Zatsikha Y. Long-wavelength borondipyrromethenes with conjugated substituents

The dissertation is devoted to the synthesis and investigation of the spectroscopic and electrochemical properties of BODIPY dyes, and polymethine dyes on BODIPY core. A method of the preparation of symmetrical anionic and cationic polymethine dyes on BODIPY framework with the same geometry and opposite charges has been developed. Spectral properties and parameters, resulted from the quantum-chemical analysis, suggest that this dye is closely related to the anionic analogue, based on the same framework. The only difference between the symmetrical dyes of both types is the energy of the molecular orbitals, which is higher for the anionic dye. It was shown that these dyes have the similar spectroscopic properties. The similarity of their electronic structure has been confirmed by quantum-chemical calculations. 2,6-Chlorine substituted BODIPY dye was synthesized. The range of polymethine substituted dyes on Cl-BODIPY has been obtained. It was shown that these dyes are merocyanines. Borondipyrromethene group acts as an electronwithdrawing end group this chromophoric system. The transformation of the BODIPY chromophoric system into the polymethine one through intermediate polyene system was analyzed. The factors that affect on it were investigated. Spectral properties of unsymmetrical dyes may be changed in a wide range by combining the second end core. The wide ranges of mono- and bispyrridoneannelated BODIPY dyes have been synthesized. Developed the opportunities for modification of the physicochemical parameters for the special practical purposes through combining the substituents in these systems. The prepared stable dyes are intense fluorophores with emission maximum in the region of 610-615 nm which may be further red-shifted by the transition to styryl derivatives. These dyes can be used in biomedical research for the fluorescent labeling of biomolecules via the amide bond formation or click reactions, membrane studies, etc. It was found that tautomerism is peculiar for the protonated derivatives of the anionic BODIPY dyes. These tautomeric forms belong to the different chromophoric systems, which provide the new approaches for the construction of long-wavelength dual fluorescent probe design. A number of ferrocene and fullerene substituted redox-BODIPY dyes has been synthesized. The analysis of their spectroscopic, electrochemical, and quantum-chemical calculations shows, that these systems are prospective candidates for the constructions of photovoltaic devices