A new ruthenium(II) cage complex with polar terminal groups in the apical substituents has been synthesized; the molecular design of the complex contributes to the effective immobilization of it due to the adsorption on the surface of a heat-resistant highly porous silicate fibrous material used as a support. The complex has been synthesized by the template condensation of cyclohexanedione-1,2-dioxime (nioxime) and 4-(hydroxymethyl)phenylboronic acid on the ruthenium(II) ion using a [Ru(CH3CN)3(COD)Cl](BF4) solvatocomplex as a source of Ru2+ cations. The composition and structure of the synthesized macrobicyclic compound have been determined using data of elemental analysis, MALDI-TOF mass spectrometry, 1H and 13C{1H} NMR spectroscopy, and X-ray diffraction analysis. It has been shown that the synthesized hybrid material with immobilized ruthenium clathrochelate catalyzes the dry reforming of methane. The productivity of the catalyst system at 900°C achieves 9437 mol CO and 11797 mol H2 per gram-atom of ruthenium per hour.

New ruthenium(II) clathrochelate with terminal polar and H+- acidic carboxyl groups, designed for its effective immobilization on a surface of the highly porous silicate fibrous material TZMK, was obtained using the template condensation of cyclohexanedione-1,2-dioxime (nioxime) and 4-carboxyphenylboronic acid on the ruthenium(II) ion as a matrix; the solvatocomplex [Ru(CH3CN)(3)(COD)Cl](BF4) was used as a source of Ru2+ cations. Thus obtained ruthenium(II) clathrochelate was characterized using elemental analysis, MALDI-TOF mass, UV- vis, H-1 and C-13{H-1} NMR spectra, and by the single crystal X-ray diffraction experiment as well. The hybrid TZMK-based catalytic material, prepared by its immobilization on a surface of this ceramic support, was tested as a catalyst of dry reforming of methane. At the rate of a feeding of the initial reagents (CH4:CO2 =1) equal to 12.7 g(-1)center dot L per h, their conversions at 900 degrees C fall in the ranges 7-8 and 11-13 %, respectively, while the yields of H-2 and CO were from 2.2 to 2.5% and 4.4 to 4.6 %, respectively. The CO performance of this ruthenium-containing hybrid system reaches approximately 560 mL center dot g(-1) (cat) per h, thus corresponding to 4.3 mol/g-atom of Ru per h. Decrease in the rate of an initial reagents feeding up to 6.4 mol center dot L-1 per h caused an increase in the conversions of CH4 and CO2 up to 14 - 15 and 26 - 28 %, respectively, with a simultaneous increase in the yields of H-2 and CO up to 5.3 - 6.3 and 11 - 12 %, respectively. In the latter case, the CO performance reaches 724 mL center dot g(-1)(cat) per h (5.4 mol/g-atom of Ru per h).

The structural evolution of three electrocatalytic systems for hydrogen evolution reaction using iron, cobalt, and ruthenium(II) clathrochelate complexes as catalysts in a water electrolyzer is studied by X-ray absorption near-edge structure (XANES)/extended X-ray absorption fine structure (EXAFS) spectroscopy. The complexes are shown to display essentially different robustness under water electrolysis conditions in pilot-scale hydrogen generators. The iron and cobalt(II) clathrochelates preserve their cage, macrobicyclic structure, and the encapsulated metal(II) ion is reduced to metal(I) cation; whereas in the case of ruthenium(II) clathrochelate, the cage complex undergoes partial decomposition to form sulfur-containing products of decomposition of the encapsulating macrobicyclic hexasulfide ligand, which results in the accumulation of the ruthenium disulfide RuS 2 in used clathrochelate-containing cathode material. Taking into account our experimental data on the chemical transformation of clathrochelate electrocatalysts under the conditions of 2Н + /Н 2 reaction, we discuss the possibilities for boosting the efficiency of electrocatalytic systems based on this class of coordination compounds.

A new method for the synthesis of sulfonated polynaphthylimides has been developed on the basis of the postsulfonation of high-molecular-mass polynaphthylimides with a sulfuric acid-oleum mixture. Sulfonated polymers of this type have been obtained from the polycondensation products of 5-phenylthiophenylene-1,3-diamine with dianhydrides of 1,4,5,8-naphthalenetetracarboxylic acid and 4,4′-(1,4-phenylenedicarbonyl)-bis-naphthalene-1,8-dicarboxylic acid. It has been shown that hydrogen peroxide oxidation of sulfide bridge groups of these polymers in an acidic medium yields high-molecular-mass compounds that contain sulfonic bridge fragments and, therefore, have increased thermal stabilities and enhanced proton conductivities.

New polynaphthylimides containing thiophenoxide substituents are prepared via the interaction of 5-phenylthiophenylene-1,3-diamine with dianhydrides of naphthalene-1,4,5,8-tetracarboxylic acid and 4,4′-(1,4-phenylenedicarbonyl)-bis(naphthalene-1,8-dicarboxylic acid) under the conditions of high-temperature polycyclocondensation in phenolic solvents. The polymer-analogous oxidation of sulfide groups to sulfone groups yields previously undescribed polynaphthylimides with phenylsulfone substituents.

Key advances in the synthesis, characterization, and application of poly(arylene oxides) containing sulfo acid groups in main chains of macromolecules and side substituents are surveyed. The main advantages and drawbacks of various approaches to the synthesis of these polymers, such as postsulfonation of poly(arylene oxides), polycondensation with the use of sulfonated monomers, and transformations of polymers containing reactive groups, are analyzed.

PEMFC Fuel Cell uses a polymer membrane as an electrolyte. It is used in all applications with dynamic loads, especially in mobile applications but also as combined heat and power units in households. The development of the membranes ion-conductivity has much increased over the last 30 years. Today "Nafion"-based membranes achieve a power density up to 1 W/cm(2) active area. In the last 10 years the successful adoption of the PEMFC in different prototypes could be demonstrated. For a market-introduction a few "teething problem" like life-time and costs have to be solved.In this context scientists have high expectations in the development of high-temperature membranes. Cells with these temperatures can be operated over 373 K.Regarding our investigations on the synthesis of aromatic condensation monomers and polymers based on 2,4,6-trinitrotoluene (TNT) we have developed new sidechain-sulfonated aromatic diamines (SCSADAs) and polymers there from. Generally these diamines are prepared using multistep synthetic procedures; as a result they are expensive and unavailable. Our approach shows that the acidic groups on the pendant phenyl groups are more stable to hydrolysis than those with acidic groups directly attached to themain chains. Acidifiedpolymers are stable up to 423 K.

A new aromatic sulfo-group-containing diamine, 3,5-diaminodiphenyloxide-4′-sulfonic acid, has been synthesized via step-by-step transformations of 1,3,5-trinitrobenzene resulting from the demethylation of 2,4,6-trinitrotoluene. Triethylammonium salts of corresponding sulfonated polynaphthylimides are obtained through the interaction of this diamine with 1,4,5,8-naphthalenetetracarboxylic and isophthaloylbis(naphthalic) dianhydrides in phenol in the presence of triethylamine, benzoic acid, and benzimidazole. The acidification of these salts yields the desired sulfonated polynaphthylimides, which are of interest as proton-exchange membranes.

New poly(arylene ethers) containing side sulfo groups have been synthesized through the copolycondensation of 3,5-dinitrodiphenyl sulfone 4′-sulfonic acid and 4,4′-dichlorodiphenyl sulfone with bicyclic aromatic bisphenols under the conditions of aromatic nucleophilic substitution. On the basis of the blends of these copolymers with sulfonated poly(arylene ester ether ketone), membranes with satisfactory mechanical characteristics and high proton conductivity have been prepared.