荷和离子结构, 它们的影响程度为离子结构>离子电荷>离子半径.     

磷酸二乙酯稀土配合物的合成与红外光谱研究

用稀土氯化物与磷酸三乙酯制备了一系列标题配合物Ln(DEP),(La=La、Sm、Eu、Ho,Yb),研究了其热分解机理。其最终产物为稀土偏磷酸盐。测定了配合物的红外光谱,对其主要吸收谱带进行了归属。红外光谱表明标题配合物与Sm(DMP)_3等磷酸二甲酯稀土配合物具有相同的配位形式和结构类型。Ln-O键基本上是离子键。     

磷酸可待因的振动光谱研究

运用密度泛函理论(DFT)计算了磷酸可待因的拉曼和红外光谱.采用B3LYP混合泛函和6-31G基函数组,同时在实验上测量了磷酸可待因的常规拉曼光谱(NRS)和红外吸收光谱(IRS),结果表明:在振动频率上理论结果与实验结果相当一致,根据理论计算的结果对磷酸可待因的振动光谱进行分析,通过理论与实验数据的比较,对磷酸可待因的所有振动谱带进行了全面地归属.     

希土D—葡萄糖酸配合物的红外和拉曼光谱及结构的研究

十五种希土D-葡萄糖酸配合物的红外和拉曼光谱非常相似,结构类同,配合物的糖酸谱带明显展宽,羧酸根的对称和反对称振动谱带相差200cm~(-1),与希土离子单齿配位,糖酸为β构型,吡喃环上的O_1和O_5也参予配位,希土离子配位数是9。     

铜(Ⅱ)离子与神经红蛋白的相互作用

利用紫外可见吸收光谱、荧光光谱、同步荧光光谱及圆二色(CD)光谱研究了铜髤离子与神经红蛋白(NGB)的相互作用。结果表明,Cu2+离子使NGB在280nm处的紫外吸收增强,说明Cu2+与NGB发生了相互作用;Cu2+使NGB内源性荧光发生猝灭,其猝灭机制为静态猝灭;同步荧光光谱表明,Cu2+使色氨酸微环境的疏水性有所降低,Cu2+对NGB的作用位点更接近于色氨酸;CD光谱显示Cu2+没有引起NGB二级结构明显的变化。     

碳笼氧化物的结构和谱学性质

碳笼氧化物对碳笼的官能团化研究具有重要意义,因而激起了人们广泛的研究兴趣。本文对碳笼氧化物C₆₀O_n、C₇₀O_n、C₇₆O_n、C₇₈O_n及C₈₀O_n的结构、电子光谱、红外光谱及核磁共振谱的研究进展进行综合评述。介绍了国内外近十几年来众多研究小组的工作,并结合作者本人在此方面的理论研究成果,进一步探索碳笼氧化物的结构特点以及光谱性质的规律性。在对C₆₀及C₇₀氧化物研究结果与实验符合的基础上,预测高碳笼氧化物的结构和光谱。     

Synthesis and structural studies of complexes of Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) with substituted chalcones

Complexes of Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) with 3-(2-pyridyl)-1-(2-hydroxy phenyl)-2-propen-1-one (PHPO), 3-(1-naphthyl)-1-(2-hydroxy phenyl)-2-propen-1-one (NHPO) and 3-(3,4-dimethoxy phenyl)-1-(2-hydroxy phenyl)-2-propen-1-one (DMPHPO) have been synthesized and characterized by analytical, conductivity, thermal, magnetic, infrared, electronic and electron spin resonance data. Based on analytical data the stoichiometry of the complexes has been found to be 1 : 2. The conductivity data show that all these complexes are non-electrolytes. The infrared spectral data indicate that the ligand PHPO acts as uninegative tridentately towards Co(II) and Ni(II) and bidentately with Cu(II), Zn(II) and Cd(II). Ligands like NHPO and DMPHPO act as uninegative bidentately with all the metal ions. The electronic spectral data suggest that all the Co(II) complexes and Ni(II) of PHPO complex are octahedral and all the Cu(II) and Ni(II) of NHPO and DMPHPO complex are square-planar. The complex of Zn(II) and Cd(II) are tetrahedral. ESR parameters of Cu(II) complexes have been calculated and relevant conclusions have been drawn with respect to the nature of bonds present in them.     

Chlorofluorieren mit Trifluormethylhypochlorit CF3OCl. Darstellung und spektroskopische Charakterisierung von Trifluormethyliodchloridfluorid CF3I(Cl)F

Chlorofluorinate with Trifluoromethylhypochlorite CF₃OCl. Preparation and Spectroscopic Characterization of Trifluormethyliodinechloridefluoride CF₃I(Cl)F The preparation of a new iodine(III) compound, trifluormethyliodinechloridefluoride CF₃I(Cl)F, via oxidative addition of trifluoromethylhypochlorite CF₃OCl to trifluoromethyliodide CF₃I is described. The thermolabile compound has been characterized by i.r., Raman, ¹⁹F NMR, and mass spectroscopy.     

5,10,15,20-四(对氯苯基)卟啉羟基稀土配合物的光谱研究

研究了四(对氯苯基)卟啉及其羟基稀土配合物的紫外-可见光谱、红外光谱和拉曼光谱,对主要谱带进行了经验归属,讨论了中心离子对紫外光谱和共振拉曼光谱结构敏感带频率的影响.     

Derivate von Tricyanmethan. 2. Untersuchungen über Methyltricyanmethan (1,1,1-Tricyanethan) [1]

Derivatives of Tricyanomethane. 2. Studies on Methyl Tricyanomethane (1,1,1-Tricyanoethane) The title compound H₃C? C(CN)₃ has been characterized by means of nuclear magnetic resonance, vibrational, and mass spectra.     

Diffuse reflection FTIR spectral database of dyes and pigments

24 pigments commonly used in art have been characterized by diffuse reflection infrared spectroscopy (DR). All of the compounds have also been characterized by means of infrared absorption spectroscopy to demonstrate the reliability of the DR technique. This is the first record of the use of this technique as an analytical tool in conservation science, and the results appear to be promising for the identification of unknown pigments used on historical and artwork artifacts. Although the DR technique used here is not nondestructive, it can still be usefully applied to the analysis of artwork since it requires only a very small quantity of sample for analysis.     

The role of TiO2 in the B2O3–Na2O–PbO–Al2O3 glass system

Optical and vibrational studies have been carried out on 60B₂O₃·(20−x)Na₂O·10PbO·10Al₂O₃:xTiO₂ (x=0, 1, 2, 3, 4, and 5 mol%) glasses, in order to understand the role of TiO₂ in the 60B₂O₃·20Na₂O·10PbO·10Al₂O₃ glass matrix. The X-ray patterns reveal homogeneous glasses over the entire compositional range. The absorption spectra show that the energy of the optical band gap (ΔE_opt) and Urbach's energy (E_U) decreases as TiO₂ content increases. The changes observed in the Raman and IR spectra are related to the BO₄→BO₃ back conversion effect and the appearance of “loose” BO₄⁻ groups. The data indicate that titanium ions act as a network modifier.     

Dinitramide and its salts

The vibrational and electronic spectra of dinitramide salts MN(NO₂)₂ (M=K, Na, Li, NH₄, Fe, Ag, Mn, Mg, Rb, C(NH₂)₃) have been studied. The IR and Raman spectra of solutions and melts of the salts have been satisfactorily interpreted on the basis of the anion model withC _2v symmetry. The complication of the spectra in the crystalline phase has been explained by restructurization of the anion that reduces its symmetry and makes the nitro groups nonequivalent.For part 6, seeIzv. Akad. Nauk, Ser. Khim., 1995, 113 [Russ. Chem. Bull.,44, 108 (Engl. Transl.)].Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1508–1512, August, 1995.     

Preparation and investigation of the crystals formed in the buckminsterfullerene-tetraselenotetracene-carbon disulfide system

Crystals containing up to 30 wt. % CS₂, according to the data of IR and X-ray photoelectron spectroscopy, were isolated from the C₆₀-TSeT-CS₂ (TSeT is tetraselenotetracene) system. The unusually high concentration of carbon disulfide results in the complete sublimation of the crystals at a relatively high temperature (520 °C). The electron energy loss spectra of the crystals obtained were measured and analyzed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 845–848, May, 1995.This work was financially supported by the Russian Foundation for Basic Research (Projects No. 93-03-18002, 93-03-18705, and 93-03-5650).