The thesis is devoted to the processes with the participation of chemically and electrochemically generated particles in the dublet electronic state, namely generation of the chemi- (CL) and electrochemiluminescence (ECL), interaction with solid state substrates and formation of the polymeric chains with system of conjugated pi-bonds. The mechanisms of the CL and ECL generation during reduction of the peroxydisulfate-anions in the aqueous solutions and arenediazonium salts (DAS) in the aprotic medium, during electrochemical oxidation of the aromatic carboxyacids (Kolbe electrosynthesis) and luminol, and also acridine/acridane and its precursor N-phenyl-ortho-aminobenzoic acid in the acetonitrile solutions were proposed. The influence of such factors as a current density / electrode potential, electrolyte composition, nature of solvent, presence of the catalytically active compounds on the intensity of light radiation has been studied. The special attention was spared to the role of the molecular oxygen and its active forms and also to the influence of the nature of electrode material on the processes of luminescence generation. For the first time the possibility of the CL and ECL use in the material science, exactly for the study of the processes of radical polymerization, for the determination of the morphology of metals and semiconductors surface, for the functionalization and modification of surfaces, for the characterization of the state and structure of the surface layers on the different substrates was shown. The restrictions for the use of the ECL phenomenon in the electrochemical preparative synthesis for the determination of the process optimal conditions has been formulated. It was shown, that the chemically or electrochemically generated free radicals products of the DAS reduction reacts actively with the surface of the solids. It was detected for the first time, that the chemical reduction of DAS by the alkaline, alkaline-earth elements and also by the Fe, Cu, Cr, Ni, Al, and Mg is accompanies by the active dissolution-ionization of the metals. This process is double-stage on the copper and magnesium substrates: the formation of the covalently grafted to the metal-substrate surface mono- or multilayer, which forms an intermediates of the arenediazonium-cations reduction, precedes dissolution. The influence of the diazocation nature on the rate of copper-DAS interaction has been studied and structure of produced products was determined. Moreover, the thermolysis of the phenyldiazonium tetrafluoroborate in the solid state (Baltz-Schiemann reaction) has been studied. The chain mechanism of the DAS decomposition was proposed for the explanation of the registered avalanche acceleration of the DAS destruction after the induction period. The mechanism of the oxidative polycondensation of aniline and its derivatives has been studied. It was shown, that the process is initiated by the cation-radicals of initial monomer. These particles during chemical initiation of polycondensation forms during the decomposition of the stoichiometric (1 : 1) reaction complex of initial monomer and peroxydisulfate-anion. The recombination of the free radical intermediates proceeds according to the "head-to-tail" type, which is possible after the isomerization of the primary benzenoid cation-radicals in the particles of quinoid type. The further chain growth occurs in accordance with analogous as for the monomer algorithm. By the example of nitro- and oxymethyl-anilines the influence of the substituent in the aromatic ring on the reactivity of the derivatives in comparison with aniline during oxidative polycondensation reaction was estimated. In addition, for the first time the successful chemical synthesis of the polyluminol was carried out and optimal conditions of reaction implementation were determined. The most probable structures for the produced polymeric products were proposed on the basis on results of spectral measurements and element analysis. For the first time it was detected, that the electrochemical synthesis of polyaniline under the high potentials of working electrode is accompanied by the weak luminescence. It was shown, that source of this phenomenon is destruction of the oxidized form of polyaniline pernigraniline.
