The controllable of BODIPY dimers without installing blocking groups as both fluorescence and singlet oxygen generators
Abstract We compared a range of BODIPY dimer derivatives without installing blocking groups by optimizing geometry structures and analyzing energies, frontier molecular orbitals, Chole&Cele map, electron density difference, spin‐orbit coupling (SOC) matrix and decay rate constants from excited s...
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| Format: | Article |
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Wiley
2025-03-01
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| Series: | Smart Molecules |
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| Online Access: | https://doi.org/10.1002/smo.20240023 |
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| author | Jianfang Cao Tianci Zhang Xinyu Chen Xue Ma Jiangli Fan |
| author_facet | Jianfang Cao Tianci Zhang Xinyu Chen Xue Ma Jiangli Fan |
| author_sort | Jianfang Cao |
| collection | DOAJ |
| description | Abstract We compared a range of BODIPY dimer derivatives without installing blocking groups by optimizing geometry structures and analyzing energies, frontier molecular orbitals, Chole&Cele map, electron density difference, spin‐orbit coupling (SOC) matrix and decay rate constants from excited states. The dihedral angles of the β‐β‐linked BODIPY dimer and the α‐α‐linked BODIPY dimer tend to flatten in the T1 state, which is detrimental to the occurrence of the intersystem crossing (ISC). Conversely, the dihedral angle of the meso‐β‐linked BODIPY dimer, the meso‐meso‐linked BODIPY dimer and α‐γ‐linked BODIPY dimer is within the range of 125°–143° in the T1 state, facilitating ISC and the generation of singlet oxygen. Notably, the transition from S1 to S0 involving lowest unoccupied molecular orbital to highest occupied molecular orbital with long‐wavelength emission and moderate oscillator strength underpins the remarkable long emission peaks observed experimentally for α‐γ‐linked BODIPY dimer. Moreover, the apparent SOC matrix enhances the ISC process, resulting in a respectable efficiency in generating singlet oxygen for this dimer. In meso‐β‐linked BODIPY, meso‐meso‐linked BODIPY, and α‐γ‐linked BODIPY, the S1→T1 process is characterized by a significant charge transfer, specifically transitioning from the 1CT state to the 3LE state, indicative of a spin‐orbit charge transfer ISC (SOCT‐ISC) mechanism. The ability to regulate the photosensitivity of BODIPY dimers by adjusting the dihedral angle between the two units in the T1 state unveils new avenues for designing high‐performance photosensitizers for both therapeutic and imaging applications. |
| format | Article |
| id | doaj-art-a7092e9a8be247a4b7b5059b6703f45d |
| institution | Kabale University |
| issn | 2751-4587 2751-4595 |
| language | English |
| publishDate | 2025-03-01 |
| publisher | Wiley |
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| series | Smart Molecules |
| spelling | doaj-art-a7092e9a8be247a4b7b5059b6703f45d2025-08-20T03:41:15ZengWileySmart Molecules2751-45872751-45952025-03-0131n/an/a10.1002/smo.20240023The controllable of BODIPY dimers without installing blocking groups as both fluorescence and singlet oxygen generatorsJianfang Cao0Tianci Zhang1Xinyu Chen2Xue Ma3Jiangli Fan4School of Chemical Engineering Ocean and Life Sciences Dalian University of Technology Panjin ChinaSchool of Chemical Engineering Ocean and Life Sciences Dalian University of Technology Panjin ChinaSchool of Chemical Engineering Ocean and Life Sciences Dalian University of Technology Panjin ChinaSchool of Chemical Engineering Ocean and Life Sciences Dalian University of Technology Panjin ChinaState Key Laboratory of Fine Chemicals Dalian University of Technology Dalian ChinaAbstract We compared a range of BODIPY dimer derivatives without installing blocking groups by optimizing geometry structures and analyzing energies, frontier molecular orbitals, Chole&Cele map, electron density difference, spin‐orbit coupling (SOC) matrix and decay rate constants from excited states. The dihedral angles of the β‐β‐linked BODIPY dimer and the α‐α‐linked BODIPY dimer tend to flatten in the T1 state, which is detrimental to the occurrence of the intersystem crossing (ISC). Conversely, the dihedral angle of the meso‐β‐linked BODIPY dimer, the meso‐meso‐linked BODIPY dimer and α‐γ‐linked BODIPY dimer is within the range of 125°–143° in the T1 state, facilitating ISC and the generation of singlet oxygen. Notably, the transition from S1 to S0 involving lowest unoccupied molecular orbital to highest occupied molecular orbital with long‐wavelength emission and moderate oscillator strength underpins the remarkable long emission peaks observed experimentally for α‐γ‐linked BODIPY dimer. Moreover, the apparent SOC matrix enhances the ISC process, resulting in a respectable efficiency in generating singlet oxygen for this dimer. In meso‐β‐linked BODIPY, meso‐meso‐linked BODIPY, and α‐γ‐linked BODIPY, the S1→T1 process is characterized by a significant charge transfer, specifically transitioning from the 1CT state to the 3LE state, indicative of a spin‐orbit charge transfer ISC (SOCT‐ISC) mechanism. The ability to regulate the photosensitivity of BODIPY dimers by adjusting the dihedral angle between the two units in the T1 state unveils new avenues for designing high‐performance photosensitizers for both therapeutic and imaging applications.https://doi.org/10.1002/smo.20240023BODIPY dimersdensity functional calculationsdual‐functioning photosensitizersspin‐orbit coupling |
| spellingShingle | Jianfang Cao Tianci Zhang Xinyu Chen Xue Ma Jiangli Fan The controllable of BODIPY dimers without installing blocking groups as both fluorescence and singlet oxygen generators Smart Molecules BODIPY dimers density functional calculations dual‐functioning photosensitizers spin‐orbit coupling |
| title | The controllable of BODIPY dimers without installing blocking groups as both fluorescence and singlet oxygen generators |
| title_full | The controllable of BODIPY dimers without installing blocking groups as both fluorescence and singlet oxygen generators |
| title_fullStr | The controllable of BODIPY dimers without installing blocking groups as both fluorescence and singlet oxygen generators |
| title_full_unstemmed | The controllable of BODIPY dimers without installing blocking groups as both fluorescence and singlet oxygen generators |
| title_short | The controllable of BODIPY dimers without installing blocking groups as both fluorescence and singlet oxygen generators |
| title_sort | controllable of bodipy dimers without installing blocking groups as both fluorescence and singlet oxygen generators |
| topic | BODIPY dimers density functional calculations dual‐functioning photosensitizers spin‐orbit coupling |
| url | https://doi.org/10.1002/smo.20240023 |
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