Long-lived organic room-temperature phosphorescence from amorphous polymer systems

Long-lived organic room-temperature phosphorescence (RTP) materials have recently drawn extensive attention because of their promising applications in information security, biological imaging, optoelectronic devices, and intelligent sensors. In contrast to conventional fluorescence, the RTP phenomen...

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Main Authors: Guo, Jingjing, Yang, Chaolong, Zhao, Yanli
Other Authors: School of Materials Science and Engineering
Format: Journal Article
Language:English
Published: 2022
Subjects:
Online Access:https://hdl.handle.net/10356/162484
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author Guo, Jingjing
Yang, Chaolong
Zhao, Yanli
author2 School of Materials Science and Engineering
author_facet School of Materials Science and Engineering
Guo, Jingjing
Yang, Chaolong
Zhao, Yanli
author_sort Guo, Jingjing
collection NTU
description Long-lived organic room-temperature phosphorescence (RTP) materials have recently drawn extensive attention because of their promising applications in information security, biological imaging, optoelectronic devices, and intelligent sensors. In contrast to conventional fluorescence, the RTP phenomenon originates from the slow radiative transition of triplet excitons. Thus, enhancing the intersystem crossing (ISC) rate from the lowest excited singlet state (S1) to the excited triplet state and suppressing the nonradiative relaxation channels of the lowest excited triplet state (T1) are reasonable methods for realizing highly efficient RTP in purely organic materials. Over the past few decades, many strategies have been designed on the basis of the above two crucial factors. The introduction of heavy atoms, aromatic carbonyl groups, and other heteroatoms with abundant lone-pair electrons has been demonstrated to strengthen the spin-orbit coupling, thereby successfully facilitating the ISC process. Furthermore, the rigid environment is commonly constructed through crystal engineering to restrict intramolecular motions and intermolecular collisions to decrease excited-state energy dissipation. However, most crystal-based organic RTP materials suffer from poor processability, flexibility, and reproducibility, becoming a thorny obstacle to their practical application.Amorphous organic polymers with long-lived RTP characteristics are more competitive in materials science. The intertwined structures and long chains of polymers not only ensure the rigid environment with multiple interactions but also protect triplet excitons from the surroundings, which are conducive to realizing ultralong and bright RTP emission. Exploring the fabrication strategies, intrinsic mechanisms, and practical applications of organic long-lived RTP polymers is highly desirable but remains a formidable challenge. In particular, intelligent organic RTP polymer systems that are capable of dynamically responding to external stimuli (e.g., light, temperature, oxygen, and humidity) have been rarely reported. To develop multifunctional RTP materials and expand their potential applications, a great amount of effort has been expended.This Account gives a summary of the significant advances in amorphous organic RTP polymer systems, especially smart stimulus-responsive ones, focusing on the construction of a rigid environment to suppress nonradiative deactivation by abundant inter/intramolecular interactions. The typical interactions in RTP polymer systems mainly include hydrogen bonding, ionic bonding, and covalent bonding, which can change the molecular electronic structures and affect the energy dissipation channels of the excited states. An in-depth understanding of intrinsic mechanisms and an extensive exploration of potential applications for excitation-dependent color-tunable, ultraviolet (UV) irradiation-activated, temperature-dependent, water-responsive, and circularly polarized RTP polymer systems are distinctly illustrated in this Account. Furthermore, we propose some detailed perspectives in terms of materials design, mechanism exploration, and promising application potential with the hope to provide helpful guidance for the future development of amorphous organic RTP polymers.
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spelling ntu-10356/1624842022-10-25T03:08:58Z Long-lived organic room-temperature phosphorescence from amorphous polymer systems Guo, Jingjing Yang, Chaolong Zhao, Yanli School of Materials Science and Engineering School of Physical and Mathematical Sciences Engineering::Materials Science::Chemistry Hydrogen Bond Reproducibility Long-lived organic room-temperature phosphorescence (RTP) materials have recently drawn extensive attention because of their promising applications in information security, biological imaging, optoelectronic devices, and intelligent sensors. In contrast to conventional fluorescence, the RTP phenomenon originates from the slow radiative transition of triplet excitons. Thus, enhancing the intersystem crossing (ISC) rate from the lowest excited singlet state (S1) to the excited triplet state and suppressing the nonradiative relaxation channels of the lowest excited triplet state (T1) are reasonable methods for realizing highly efficient RTP in purely organic materials. Over the past few decades, many strategies have been designed on the basis of the above two crucial factors. The introduction of heavy atoms, aromatic carbonyl groups, and other heteroatoms with abundant lone-pair electrons has been demonstrated to strengthen the spin-orbit coupling, thereby successfully facilitating the ISC process. Furthermore, the rigid environment is commonly constructed through crystal engineering to restrict intramolecular motions and intermolecular collisions to decrease excited-state energy dissipation. However, most crystal-based organic RTP materials suffer from poor processability, flexibility, and reproducibility, becoming a thorny obstacle to their practical application.Amorphous organic polymers with long-lived RTP characteristics are more competitive in materials science. The intertwined structures and long chains of polymers not only ensure the rigid environment with multiple interactions but also protect triplet excitons from the surroundings, which are conducive to realizing ultralong and bright RTP emission. Exploring the fabrication strategies, intrinsic mechanisms, and practical applications of organic long-lived RTP polymers is highly desirable but remains a formidable challenge. In particular, intelligent organic RTP polymer systems that are capable of dynamically responding to external stimuli (e.g., light, temperature, oxygen, and humidity) have been rarely reported. To develop multifunctional RTP materials and expand their potential applications, a great amount of effort has been expended.This Account gives a summary of the significant advances in amorphous organic RTP polymer systems, especially smart stimulus-responsive ones, focusing on the construction of a rigid environment to suppress nonradiative deactivation by abundant inter/intramolecular interactions. The typical interactions in RTP polymer systems mainly include hydrogen bonding, ionic bonding, and covalent bonding, which can change the molecular electronic structures and affect the energy dissipation channels of the excited states. An in-depth understanding of intrinsic mechanisms and an extensive exploration of potential applications for excitation-dependent color-tunable, ultraviolet (UV) irradiation-activated, temperature-dependent, water-responsive, and circularly polarized RTP polymer systems are distinctly illustrated in this Account. Furthermore, we propose some detailed perspectives in terms of materials design, mechanism exploration, and promising application potential with the hope to provide helpful guidance for the future development of amorphous organic RTP polymers. Ministry of Education (MOE) National Research Foundation (NRF) This research is supported by the National Natural Science Foundation of China (21875025), the Singapore National Research Foundation Investigatorship (NRF-NRFI2018-03), and the Ministry of Education Singapore under the Academic Research Funds (RG3/21 and MOET2EP10120-0003). 2022-10-25T03:08:58Z 2022-10-25T03:08:58Z 2022 Journal Article Guo, J., Yang, C. & Zhao, Y. (2022). Long-lived organic room-temperature phosphorescence from amorphous polymer systems. Accounts of Chemical Research, 55(8), 1160-1170. https://dx.doi.org/10.1021/acs.accounts.2c00038 0001-4842 https://hdl.handle.net/10356/162484 10.1021/acs.accounts.2c00038 35394748 2-s2.0-85128529001 8 55 1160 1170 en NRF-NRFI2018-03 RG3/21 MOET2EP10120-0003 Accounts of Chemical Research © 2022 American Chemical Society. All rights reserved.
spellingShingle Engineering::Materials
Science::Chemistry
Hydrogen Bond
Reproducibility
Guo, Jingjing
Yang, Chaolong
Zhao, Yanli
Long-lived organic room-temperature phosphorescence from amorphous polymer systems
title Long-lived organic room-temperature phosphorescence from amorphous polymer systems
title_full Long-lived organic room-temperature phosphorescence from amorphous polymer systems
title_fullStr Long-lived organic room-temperature phosphorescence from amorphous polymer systems
title_full_unstemmed Long-lived organic room-temperature phosphorescence from amorphous polymer systems
title_short Long-lived organic room-temperature phosphorescence from amorphous polymer systems
title_sort long lived organic room temperature phosphorescence from amorphous polymer systems
topic Engineering::Materials
Science::Chemistry
Hydrogen Bond
Reproducibility
url https://hdl.handle.net/10356/162484
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AT yangchaolong longlivedorganicroomtemperaturephosphorescencefromamorphouspolymersystems
AT zhaoyanli longlivedorganicroomtemperaturephosphorescencefromamorphouspolymersystems