Cross-linked polyphosphazene nanospheres boosting long-lived organic room-temperature phosphorescence
Long-lived organic room-temperature phosphorescence (RTP) has sparked intense explorations, owing to the outstanding optical performance and exceptional applications. Because triplet excitons in organic RTP experience multifarious relaxation processes resulting from their high sensitivity, spin mult...
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sg-ntu-dr.10356-1617452022-09-19T02:44:30Z Cross-linked polyphosphazene nanospheres boosting long-lived organic room-temperature phosphorescence Zhang, Yongfeng Chen, Xiaohong Xu, Jianrong Zhang, Qinglun Gao, Liang Wang, Zhonghao Qu, Lunjun Wang, Kaiti Li, Youbing Cai, Zhengxu Zhao, Yanli Yang, Chaolong School of Physical and Mathematical Sciences Science::Chemistry Nonradiative Decays Phosphorescence Materials Long-lived organic room-temperature phosphorescence (RTP) has sparked intense explorations, owing to the outstanding optical performance and exceptional applications. Because triplet excitons in organic RTP experience multifarious relaxation processes resulting from their high sensitivity, spin multiplicity, inevitable nonradiative decay, and external quenchers, boosting RTP performance by the modulated triplet-exciton behavior is challenging. Herein, we report that cross-linked polyphosphazene nanospheres can effectively promote long-lived organic RTP. Through molecular engineering, multiple carbonyl groups (C═O), heteroatoms (N and P), and heavy atoms (Cl) are introduced into the polyphosphazene nanospheres, largely strengthening the spin-orbit coupling constant by recalibrating the electronic configurations between singlet (Sn) and triplet (Tn) excitons. In order to further suppress nonradiative decay and avoid quenching under ambient conditions, polyphosphazene nanospheres are encapsulated with poly(vinyl alcohol) matrix, thus synchronously prompting phosphorescence lifetime (173 ms longer), phosphorescence efficiency (∼12-fold higher), afterglow duration time (more than 20 s), and afterglow absolute luminance (∼19-fold higher) as compared with the 2,3,6,7,10,11-hexahydroxytriphenylene precursor. By measuring the emission intensity of the phosphorescence, an effective probe based on the nanospheres is developed for visible, quantitative, and expeditious detection of volatile organic compounds. More significantly, the obtained films show high selectivity and robustness for anisole detection (7.1 × 10-4 mol L-1). This work not only demonstrates a way toward boosting the efficiency of RTP materials but also provides a new avenue to apply RTP materials in feasible detection applications. Ministry of Education (MOE) This work was financially supported by the National Natural Science Foundation of China (21875025), the Innovation Research Group at Institutions of Higher Education in Chongqing (CXQT19027), the Chongqing Talent Program, the Science and Technology Project of Banan District, the Innovation Support Plan for the Returned Overseas of Chongqing (cx2020052), and the Open Fund of Guangdong Provincial Key Laboratory of Luminescence from Molecular Aggregates (2021-kllma-03). The research was also supported by the Singapore Ministry of Education Academic Research Funds (RG3/21 and MOET2EP10120-0003). 2022-09-19T02:44:30Z 2022-09-19T02:44:30Z 2022 Journal Article Zhang, Y., Chen, X., Xu, J., Zhang, Q., Gao, L., Wang, Z., Qu, L., Wang, K., Li, Y., Cai, Z., Zhao, Y. & Yang, C. (2022). Cross-linked polyphosphazene nanospheres boosting long-lived organic room-temperature phosphorescence. Journal of the American Chemical Society, 144(13), 6107-6117. https://dx.doi.org/10.1021/jacs.2c02076 0002-7863 https://hdl.handle.net/10356/161745 10.1021/jacs.2c02076 35316063 2-s2.0-85127566024 13 144 6107 6117 en RG3/21 MOET2EP10120-0003 Journal of the American Chemical Society © 2022 American Chemical Society. All rights reserved. |
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Science::Chemistry Nonradiative Decays Phosphorescence Materials Zhang, Yongfeng Chen, Xiaohong Xu, Jianrong Zhang, Qinglun Gao, Liang Wang, Zhonghao Qu, Lunjun Wang, Kaiti Li, Youbing Cai, Zhengxu Zhao, Yanli Yang, Chaolong Cross-linked polyphosphazene nanospheres boosting long-lived organic room-temperature phosphorescence |
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Long-lived organic room-temperature phosphorescence (RTP) has sparked intense explorations, owing to the outstanding optical performance and exceptional applications. Because triplet excitons in organic RTP experience multifarious relaxation processes resulting from their high sensitivity, spin multiplicity, inevitable nonradiative decay, and external quenchers, boosting RTP performance by the modulated triplet-exciton behavior is challenging. Herein, we report that cross-linked polyphosphazene nanospheres can effectively promote long-lived organic RTP. Through molecular engineering, multiple carbonyl groups (C═O), heteroatoms (N and P), and heavy atoms (Cl) are introduced into the polyphosphazene nanospheres, largely strengthening the spin-orbit coupling constant by recalibrating the electronic configurations between singlet (Sn) and triplet (Tn) excitons. In order to further suppress nonradiative decay and avoid quenching under ambient conditions, polyphosphazene nanospheres are encapsulated with poly(vinyl alcohol) matrix, thus synchronously prompting phosphorescence lifetime (173 ms longer), phosphorescence efficiency (∼12-fold higher), afterglow duration time (more than 20 s), and afterglow absolute luminance (∼19-fold higher) as compared with the 2,3,6,7,10,11-hexahydroxytriphenylene precursor. By measuring the emission intensity of the phosphorescence, an effective probe based on the nanospheres is developed for visible, quantitative, and expeditious detection of volatile organic compounds. More significantly, the obtained films show high selectivity and robustness for anisole detection (7.1 × 10-4 mol L-1). This work not only demonstrates a way toward boosting the efficiency of RTP materials but also provides a new avenue to apply RTP materials in feasible detection applications. |
author2 |
School of Physical and Mathematical Sciences |
author_facet |
School of Physical and Mathematical Sciences Zhang, Yongfeng Chen, Xiaohong Xu, Jianrong Zhang, Qinglun Gao, Liang Wang, Zhonghao Qu, Lunjun Wang, Kaiti Li, Youbing Cai, Zhengxu Zhao, Yanli Yang, Chaolong |
format |
Article |
author |
Zhang, Yongfeng Chen, Xiaohong Xu, Jianrong Zhang, Qinglun Gao, Liang Wang, Zhonghao Qu, Lunjun Wang, Kaiti Li, Youbing Cai, Zhengxu Zhao, Yanli Yang, Chaolong |
author_sort |
Zhang, Yongfeng |
title |
Cross-linked polyphosphazene nanospheres boosting long-lived organic room-temperature phosphorescence |
title_short |
Cross-linked polyphosphazene nanospheres boosting long-lived organic room-temperature phosphorescence |
title_full |
Cross-linked polyphosphazene nanospheres boosting long-lived organic room-temperature phosphorescence |
title_fullStr |
Cross-linked polyphosphazene nanospheres boosting long-lived organic room-temperature phosphorescence |
title_full_unstemmed |
Cross-linked polyphosphazene nanospheres boosting long-lived organic room-temperature phosphorescence |
title_sort |
cross-linked polyphosphazene nanospheres boosting long-lived organic room-temperature phosphorescence |
publishDate |
2022 |
url |
https://hdl.handle.net/10356/161745 |
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1745574646937288704 |