A new lead cyanoferrate(III) with a mixed anionic sublattice Pb-2[Fe(CN)(6)] center dot NO3 center dot 5.5H(2)O was synthesizcd, and its structure and thermal properties were studied. The compound crystallizes in the monoclinic system. The structure is stabilized by water molecules that combine the main structural elements through bridging (Pb-O-w-Pb) and hydrogen ((OH)-H-...-O) bonds. The destruction of the crystal hydrate of lead cyanoferrate(Ill) takes place in the temperature range 120-150 degrees C. The thermolysis yields anhydrous Pb1.5Fe(CN)(6) (trigonal) and Pb(NO3)(2) (cubic), which were identified by X-ray powder diffraction and IR spectroscopy.

The IR and Raman spectra of crystal hydrates and anhydrous phases of p-element (tin, lead) cyanoferrate(II) and cyanoferrate(III) complexes are systematically investigated. Tendencies of the evolution of the vibrational stretching frequencies v(CdropN), v(Fe-C), and v(OH) are determined as functions of the composition, structural type of the compound, the existence of molecular water in the crystal lattice of the cyanoferrate (CF), the main bond strength, the outer-sphere cation radius, and the iron oxidation number. The vibrational spectra are matched to the overlap population parameters of the Sn(Pb)-N and Fe-C crystal orbitals derived from quantum-chemical zone calculations.

H-1 and Li-7 NMR spectroscopy have been used as tools for studying lithium ion mobility in the products of ion exchange on zirconium hydrogen phosphate LixH1-xZr(PO4)(2) . nH(2)O. An increase in the proton substitution level both significantly decreases the fraction of mobile lithium ions and increases the ion mobility in this fraction. The mobility activation energy of lithium ions is as low as 8.5-9 kJ/mol. The results are analyzed with reference to the cation mobility in these systems derived from potentiometric titration kinetic data. Discussion is carried out in terms of the notions of interfacial sorption phenomena.

The ionic conductivities of heteropoly acids were measured using impedance spectroscopy in the temperature range 15-400 degreesC. The proton migration activation energies were determined. The contents of hydrogen-containing species of tungstic 12-heteropoly acids with a varied number of acid protons-H3PW12O40 . nH(2)O (n = 6.5,23), H4SiW12O40 . nH(2)O (n = 9, 18), and H5GaW12O40 . nH(2)O (n = 10, 13)-were determined by H-1 NMR and thermogravimetry. The proton-proton distances in the H2O and H3O+ species of the heteropoly acids were found to depend on their annealing temperature. Tungstophosphoric acid was demonstrated to have an optimal relationship between the strengths of the H-bonds of acid protons and water molecules and of water protons to oxygen atoms, so that this acid is a better proton conductor than tungstophosphoric and tungstogallic acids.

NMR of 51 V and 27 Na in monocrystals β- Na x V 2O5(x=0.22, 0.27, 0.33) has been studied between 80 K and 400 K. Temperature dependences of hyperfine interactions have been investigated. In all compositions under study, a phase transition has been observed, its temperature has decreased with a reducing natrium content. A joint analysis of magnetic susceptibilities and resonance shifts showed that the phase transition has been connected with a gap formation at the Fermi level. Investigations of quadrupole effects and electroconductivities allowed to establish that the phase transition has been accompanied by a charge density wave development. On the basis of NMR measurements, an electron localization region has been evaluated. The results have been compared with electrophysical data.

In the frequency interval 3.9-20 MHz, we have obtained the Na-23 and V-51 NMR spectra for single crystals of NaxV2O5 (x = 0.22; 0.27; 0.33). We have shown that the magnetic properties of the given compounds are sufficiently correctly described in the delocalized electron approximation. On the basis of comparison of the experimental parameters of the electric field gradients and the values of the gradients obtained as a result of calculations of the electronic structure, we have established that the Fermi level is formed by the 3d states of electrons at the V1 and V3 positions.

We shall present the results of an investigation of the current-voltage characteristics and of the temperature dependence of the conductivity σ(T) determined under dc conditions at temperatures in the range 77-300 K. In these experiments we used a Na 0.33 V 2 O 5 single crystal elongated along the b axis

In the frequency interval 3.9-20 MHz, we have obtained the 23Na and 51V NMR spectra for single crystals of NaxV205 (x = 0.22; 0.27; 0.33). We have shown that the magnetic properties of the given compounds are sufficiently correctly described in the delocalized electron approximation. On the basis of comparison of the experimental parameters of the electric field gradients and the values of the gradients obtained as a result of calculations of the electronic structure, we have established that the Fermi level is formed by the 3d states of electrons at the V I and V 3 positions. Oxide vanadium bronzes, type $ NaxV20 s (0.2 j x j 0.4), belong to the class of inorganic quasi-one-dimensional conductors [i]. The structure of the $-NaxV205 belongs to monoclinic syngony, the angle between the a and c axes is equal to 109 ~ [2]. In this structure, we observe three nonequivalent positions for the vanadium atoms: V l and V 2 are found within distorted oxygen octahedra, and V 3 is found in an environment of five oxygen atoms. The octahedra and trigonal bipyramids make up three types of chains along the b axis. The free spaces between the chains form channels passing parallel to the b axis, into which the sodi,mm ions are incorporated. The observed conductivity along the b axis is equal to i00 ohm-l'cm -I at 300 K, which is two orders of magnitude higher than the conductivity in the direction perpendicular to the b axis, and its temperature dependence is like that of a semiconductor [i]. In [3, 4], it was established that upon insertion of alkali metal atoms into the channels, they lose an electron to the vanadium-oxygen subsystem, but the question concerning the nature of the localization of these electrons has not yet been answered. The presence of anisotropy in the conductivity indicates that charge transfer ,is accomplished along the vanadium chains, but there is no reliable information on the selective role of the chains.