Excited state dynamics of azanaphthalenes reveal opportunities for the rational design of photoactive molecules
Abstract Various photoactive molecules contain motifs built on aza-aromatic heterocycles, although a detailed understanding of the excited state photophysics and photochemistry in such systems is not fully developed. To help address this issue, the non-adiabatic dynamics operating in azanaphthalenes...
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| Format: | Article |
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Nature Portfolio
2025-01-01
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| Series: | Communications Chemistry |
| Online Access: | https://doi.org/10.1038/s42004-024-01403-z |
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| author | Malcolm Garrow Lauren Bertram Abi Winter Andrew W. Prentice Stuart W. Crane Paul D. Lane Stuart J. Greaves Martin J. Paterson Adam Kirrander Dave Townsend |
| author_facet | Malcolm Garrow Lauren Bertram Abi Winter Andrew W. Prentice Stuart W. Crane Paul D. Lane Stuart J. Greaves Martin J. Paterson Adam Kirrander Dave Townsend |
| author_sort | Malcolm Garrow |
| collection | DOAJ |
| description | Abstract Various photoactive molecules contain motifs built on aza-aromatic heterocycles, although a detailed understanding of the excited state photophysics and photochemistry in such systems is not fully developed. To help address this issue, the non-adiabatic dynamics operating in azanaphthalenes under hexane solvation was studied following 267 nm excitation using ultrafast transient absorption spectroscopy. Specifically, the species quinoline, isoquinoline, quinazoline, quinoxaline, 1,6-naphthyridine, and 1,8-naphthyridine were investigated, providing a systematic variation in the relative positioning of nitrogen heteroatom centres within a bicyclic aromatic structure. Our results indicate considerable differences in excited state lifetimes, and in the propensity for intersystem crossing vs internal conversion across the molecular series. The overall pattern of behaviour can be explained in terms of potential energy barriers and spin-orbit coupling effects, as demonstrated by extensive quantum chemistry calculations undertaken at the SCS-ADC(2) level of theory. The fact that quantum chemistry calculations can achieve such detailed and nuanced agreement with experimental data across a full set of six molecules exhibiting subtle variations in their composition provides an excellent example of the current state-of-the-art and is indicative of future opportunities for rational design of photoactive molecules. |
| format | Article |
| id | doaj-art-a1bc9ef1f9ff4db596a13273a19a6317 |
| institution | Kabale University |
| issn | 2399-3669 |
| language | English |
| publishDate | 2025-01-01 |
| publisher | Nature Portfolio |
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| series | Communications Chemistry |
| spelling | doaj-art-a1bc9ef1f9ff4db596a13273a19a63172025-01-12T12:11:17ZengNature PortfolioCommunications Chemistry2399-36692025-01-018111110.1038/s42004-024-01403-zExcited state dynamics of azanaphthalenes reveal opportunities for the rational design of photoactive moleculesMalcolm Garrow0Lauren Bertram1Abi Winter2Andrew W. Prentice3Stuart W. Crane4Paul D. Lane5Stuart J. Greaves6Martin J. Paterson7Adam Kirrander8Dave Townsend9Institute of Chemical Sciences, Heriot-Watt UniversityPhysical and Theoretical Chemistry Laboratory, Department of Chemistry, University of OxfordInstitute of Photonics & Quantum Sciences, Heriot-Watt UniversityInstitute of Chemical Sciences, Heriot-Watt UniversityInstitute of Photonics & Quantum Sciences, Heriot-Watt UniversityInstitute of Chemical Sciences, Heriot-Watt UniversityInstitute of Chemical Sciences, Heriot-Watt UniversityInstitute of Chemical Sciences, Heriot-Watt UniversityPhysical and Theoretical Chemistry Laboratory, Department of Chemistry, University of OxfordInstitute of Chemical Sciences, Heriot-Watt UniversityAbstract Various photoactive molecules contain motifs built on aza-aromatic heterocycles, although a detailed understanding of the excited state photophysics and photochemistry in such systems is not fully developed. To help address this issue, the non-adiabatic dynamics operating in azanaphthalenes under hexane solvation was studied following 267 nm excitation using ultrafast transient absorption spectroscopy. Specifically, the species quinoline, isoquinoline, quinazoline, quinoxaline, 1,6-naphthyridine, and 1,8-naphthyridine were investigated, providing a systematic variation in the relative positioning of nitrogen heteroatom centres within a bicyclic aromatic structure. Our results indicate considerable differences in excited state lifetimes, and in the propensity for intersystem crossing vs internal conversion across the molecular series. The overall pattern of behaviour can be explained in terms of potential energy barriers and spin-orbit coupling effects, as demonstrated by extensive quantum chemistry calculations undertaken at the SCS-ADC(2) level of theory. The fact that quantum chemistry calculations can achieve such detailed and nuanced agreement with experimental data across a full set of six molecules exhibiting subtle variations in their composition provides an excellent example of the current state-of-the-art and is indicative of future opportunities for rational design of photoactive molecules.https://doi.org/10.1038/s42004-024-01403-z |
| spellingShingle | Malcolm Garrow Lauren Bertram Abi Winter Andrew W. Prentice Stuart W. Crane Paul D. Lane Stuart J. Greaves Martin J. Paterson Adam Kirrander Dave Townsend Excited state dynamics of azanaphthalenes reveal opportunities for the rational design of photoactive molecules Communications Chemistry |
| title | Excited state dynamics of azanaphthalenes reveal opportunities for the rational design of photoactive molecules |
| title_full | Excited state dynamics of azanaphthalenes reveal opportunities for the rational design of photoactive molecules |
| title_fullStr | Excited state dynamics of azanaphthalenes reveal opportunities for the rational design of photoactive molecules |
| title_full_unstemmed | Excited state dynamics of azanaphthalenes reveal opportunities for the rational design of photoactive molecules |
| title_short | Excited state dynamics of azanaphthalenes reveal opportunities for the rational design of photoactive molecules |
| title_sort | excited state dynamics of azanaphthalenes reveal opportunities for the rational design of photoactive molecules |
| url | https://doi.org/10.1038/s42004-024-01403-z |
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