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Recently, a series of 8(meso)-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 meso-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 meso-2-pyridyl-BODIPY structure.
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8(meso)-Pyridyl-BODIPYs: Effects of 2,6-Substitution with Electron-Withdrawing Nitro, Chloro, and Methoxycarbonyl Groups
The introduction of electron-withdrawing groups on 8(meso)-pyridyl-BODIPYs tends to increase the fluorescence quantum yields of this type of compound due to the decrease in electronic charge density on the BODIPY core. A new series of 8(meso)-pyridyl-BODIPYs bearing a 2-, 3-, or 4-pyridyl group was synthesized and functionalized with nitro and chlorine groups at the 2,6-positions. The 2,6-methoxycarbonyl-8-pyridyl-BODIPYs analogs were also synthesized by condensation of 2,4-dimethyl-3-methoxycarbonyl-pyrrole with 2-, 3-, or 4-formylpyridine followed by oxidation and boron complexation. The structures and spectroscopic properties of the new series of 8(meso)-pyridyl-BODIPYs were investigated both experimentally and computationally. The BODIPYs bearing 2,6-methoxycarbonyl groups showed enhanced relative fluorescence quantum yields in polar organic solvents due to their electron-withdrawing effect. However, the introduction of a single nitro group significantly quenched the fluorescence of the BODIPYs and caused hypsochromic shifts in the absorption and emission bands. The introduction of a chloro substituent partially restored the fluorescence of the mono-nitro-BODIPYs and induced significant bathochromic shifts.
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- PAR ID:
- 10425624
- Date Published:
- Journal Name:
- Molecules
- Volume:
- 28
- Issue:
- 12
- ISSN:
- 1420-3049
- Page Range / eLocation ID:
- 4581
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.3390/molecules28124581
