Effect of substituents on spectral, luminescent, and time-resolved spectral properties of 2,6-diarylidene derivatives of cyclohexanone

Abstract

Spectral, luminescent, and time-resolved properties of 2,6-dibenzylidene cyclohexanone and its symmetric derivatives in the para-position of benzene ring (dimethoxy, dimethylthio, and bis-N,N-diethylamino groups) have been studied in media of different polarity (cyclohexane, acetonitrile, dimethylsulfoxide, and methanol). Introduction of electro-donating substituents to dibenzylidene cyclohexanone results in the red shift of the absorption maximum by 81–138 nm upon passing from the nonpolar to polar medium. Bis(N,N-diethylamino)dibenzylidene cyclohexanone fluoresces in polar solvents, acetonitrile, dimethylsulfoxide and methanol. The bathofluoric shift on passing from acetonitrile to methanol is 39 nm. The relative quantum yield of fluorescence in acetonitrile is seven times that in methanol. An intermediate species absorbing in the range of 400–560 nm with a maximum at 430–460 nm has been observed under the action of the laser pulse on dibenzylidene cyclohexanone solutions in acetonitrile. The intermediate species has a lifetime of 40, 20, and 7 μs for dibenzylidene cyclohexanone and its dimethylthio and dimethoxy derivatives, respectively.