Synthesis, structure, electrochemistry, and photophysics of 2,5-dibenzylidenecyclopentanones containing in benzene rings substituents different in polarity

Abstract

A series of cross-conjugated dienones was synthesized to study the dependence of physicochemical characteristics on the nature of substituents in the aromatic groups of symmetric cyclopentanone dibenzylidene derivatives. The structure of compounds was established by electronic, IR, and NMR spectroscopy and X-ray diffraction study. All the compounds obtained possess the E,E-geometry. In the crystalline state, the arrangement of the dienone molecules is unfavorable for the intermolecular [2+2] photocycloaddition to take place. The low-temperature phases transition for unsubstituted diphenyl derivative of cyclopentanone was detected using variable-temperature X-ray diffraction and differential scanning calorimetry. Oxidation and reduction potentials of the dienones were measured by cyclic voltammetry. Their dependence on the nature and placement of substituents in the benzene rings was demonstrated. A linear correlation (R = 0.9343) between the difference of electrochemical oxidation and reduction potentials and the energy of the long-wavelength absorption maximum was found, that allows us to recommend the use of the data obtained in the correlation analysis of other compounds of this class.