Exploring intermolecular singlet fission in pyrene-fused azaacenes film
Singlet fission (SF), a process that involves the conversion of one singlet exciton (S1) into a pair of triplet excitons (T1), holds great technological promise for photovoltaics. Typical SF materials necessitate that the singlet energy (ES1) be at least twice that of the triplet energy (ET1) or th...
| Main Authors: | , , , , , , , , , |
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| Format: | Journal Article |
| Language: | English |
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2023
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| Online Access: | https://hdl.handle.net/10356/171353 |
| _version_ | 1811677728595771392 |
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| author | Guo, Yuanyuan Feng, Minjun Zhang, Zhongbo Ye, Senyun Wang, Yue Zhang, Qiannan Furuhashi, Tomoki Jia, Dongming Zhang, Qichun Sum, Tze Chien |
| author2 | School of Physical and Mathematical Sciences |
| author_facet | School of Physical and Mathematical Sciences Guo, Yuanyuan Feng, Minjun Zhang, Zhongbo Ye, Senyun Wang, Yue Zhang, Qiannan Furuhashi, Tomoki Jia, Dongming Zhang, Qichun Sum, Tze Chien |
| author_sort | Guo, Yuanyuan |
| collection | NTU |
| description | Singlet fission (SF), a process that involves the conversion of one singlet exciton (S1) into a pair of triplet excitons (T1), holds great technological promise for photovoltaics. Typical SF materials necessitate that
the singlet energy (ES1) be at least twice that of the triplet energy (ET1) or that, equivalently, ESd1 be less than twice the singlet−triplet energy splitting (ΔES1−T1). Based on these design principles, we have developed a series of linearly arranged pyrene-fused azaacenes with varying conjugation lengths, featuring four, five, and six aromatic rings. These molecules exhibit distinct excited-state dynamics in both solution and films. With increasing conjugation length, the ES1 values decrease correspondingly from 2.51 to 2.09 eV. Time-resolved spectroscopy and quantum chemistry calculations reveal that ΔES1−T1 increases from 0.38 to 1.13 eV, which is attributed to the increasing molecular frontier orbital overlaps. These systematic trends result in an intersystem crossing in the short-conjugated backbone (four aromatic rings). Conversely, the long-conjugated backbone of six aromatic rings exhibits an ultrafast intermolecular SF process. These findings regarding this newest addition to the collection of SF materials provide guidance on the construction of molecules for desired optoelectronic properties. |
| first_indexed | 2024-10-01T02:41:59Z |
| format | Journal Article |
| id | ntu-10356/171353 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T02:41:59Z |
| publishDate | 2023 |
| record_format | dspace |
| spelling | ntu-10356/1713532023-11-27T15:34:33Z Exploring intermolecular singlet fission in pyrene-fused azaacenes film Guo, Yuanyuan Feng, Minjun Zhang, Zhongbo Ye, Senyun Wang, Yue Zhang, Qiannan Furuhashi, Tomoki Jia, Dongming Zhang, Qichun Sum, Tze Chien School of Physical and Mathematical Sciences School of Materials Science and Engineering Science::Physics::Optics and light Singlet Fission Pyrene-Fused Azaacenes Singlet fission (SF), a process that involves the conversion of one singlet exciton (S1) into a pair of triplet excitons (T1), holds great technological promise for photovoltaics. Typical SF materials necessitate that the singlet energy (ES1) be at least twice that of the triplet energy (ET1) or that, equivalently, ESd1 be less than twice the singlet−triplet energy splitting (ΔES1−T1). Based on these design principles, we have developed a series of linearly arranged pyrene-fused azaacenes with varying conjugation lengths, featuring four, five, and six aromatic rings. These molecules exhibit distinct excited-state dynamics in both solution and films. With increasing conjugation length, the ES1 values decrease correspondingly from 2.51 to 2.09 eV. Time-resolved spectroscopy and quantum chemistry calculations reveal that ΔES1−T1 increases from 0.38 to 1.13 eV, which is attributed to the increasing molecular frontier orbital overlaps. These systematic trends result in an intersystem crossing in the short-conjugated backbone (four aromatic rings). Conversely, the long-conjugated backbone of six aromatic rings exhibits an ultrafast intermolecular SF process. These findings regarding this newest addition to the collection of SF materials provide guidance on the construction of molecules for desired optoelectronic properties. Ministry of Education (MOE) National Research Foundation (NRF) Submitted/Accepted version This research/project was supported by the Ministry of Education under its AcRF Tier 2 grants (MOE-2019-T2-1-006, MOE-2019-T2-1-097, and MOE-T2EP50120-0004) and the National Research Foundation (NRF) Singapore under its NRF Investigatorship (NRF-NRFI2018-04). Q.Z. thanks the funding support from the City University of Hong Kong (9380117, 7005620, and 7020040) and the Hong Kong Institute for Advanced Study, City University of Hong Kong, Hong Kong, P. R. China. D.J. acknowledges funding from the Natural Science Basic Research Program of Shaanxi (2022JQ-062). 2023-11-22T01:20:45Z 2023-11-22T01:20:45Z 2023 Journal Article Guo, Y., Feng, M., Zhang, Z., Ye, S., Wang, Y., Zhang, Q., Furuhashi, T., Jia, D., Zhang, Q. & Sum, T. C. (2023). Exploring intermolecular singlet fission in pyrene-fused azaacenes film. Chemistry of Materials, 35(21), 9040-9049. https://dx.doi.org/10.1021/acs.chemmater.3c01703 0897-4756 https://hdl.handle.net/10356/171353 10.1021/acs.chemmater.3c01703 21 35 9040 9049 en MOE2019-T2-1-006 MOE2019-T2-1-097 MOE-T2EP50120-0004 NRF-NRFI-2018-04 Chemistry of Materials 10.21979/N9/SYCX3M © 2023 American Chemical Society. All rights reserved. This article may be downloaded for personal use only. Any other use requires prior permission of the copyright holder. The Version of Record is available online at http://doi.org/10.1021/acs.chemmater.3c01703. application/pdf application/pdf |
| spellingShingle | Science::Physics::Optics and light Singlet Fission Pyrene-Fused Azaacenes Guo, Yuanyuan Feng, Minjun Zhang, Zhongbo Ye, Senyun Wang, Yue Zhang, Qiannan Furuhashi, Tomoki Jia, Dongming Zhang, Qichun Sum, Tze Chien Exploring intermolecular singlet fission in pyrene-fused azaacenes film |
| title | Exploring intermolecular singlet fission in pyrene-fused azaacenes film |
| title_full | Exploring intermolecular singlet fission in pyrene-fused azaacenes film |
| title_fullStr | Exploring intermolecular singlet fission in pyrene-fused azaacenes film |
| title_full_unstemmed | Exploring intermolecular singlet fission in pyrene-fused azaacenes film |
| title_short | Exploring intermolecular singlet fission in pyrene-fused azaacenes film |
| title_sort | exploring intermolecular singlet fission in pyrene fused azaacenes film |
| topic | Science::Physics::Optics and light Singlet Fission Pyrene-Fused Azaacenes |
| url | https://hdl.handle.net/10356/171353 |
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