Synthesis and crystal structural study of ternary molybdate NaMg3In(MoO4)5

We have synthesized single crystals of a temary molybdate NaMg₃In(MoO₄)₅ and cam'ed out an X-ray structural study (a KM-4 automatic difiactometer, MoK, radiation, 4503 F, R = 0.047). The triclinic unit cell dimensions are a = 7.0476(7), b = 17.935(2), c = 6.9849(7)Å, = 87.650(9), = 100.980(8), = 92.510(9)°, V= 865.5(2) A³, Z = 2, and space group P^–1. The crystal structure involves MoO₄ tetrahedra and (Mg, In)0₆ octahedra forming a three-dimensional framework with Na atoms located in its cavities. The compound melts at 990°C with decomposition.Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences. Institute of Physics, Siberian Branch, Russian Academy of Sciences. Buryatian Institute of Natural Sciences, Siberian Branch, Russian Academy of Sciences. Translated fromZhurnal Strukturnoi Khimii, Vol. 34, No. 5, pp. 147–151, September–October, 1993.Translated by T. Yudanova     

Quantum-Chemical Study of Proton Transfer and Photoreactions of Quinolone Derivatives

The possible routes of deactivation of electronically excited states of 4-methyl-7-hydroxy-2-quinolone and its protolytic forms were analyzed. The relative contribution of radiative and nonradiative deactivation channels of electronic excitation energy was determined, and the rate constants of photophysical processes (internal conversion and intersystem crossing) occurring upon light absorption by these forms were estimated.     

Synthesis and psychotropic properties of furyl- and thienyl-germatranes

Trihalogermyl-furans and -thiophenes were prepared by inserting germanium dibromide (GeBr₂) generated from the dibromogermane(II) dioxanate complex into the carbon-halogen bond of halo-furans and -thiophenes. Their ethanolysis and transesterification by triethanolamine yielded the germatranes which were subjected to psychotropic activity assays. The psychotropic properties of germatranes were found to depend on the type of the heterocycle and on the position of the germatrane moiety.     

Intramolecular Dynamics and Molecular Structure of Europium(III) Chelate Complexes with Crown Ethers as Studied by NMR Spectroscopy

Earlier the intramolecular inversion of the 18-crown-6 molecules was found in the complex ion pairs [Ln(ptfa)₂ (18-crown-6)]⁺ [Ln(ptfa)₄]⁻ (H₂O)₄ where Ln = La(1), Ce (2), Pr (3), Nd (4), and ptfa is 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione. In this work the peculiarities of the molecular structure and dynamics were studied for [Eu(ptfa)₂ (18-crown-6)]⁺ [Eu(ptfa)₄]⁻ (H₂O)₄ (5) by NMR spectroscopy techniques. Through VT-NMR spectra analysis the temperature dependence was obtained for the rate constant. The free energy ΔG^‡(320) of 18-crown-6 ring inversion activation was found to be 65 ± 5 kJ mol⁻¹ for 5 in CDCl₃. This result is comparable with the earlier data [S.P. Babailov and D.A. Mainichev: J. Inclusion Phenom. Macrocyclic Chem. 43, 187–193 (2002)] for complexes 2, 3, 4 in deuterated toluene (ΔG^‡(320)=65 ± 9, 64 ± 9, 64 ± 9 kJ mol⁻¹ respectively). It was found by relaxation NMR spectroscopy that the effective distance between Ln and protons of the crown molecule is 4.5 ± 0.2 Å. The analysis of structural parameters testifies that the crown ether and chelated anions are in the first coordination sphere of a Ln cation. Obtained geometrical parameters show that the complex cations of Eu, Ce and Pr have similar spatial structures.This revised version was published online in July 2005 with a corrected issue number.     

NMR Studies of Mixed-Ligand Lanthanide Complexes in Solution: Pseudorotation and Ring Inversion of 18-Crown-6 Molecule in Cerium Subgroup Chelates

¹H and ¹³C NMR measurements are reported for the CDCl₃ and CD₂Cl₂ solutions of [La(NO₃)₃(18-crown-6)] (I), [Pr(NO₃)₃(18-crown-6)] (II) and [Ce(NO₃)₃(18-crown-6)] (III) complexes. Temperature dependencies of the ¹H NMR spectra of II have been analyzed using the dynamic NMR methods for multi-site exchange. Two types of conformational dynamic processes in II were identified (the first one with activation enthalpy ΔH ^‡=26 ± 4 kJ/mol is conditioned by interconversion of complex enantiomeric form and pseudorotation of macrocycle molecule upon the C ₂ symmetry axis, the second one with ΔH ^‡=46 ± 5 kJ/mol is conditioned by macrocycle molecule inversion). Studies of the values of the lanthanide-induced shifts revealed that the structure of complexes in solution is similar to that reported for the complex I in the crystal state.This revised version was published online in July 2005 with a corrected issue number.     

Calcium Phosphate Dental Materials Prodused with the Help of Natural Alumosilicates

Abstract

Calcium phosphates are well known to be perspective as biomaterials, for example. the dental ones. There are two tendencies in investigation and design of such materials. They are the search of porous biomaterials and development of dense bioceramics on the basic of hydroxópatite and crystallized calcium phosphate glasses. Control of glasses crystallization with the help of modificators and nucleating agents is the main way for producing dense biomaterials [1, 2]. We used natural alumosiiicates, for example, kaolin as a reagent and modificator for calcium polyphosphate to achieve a good quality of materials without stages of glass formation and glass crystallization.