Department of Inorganic Chemistry, Ivanovo State University of Chemistry and Technology 7, Sheremetevsky Ave, Ivanovo 153000, Russia.
Department of Inorganic Chemistry, Ivanovo State University of Chemistry and Technology 7, Sheremetevsky Ave, Ivanovo 153000, Russia.
Spectrochim Acta A Mol Biomol Spectrosc. 2021 Jul 5;255:119683. doi: 10.1016/j.saa.2021.119683. Epub 2021 Mar 10.
A simple semiempiric phenomenological approach is developed for quantifying the solvent effect on the absorption and emission properties of BODIPYs. It is based on a new rule describing the linear relationship between the difference (Stokes shift) and the sum (double Gibbs free energy of electron transfer) for absorption and emission wavenumbers derived from a combination of solvent functions of Liptay theory. This rule is correspondent to changes of dipole moments in the ground and excited states. High reliability and advantages of the developed approach in comparison with traditional methods of the analysis of the solvatochromism based on Dimroth-Reichard and Lippert-Mataga solvent scales are illustrated for selected BODIPYs exhibiting positive, negative, and near-zero solvatochromism.
本文提出了一种简单的经验半唯象方法，用于量化溶剂效应对 BODIPYs 吸收和发射性质的影响。它基于一个新规则，该规则描述了由 Liptay 理论的溶剂函数组合得出的吸收和发射波数的差异（斯托克斯位移）与和（电子转移的双吉布斯自由能）之间的线性关系。该规则与在基态和激发态中偶极矩的变化相对应。本文通过选择具有正、负和近零溶剂化变色的 BODIPYs，说明了与基于 Dimroth-Reichard 和 Lippert-Mataga 溶剂标度的传统溶剂化变色分析方法相比，所开发方法的高可靠性和优势。
