Singlet fission initiating organic photosensitizations
Abstract The feasibility of singlet fission (SF) in organic photosensitizers is investigated through spin-flip long-range corrected time-dependent density functional theory. This study focuses on four major organic photosensitizer molecules: benzophenone, boron-dipyrromethene, methylene blue, and ro...
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2024-01-01
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| Series: | Scientific Reports |
| Online Access: | https://doi.org/10.1038/s41598-023-50860-4 |
| _version_ | 1797355823189458944 |
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| author | Takao Tsuneda Tetsuya Taketsugu |
| author_facet | Takao Tsuneda Tetsuya Taketsugu |
| author_sort | Takao Tsuneda |
| collection | DOAJ |
| description | Abstract The feasibility of singlet fission (SF) in organic photosensitizers is investigated through spin-flip long-range corrected time-dependent density functional theory. This study focuses on four major organic photosensitizer molecules: benzophenone, boron-dipyrromethene, methylene blue, and rose bengal. Calculations demonstrate that all these molecules possess moderate $$\pi$$ π -stacking energies and closely-lying singlet (S) and quintet (triplet–triplet, TT) excitations, satisfying the essential conditions for SF: (1) Near-degenerate low-lying S and (TT) excitations with a significant S–T energy gap, and (2) Moderate $$\pi$$ π -stacking energy of chromophores, slightly higher than solvation energy, enabling dissociation for triplet-state chromophore generation. Moreover, based on the El-Sayed rule, intersystem crossing is found to simultaneously proceed at very slow rates in all these photosensitizers. This is attributed to the fact that the lowest singlet excitation of the monomers partly involves $$n\pi ^*$$ n π ∗ transitions alongside the main $$\pi \pi ^*$$ π π ∗ transitions. The proposed mechanisms are strongly substantiated by comparisons with experimental studies. |
| first_indexed | 2024-03-08T14:17:42Z |
| format | Article |
| id | doaj.art-ea4acfd1e87140ab852a88106c9f45f1 |
| institution | Directory Open Access Journal |
| issn | 2045-2322 |
| language | English |
| last_indexed | 2024-03-08T14:17:42Z |
| publishDate | 2024-01-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Scientific Reports |
| spelling | doaj.art-ea4acfd1e87140ab852a88106c9f45f12024-01-14T12:20:26ZengNature PortfolioScientific Reports2045-23222024-01-0114111610.1038/s41598-023-50860-4Singlet fission initiating organic photosensitizationsTakao Tsuneda0Tetsuya Taketsugu1Department of Chemistry, Faculty of Science, Hokkaido UniversityDepartment of Chemistry, Faculty of Science, Hokkaido UniversityAbstract The feasibility of singlet fission (SF) in organic photosensitizers is investigated through spin-flip long-range corrected time-dependent density functional theory. This study focuses on four major organic photosensitizer molecules: benzophenone, boron-dipyrromethene, methylene blue, and rose bengal. Calculations demonstrate that all these molecules possess moderate $$\pi$$ π -stacking energies and closely-lying singlet (S) and quintet (triplet–triplet, TT) excitations, satisfying the essential conditions for SF: (1) Near-degenerate low-lying S and (TT) excitations with a significant S–T energy gap, and (2) Moderate $$\pi$$ π -stacking energy of chromophores, slightly higher than solvation energy, enabling dissociation for triplet-state chromophore generation. Moreover, based on the El-Sayed rule, intersystem crossing is found to simultaneously proceed at very slow rates in all these photosensitizers. This is attributed to the fact that the lowest singlet excitation of the monomers partly involves $$n\pi ^*$$ n π ∗ transitions alongside the main $$\pi \pi ^*$$ π π ∗ transitions. The proposed mechanisms are strongly substantiated by comparisons with experimental studies.https://doi.org/10.1038/s41598-023-50860-4 |
| spellingShingle | Takao Tsuneda Tetsuya Taketsugu Singlet fission initiating organic photosensitizations Scientific Reports |
| title | Singlet fission initiating organic photosensitizations |
| title_full | Singlet fission initiating organic photosensitizations |
| title_fullStr | Singlet fission initiating organic photosensitizations |
| title_full_unstemmed | Singlet fission initiating organic photosensitizations |
| title_short | Singlet fission initiating organic photosensitizations |
| title_sort | singlet fission initiating organic photosensitizations |
| url | https://doi.org/10.1038/s41598-023-50860-4 |
| work_keys_str_mv | AT takaotsuneda singletfissioninitiatingorganicphotosensitizations AT tetsuyataketsugu singletfissioninitiatingorganicphotosensitizations |