Substituent Effects on the Photophysical Properties of a Series of 8(<i>meso</i>)-Pyridyl-BODIPYs: A Computational Analysis of the Experimental Data

Recently, a series of 8(<i>meso</i>)-pyridyl-BODIPYs (2-pyridyl, 3-pyridyl, and 4-pyridyl) and their 2,6-substituted derivatives were synthesized and their structure and photophysical properties were studied both experimentally and computationally. One of the main observed trends was tha...

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Main Authors: Petia Bobadova-Parvanova, Dylan Goliber, Elijuah Hernandez, Daniel LaMaster, Maria da Graça H. Vicente
Format: Article
Language:English
Published: MDPI AG 2024-11-01
Series:Physchem
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Online Access:https://www.mdpi.com/2673-7167/4/4/34
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Summary:Recently, a series of 8(<i>meso</i>)-pyridyl-BODIPYs (2-pyridyl, 3-pyridyl, and 4-pyridyl) and their 2,6-substituted derivatives were synthesized and their structure and photophysical properties were studied both experimentally and computationally. One of the main observed trends was that the 2-pyridyl-BODIPYs were consistently less fluorescent than their 3-pyridyl and 4-pyridyl analogs, regardless of the 2,6-substituents. Herein, we extend our previous computational studies and model not only the ground but also the excited states of the entire series of previously synthesized <i>meso</i>-pyridyl-BODIPYs with the aim of explaining the observed differences in the emission quantum yields. To better understand the trends and the effect of 2- and 2,6-substitution on the photophysical and electron-density-related properties, we also model the ground and excited states of BODIPYs that were not synthesized experimentally, however represent a logical part of the series. We calculate a variety of molecular properties and propose that the experimentally observed low quantum yields for all 2-pyridyl-BODIPYs could be due to the very flat potential energy surfaces with respect to the rotation of the 2-pyridyl ring in the excited states, and the stability of a non-planar and significantly less fluorescent <i>meso</i>-2-pyridyl-BODIPY structure.
ISSN:2673-7167