Molecular stacking controlling coherent and incoherent singlet fission in polymorph rubrene single crystals
Abstract Singlet fission (SF) is an appealing process where one photoexcited singlet transforms to two triplets, which can overcome thermalization energy loss and improve solar cell efficiency. However, it remains unclear how intermolecular coupling, which is subject to molecular stacking, controls...
| Main Authors: | , , , , |
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| Format: | Article |
| Language: | English |
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Wiley
2023-10-01
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| Series: | Aggregate |
| Subjects: | |
| Online Access: | https://doi.org/10.1002/agt2.347 |
| _version_ | 1797653874385879040 |
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| author | Yanping Liu Xuexiao Yang Lei Ye Haibo Ma Haiming Zhu |
| author_facet | Yanping Liu Xuexiao Yang Lei Ye Haibo Ma Haiming Zhu |
| author_sort | Yanping Liu |
| collection | DOAJ |
| description | Abstract Singlet fission (SF) is an appealing process where one photoexcited singlet transforms to two triplets, which can overcome thermalization energy loss and improve solar cell efficiency. However, it remains unclear how intermolecular coupling, which is subject to molecular stacking, controls SF pathways and dynamics. Here, we prepared polymorph rubrene single crystals with different stacking geometries, including orthorhombic (Orth.), triclinic (Tri.), and monoclinic (Mono.) phases. By micro‐area ultrafast spectroscopy, we find that Orth. and Tri. phases with closer π‐π stacking exhibit co‐existing coherent and incoherent SF channels while loosely stacked Mono. phase shows only incoherent SF. Furthermore, incoherent SF is thermally activated in Orth. but barrierless in Mono. and Tri. phases. Quantum mechanical calculation reveals that different electronic coupling strength in different phases leads to different SF dynamics. This study demonstrates that molecular stacking governs SF dynamics through electronic coupling, providing guidance for designing efficient SF materials via crystal structural engineering. |
| first_indexed | 2024-03-11T16:51:06Z |
| format | Article |
| id | doaj.art-26e3fd89d1074c8c9c9add53ab2b9ea8 |
| institution | Directory Open Access Journal |
| issn | 2692-4560 |
| language | English |
| last_indexed | 2024-03-11T16:51:06Z |
| publishDate | 2023-10-01 |
| publisher | Wiley |
| record_format | Article |
| series | Aggregate |
| spelling | doaj.art-26e3fd89d1074c8c9c9add53ab2b9ea82023-10-21T07:53:27ZengWileyAggregate2692-45602023-10-0145n/an/a10.1002/agt2.347Molecular stacking controlling coherent and incoherent singlet fission in polymorph rubrene single crystalsYanping Liu0Xuexiao Yang1Lei Ye2Haibo Ma3Haiming Zhu4State Key Laboratory of Modern Optical Instrumentation, Key Laboratory of Excited‐State Materials of Zhejiang Province, Department of Chemistry Zhejiang University Hangzhou ChinaSchool of Chemistry and Chemical Engineering Nanjing University Nanjing ChinaState Key Laboratory of Modern Optical Instrumentation, Key Laboratory of Excited‐State Materials of Zhejiang Province, Department of Chemistry Zhejiang University Hangzhou ChinaSchool of Chemistry and Chemical Engineering Nanjing University Nanjing ChinaState Key Laboratory of Modern Optical Instrumentation, Key Laboratory of Excited‐State Materials of Zhejiang Province, Department of Chemistry Zhejiang University Hangzhou ChinaAbstract Singlet fission (SF) is an appealing process where one photoexcited singlet transforms to two triplets, which can overcome thermalization energy loss and improve solar cell efficiency. However, it remains unclear how intermolecular coupling, which is subject to molecular stacking, controls SF pathways and dynamics. Here, we prepared polymorph rubrene single crystals with different stacking geometries, including orthorhombic (Orth.), triclinic (Tri.), and monoclinic (Mono.) phases. By micro‐area ultrafast spectroscopy, we find that Orth. and Tri. phases with closer π‐π stacking exhibit co‐existing coherent and incoherent SF channels while loosely stacked Mono. phase shows only incoherent SF. Furthermore, incoherent SF is thermally activated in Orth. but barrierless in Mono. and Tri. phases. Quantum mechanical calculation reveals that different electronic coupling strength in different phases leads to different SF dynamics. This study demonstrates that molecular stacking governs SF dynamics through electronic coupling, providing guidance for designing efficient SF materials via crystal structural engineering.https://doi.org/10.1002/agt2.347electronic couplingsrubrenesinglet fissiontransient absorption spectroscopytriplet pair |
| spellingShingle | Yanping Liu Xuexiao Yang Lei Ye Haibo Ma Haiming Zhu Molecular stacking controlling coherent and incoherent singlet fission in polymorph rubrene single crystals Aggregate electronic couplings rubrene singlet fission transient absorption spectroscopy triplet pair |
| title | Molecular stacking controlling coherent and incoherent singlet fission in polymorph rubrene single crystals |
| title_full | Molecular stacking controlling coherent and incoherent singlet fission in polymorph rubrene single crystals |
| title_fullStr | Molecular stacking controlling coherent and incoherent singlet fission in polymorph rubrene single crystals |
| title_full_unstemmed | Molecular stacking controlling coherent and incoherent singlet fission in polymorph rubrene single crystals |
| title_short | Molecular stacking controlling coherent and incoherent singlet fission in polymorph rubrene single crystals |
| title_sort | molecular stacking controlling coherent and incoherent singlet fission in polymorph rubrene single crystals |
| topic | electronic couplings rubrene singlet fission transient absorption spectroscopy triplet pair |
| url | https://doi.org/10.1002/agt2.347 |
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