Photoinduced Dynamics of 13,13′-Diphenylpropyl-β-carotene
Carotenoids are ubiquitous pigment systems in nature which are relevant to a range of processes, such as photosynthesis, but the detailed influence of substitutions at the polyene backbone on their photophysics is still underexplored. Here, we present a detailed experimental and theoretical investig...
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MDPI AG
2023-04-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/28/8/3505 |
| _version_ | 1797604073252323328 |
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| author | Sangho Koo Yeong Hun Kim Oliver Flender Mirko Scholz Kawon Oum Thomas Lenzer |
| author_facet | Sangho Koo Yeong Hun Kim Oliver Flender Mirko Scholz Kawon Oum Thomas Lenzer |
| author_sort | Sangho Koo |
| collection | DOAJ |
| description | Carotenoids are ubiquitous pigment systems in nature which are relevant to a range of processes, such as photosynthesis, but the detailed influence of substitutions at the polyene backbone on their photophysics is still underexplored. Here, we present a detailed experimental and theoretical investigation of the carotenoid 13,13′-diphenylpropyl-β-carotene using ultrafast transient absorption spectroscopy and steady-state absorption experiments in <i>n</i>-hexane and <i>n</i>-hexadecane, complemented by DFT/TDDFT calculations. In spite of their bulkiness and their potential capability to “fold back” onto the polyene system, which could result in π-stacking effects, the phenylpropyl residues have only a minor impact on the photophysical properties compared with the parent compound β-carotene. Ultrafast spectroscopy finds lifetimes of 200–300 fs for the S<sub>2</sub> state and 8.3–9.5 ps for the S<sub>1</sub> state. Intramolecular vibrational redistribution with time constants in the range 0.6–1.4 ps is observed in terms of a spectral narrowing of the S<sub>1</sub> spectrum over time. We also find clear indications of the presence of vibrationally hot molecules in the ground electronic state (S<sub>0</sub>*). The DFT/TDDFT calculations confirm that the propyl spacer electronically decouples the phenyl and polyene π-systems and that the substituents in the 13 and 13′ positions point away from the polyene system. |
| first_indexed | 2024-03-11T04:41:10Z |
| format | Article |
| id | doaj.art-1340e3afe64e46b086eb933105e34732 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-11T04:41:10Z |
| publishDate | 2023-04-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-1340e3afe64e46b086eb933105e347322023-11-17T20:39:56ZengMDPI AGMolecules1420-30492023-04-01288350510.3390/molecules28083505Photoinduced Dynamics of 13,13′-Diphenylpropyl-β-caroteneSangho Koo0Yeong Hun Kim1Oliver Flender2Mirko Scholz3Kawon Oum4Thomas Lenzer5Department of Chemistry, Myongji University, Myongji-Ro 116, Cheoin-Gu, Yongin 17058, Gyeonggi-Do, Republic of KoreaDepartment of Chemistry, Myongji University, Myongji-Ro 116, Cheoin-Gu, Yongin 17058, Gyeonggi-Do, Republic of KoreaPhysical Chemistry 2, Department Chemistry and Biology, Faculty IV: School of Science and Technology, University of Siegen, Adolf-Reichwein-Str. 2, 57076 Siegen, GermanyPhysical Chemistry 2, Department Chemistry and Biology, Faculty IV: School of Science and Technology, University of Siegen, Adolf-Reichwein-Str. 2, 57076 Siegen, GermanyPhysical Chemistry 2, Department Chemistry and Biology, Faculty IV: School of Science and Technology, University of Siegen, Adolf-Reichwein-Str. 2, 57076 Siegen, GermanyPhysical Chemistry 2, Department Chemistry and Biology, Faculty IV: School of Science and Technology, University of Siegen, Adolf-Reichwein-Str. 2, 57076 Siegen, GermanyCarotenoids are ubiquitous pigment systems in nature which are relevant to a range of processes, such as photosynthesis, but the detailed influence of substitutions at the polyene backbone on their photophysics is still underexplored. Here, we present a detailed experimental and theoretical investigation of the carotenoid 13,13′-diphenylpropyl-β-carotene using ultrafast transient absorption spectroscopy and steady-state absorption experiments in <i>n</i>-hexane and <i>n</i>-hexadecane, complemented by DFT/TDDFT calculations. In spite of their bulkiness and their potential capability to “fold back” onto the polyene system, which could result in π-stacking effects, the phenylpropyl residues have only a minor impact on the photophysical properties compared with the parent compound β-carotene. Ultrafast spectroscopy finds lifetimes of 200–300 fs for the S<sub>2</sub> state and 8.3–9.5 ps for the S<sub>1</sub> state. Intramolecular vibrational redistribution with time constants in the range 0.6–1.4 ps is observed in terms of a spectral narrowing of the S<sub>1</sub> spectrum over time. We also find clear indications of the presence of vibrationally hot molecules in the ground electronic state (S<sub>0</sub>*). The DFT/TDDFT calculations confirm that the propyl spacer electronically decouples the phenyl and polyene π-systems and that the substituents in the 13 and 13′ positions point away from the polyene system.https://www.mdpi.com/1420-3049/28/8/3505carotenoidsultrafast laser spectroscopyDFT/TDDFT calculations |
| spellingShingle | Sangho Koo Yeong Hun Kim Oliver Flender Mirko Scholz Kawon Oum Thomas Lenzer Photoinduced Dynamics of 13,13′-Diphenylpropyl-β-carotene Molecules carotenoids ultrafast laser spectroscopy DFT/TDDFT calculations |
| title | Photoinduced Dynamics of 13,13′-Diphenylpropyl-β-carotene |
| title_full | Photoinduced Dynamics of 13,13′-Diphenylpropyl-β-carotene |
| title_fullStr | Photoinduced Dynamics of 13,13′-Diphenylpropyl-β-carotene |
| title_full_unstemmed | Photoinduced Dynamics of 13,13′-Diphenylpropyl-β-carotene |
| title_short | Photoinduced Dynamics of 13,13′-Diphenylpropyl-β-carotene |
| title_sort | photoinduced dynamics of 13 13 diphenylpropyl β carotene |
| topic | carotenoids ultrafast laser spectroscopy DFT/TDDFT calculations |
| url | https://www.mdpi.com/1420-3049/28/8/3505 |
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