Spectral Properties of Dyes with Interfragmental Charge Transfer: Solvatochromism and Solvatofluorochromism of 2-(3-Coumaroyl)-benzopyrylium Perchlorates

[摘要] The paper deals with the spectral properties of dyes with interfragmental charge transfer, in particular, derivatives of 2-(3-coumaroyl)benzopyrylium (CBP) perchlorates. The positions of long-wavelength absorption and emission bands, quantum yields, and lifetimes of fluorescence were measured, mostly in aprotic solvents. Regression analysis of the relationship between the spectral characteristics of CBP and the main solvent parameters (polarity, polarisability, nucleophilicity, and electrophilicity) was carried out. It was found that the characteristics of CBP depend mainly on two solvent parameters—polarity and/or nucleophilicity. An increase in these parameters results in a hypsochromic shift of absorption bands and a decrease of lifetimes and fluorescence intensity. The positions of the emission bands can demonstrate either hypsochromism or bathochromism, depending on the nature of the substituents. The solvatofluorochromic effects are not as strong as the solvatochromic ones. We believe that the spectral behaviour of CBP can be explained by cation depolarisation and by a decrease in the stability of nucleophilic complexes with solvent molecules that is associated with interfragmental charge transfer following excitation, relaxation, and radiative deactivation of the excited state.

[学科分类] 光谱学