Piękoś Patrycja, Lipkowski Paweł, Dehaen Wim, Wieczorek Robert, Filarowski Aleksander
Faculty of Chemistry, University of Wroclaw, F. Joliot-Curie 14, 50-383 Wrocław, Poland.
Department of Physical and Quantum Chemistry, Wrocław University of Science and Technology, Wybrzeże Wyspiańskiego 27, 50-370 Wrocław, Poland.
Molecules. 2025 May 18;30(10):2209. doi: 10.3390/molecules30102209.
This paper concerns the in silico studies of the influence of heterocyclic substituents as well as their protonated and deprotonated forms on the spectral characteristics of BODIPY (4,4-difluoro-4-bora-3a,4a-diaza--indacene) dyes. Computational studies were carried out in order to reveal the most effective method of modeling of the spectral features of fluorescent BODIPY dyes. To perform these studies, the pyrrole and imidazole derivatives of BODIPY dyes were selected, and their spectral features were investigated with DFT and TD-DFT calculations. The calculations showed that the deprotonation of the substituents leads to a bathochromic shift of the calculated absorption wavelength, while the protonation (imidazole derivative) brings about a hypsochromic shift with respect to the neutral form of the dye. The calculated spectral characteristics, considering the influence of the solvent polarity (PCM model), were correlated with the ETN solvatochromic parameter. These correlations show that the increase in the solvent polarity causes a hypsochromic shift of the calculated absorption and emission wavelengths, whereas the bathochromic shift of the wavelengths is observed for the protonated form.
本文涉及杂环取代基及其质子化和去质子化形式对BODIPY（4,4-二氟-4-硼-3a,4a-二氮杂-茚）染料光谱特性影响的计算机模拟研究。开展计算研究以揭示模拟荧光BODIPY染料光谱特征的最有效方法。为进行这些研究，选择了BODIPY染料的吡咯和咪唑衍生物，并通过密度泛函理论（DFT）和含时密度泛函理论（TD-DFT）计算研究了它们的光谱特征。计算结果表明，取代基的去质子化导致计算出的吸收波长发生红移，而质子化（咪唑衍生物）相对于染料的中性形式导致蓝移。考虑到溶剂极性的影响（极化连续介质模型，PCM），计算出的光谱特征与ETN溶剂化显色参数相关。这些相关性表明，溶剂极性的增加会导致计算出的吸收和发射波长发生蓝移，而质子化形式的波长则会发生红移。
