Study on the Phase Diagram of CsCl-CeCl3-HCl(11%)-H2O System and the Properties of the Compounds

The equilibrium solubility of CsCl-CeCl3-HCl(11%)-H2O qua-ternary system at 25℃ has been determined by the physicchemical analysis method ,and the phase diagram was plotted, Two new double salts 3CsCl.CeCl3.3H2O and CsCl.CeCl3.4H2O obtained from the complicated system were identified and characterized by XRD,TG-DTA ,DSC,UV and fluorescence spectroscopy, Studies on the fluorescence excitation and emission show that 3CsCl.CeCl3.3H2O and CsCl.CeCl3.4H2O have upconversion luminescence of infrared-visible range,and the upconversion emission intensity increases with the increase of ratio of CeCl3 in CsCl.     

Structure of the blue forms of bisphthalocyanines of rare-earth elements

Using electron spectroscopy, X-ray photoelectron spectroscopy, and ESR spectroscopy, the blue forms of bisphthalocyanines of rare-earth elements were found to have structures of sandwich-type complexes with isoelectronic phthalocyanine ligands linked with tetravalent metal ions, [Pc^2–Ln⁴⁺Pc^2–]⁰. A comparative spectral and electrochemical study of the blue and green forms oftert-butyl-substituted bisphthalocyanines was carried out for almost the whole series of rare-earth metals. Lutetium octa(perfluoro-tert-butyl)- and perchlorobisphthalocyanines were synthesized for the first time.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 425–430, March, 1995.This study was financially supported by the Russian Foundation for Basic Research (grant No. 94-03-08903).     

The photochemical interaction of polyphenylferrisiloxane with oligoorganosilanes

The photochemical interaction of polyphenylferrisiloxane with some oligoorganosilanes in benzene solutions has been studied by UV, IR, ESR, and Mössbauer spectroscopy. Silylene species formed during photolysis of oligoorganosilanes react with the high-spin iron(III) to reduce the latter to low-spin iron(II). The formation of the low-spin state of iron(II) was supported by measurements of the magnetic moments. The insertion of the silylene species into the polymer chain to form the Fe?Si bond occurs due to the photoreaction.     

Association of model peptides and dehydropeptides: N-acetyl-l-alanine- and dehydroalanine N′,N′-dimethylamides

The comparative studies on the association of Ac-ΔAla-NMe₂ and Ac-l-Ala-NMe₂ in carbon tetrachloride were performed by the analysis of their average molecular weight, dipole moments and FTIR spectra. To aid spectroscopic interpretation and gain some deeper insight into the nature of associates, the geometries of the minimum energy of the dimers of Ac-ΔAla-NMe₂ and Ac-l-Ala-NMe₂ were calculated by the B3LYP/6-31+G** method. The average molecular weight in the studied concentration range, for the ΔAla and l-Ala peptide, as determined by the osmometric method, did not exceed 1.5 and 1.2 of the monomeric mass, respectively. Accordingly, the percentage of the monomeric form (α) decreased as concentration was increased more significantly for the ΔAla analogue than for its saturated counterpart. In the studied concentrations, the dipole moment of the unsaturated compound decreases and that of its counterpart is almost constant. We identified a wider range of dimeric forms of Ac-ΔAla-NMe₂ than those of Ac-l-Ala-NMe₂. While Ac-ΔAla-NMe₂ mainly forms cyclic dimers, built of open conformers H/F, specific for α,β-dehydroamino acids, Ac-l-Ala-NMe₂ forms cyclic and linear dimers, characteristic for the usual amino acids. Ac-ΔAla-NMe₂ has a greater tendency to associate than its saturated variant, which is the result of stronger hydrogen bonds.     

双（1,2—丙二胺）合铜的TCNQ盐的合成与光谱研究

合成了导电性ＴＣＮＱ盐Ｃｕ（ｐｎ）２（ＴＣＮＱ）ｎ（ｎ＝２和３，ｐｎ＝１，２－丙二胺，ＴＣＮＱ＝７，７，８，８－四氰基对苯二醌二甲烷）。红外光谱、电子光谱和Ｘ－光电子能谱研究表明ＴＣＮＱ盐中存在ＴＣＮＱ°和ＴＣＮＱ－，ＴＣＮＱ°与ＴＣＮＱ－之间发生了部分电子转移，致使铜呈混合价态。它们的粉末室温电导率为１．１×１０－５～２．４×１０－６ｏｈｍ－１ｃｍ－１。     

Carbonyl and hydridocarbonyl complexes of ruthenium (II) and osmium (II) with tertiary arsines

Ruthenium halides (Cl and Br) react with monotertiary arsines-Ph₂RAs (R=Me, Et, Pr ⁿ ) in methoxyethanol, in the presence of aq. formaldehyde to give monocarbonyl complexes of ruthenium(II) of the type RuX₂(CO) (Ph₂RAs)₃. Carbonylation of an ethanolic solution containing ruthenium trichloride and the arsine at room temperature yieldtrans dicarbonyl compounds of the formula RuCl₂(CO)₂ (Ph₂RAs)₂. The osmium monocarbonyls OsX₂(CO) (Ph₂RAs)₃ (X=Cl, Br; R=Me, Et) react with NaBH₄ in methanol to yield complexes of the composition OsHX(CO) (Ph₂RAs)₃. The ruthenium analogues RuHCl(CO) (Ph₂RAs)₃ have also been made. Structures have been assigned to all these compounds on the basis of IR and NMR spectral results.     

Tetramethyldisilan-1,2-diyl-verbrückte Dicyclopentadienyl-und Diindenylmetalldichloride der 4. Gruppe – Kristallstruktur von

Tetramethyldisilane-1,2-diyl bridged Dicyclopentadienyl and Diindenyl Metal Dichlorides of the Group 4 Metals – Crystal Structure of Dicyclopentadienyl and diindenyl metal dichlorides of the type Cp′? SiMe₂SiMe₂? Cp′MCl₂ (Cp′ = C₅H₄, M = Ti ( 1 ), Zr ( 2 ), Hf ( 3 ); Cp′ = C₉H₇, M = Zr ( 4 ), Hf ( 5 )) were synthesized and characterized by means of their ¹H, ¹³C, ²⁹Si-n.m.r., MS, and IR spectra. The crystal structure of 2 was determined.     

pH值对聚四氨基酞菁钴膜电化学和紫外光谱性质的影响

用循环伏安法在导电玻璃(ITO)和玻碳电极(GC)上制备了聚氨基酞菁钴(CoTAPc)修饰电极(CoTAPc/GC)。探讨了pH值对CoTAPc膜的光谱和电化学性质的影响，发现其氧化还原电位与pH值有线性关系，电催化活性也随酸度的增加而增加。CoTAPc膜的紫外吸收带变化与溶液pH值及在溶液中浸泡时间有关。     

Tetrakis(thiadiazolo)porphyrazines. 3. Acid-base Properties and Stability of Tetrakis-3,4-(1,2,5-thiadiazolo)porphyrazine in Sulfuric Acid Solutions

AM1 calculations gave the proton affinities of different types of donor sites in tetrakis-3,4-(1,2,5-thiadiazolo)porphyrazine, H₂{[SN₂)₄PA}, and protonation of the meso-nitrogen atoms was found to be favored. A spectrometric study showed that the basicity of the meso-nitrogen atoms of the porphyrazine macrocycle is strongly diminished and these atoms in CF₃CO₂H are involved in an incomplete acid-base interaction (ABI) to give acid solvates, while a complete ABI (protonation) is found only in the presence of sulfuric acid. The basicity constants of the meso-nitrogen atoms were determined spectrophotometrically in CF₃CO₂H-H₂SO₄. The kinetics of decomposition of the macrocyclic chromophore in concentrated sulfuric acid was studied and a possible mechanism for this process was proposed.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 278–287, February, 2005.     

Determination of dipole moment in the ground and excited state by experimental and theoretical methods of N-nonyl acridine orange

The absorption and fluorescence spectra of N-nonyl acridine orange are determined at room temperature (298 K) in cyclohexane, benzene, carbon tetrachloride, chloroform, chlorobenzene and dichloromethane. The ground state of dipole moment was obtained by impedance measurements using Guggenheim-Debeye's method. The experimental excited state dipole moment of N-nonyl acridine orange was determined using Bakhshiev's and Kawski-Chamma-Viallet's formulae and solvent polarity parameter proposed by Reichardt. These experimental results were completed with theoretical results using quantum chemical methods. The experimental (muexp=10.76 D) and theoretical (mucal=9.9 D) dipole moments in the ground and excited state (muexp*=14.56 D) were compared.