A series of symmetrical
dibenzylidene derivatives of cyclohexanone
were synthesized with the goal of studying the physicochemical properties
of cross-conjugated dienones (ketocyanine dyes). The structures of
the products were established and studied by X-ray diffraction, NMR
spectroscopy, and electronic spectroscopy. All products had the
E
,
E
-geometry. The oxidation and reduction
potentials of the dienones were determined by cyclic voltammetry.
The potentials were shown to depend on the nature, position, and number
of substituents in the benzene rings. A linear correlation was found
between the difference of the electrochemical oxidation and reduction
potentials and the energy of the long-wavelength absorption maximum.
This correlation can be employed to analyze the properties of other
compounds of this type. The frontier orbital energies and the vertical
absorption and emission transitions were calculated using quantum
chemistry. The results are in good agreement with experimental redox
potentials and spectroscopic data.
A series of symmetrical dibenzylidene derivatives of cyclobutanone were synthesized with the goal of studying the physicochemical properties of cross-conjugated dienones (ketocyanine dyes). The structures of the products were established and studied by X-ray diffraction and by NMR and electronic spectroscopy. All the products had E,E-geometry. The oxidation and reduction potentials of the dienones were determined by cyclic voltammetry. The potentials were shown to depend on the nature, position, and number of substituents in the benzene rings. A linear correlation was found between the difference of the electrochemical oxidation and reduction potentials and the energy of the long-wavelength absorption maximum. This correlation can be employed to analyze the properties of other compounds of this type. Quantum chemistry was used to explain the observed regularities in the electrochemistry, absorption, and fluorescence of the dyes. The results are in good agreement with the experimental redox potentials and spectroscopy data.
Dependence of reactivity on substituents in the pyridine ring of the 4-methylpyridinium salts was studied in intermolecular reaction of ring transformation involving quaternary salts of pyridinium and isoquinolinium promoted by methylammonium sulfite.
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