键锁N-苯基咔唑分子内旋转制备超长室温磷光聚合物

doi:10.6023/cjoc202504028

有机化学 ›› 2025, Vol. 45 ›› Issue (11): 4178-4184.DOI: 10.6023/cjoc202504028 上一篇下一篇

研究论文

键锁N-苯基咔唑分子内旋转制备超长室温磷光聚合物

张念双^†, 秦玉静^†, 王硕博, 梁于, 杨文君, 孙其坤^*(), 薛善锋^*()

青岛科技大学高分子科学与工程学院橡塑材料与工程教育部重点实验室山东省橡塑材料与工程重点实验室山东青岛 266042

收稿日期:2025-04-27 修回日期:2025-05-28 发布日期:2025-07-17
作者简介:
^†共同第一作者
基金资助:
国家自然科学基金(52273183); 山东省自然科学基金(ZR2020QE083); 及山东省泰山学者人才工程(tsqn202211164)

Locking up Internal Rotation of N-Phenylcarbazole in Advance to Endow Ultralong Room Temperature Phosphorescence (RTP) Afterglows in Polymers

Nianshuang Zhang, Yujing Qin, Shuobo Wang, Yu Liang, Wenjun Yang, Qikun Sun^*(), Shanfeng Xue^*()

Shandong Provincial Key Laboratory of Rubber-Plastics, Key Laboratory of Rubber-Plastics of Ministry of Education, School of Polymer Science & Engineering, Qingdao University of Science &Technology, Qingdao, Shandong 266042

Received:2025-04-27 Revised:2025-05-28 Published:2025-07-17
Contact: *E-mail: qksun@qust.edu.cn; sfxue@qust.edu.cn
About author:
^†The authors contributed equally to this work
Supported by:
National Natural Science Foundation of China(52273183); Natural Science Foundation of Shandong Province(ZR2020QE083); Taishan Scholar Constructive Engineering Foundation of Shandong Province(tsqn202211164)

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摘要/Abstract

共轭有机主链的内旋转严重阻碍了超长室温磷光(RTP)材料的构筑, 使得在非晶态聚合物中实现超过2 s的超长RTP寿命极为罕见. 通过将N-(溴苯基)咔唑环化, 预先键锁苯基咔唑的内旋转, 并将所得的含氮杂环化合物掺杂到聚甲基丙烯酸甲酯(PMMA)中. 结果表明, 键锁分子内旋转可实现寿命超过2 s的超长RTP聚合物, 而未键锁的分子在PMMA中却几乎不发射RTP. 另外高能态三重态激子可以将能量转移给低能态的有机荧光染料, 从而轻松实现并获得持久的多色余辉材料, 包括白光发射. 本工作揭示了一种有效且可扩展的掺杂分子策略, 用于开发高性能超长有机RTP聚合物.

关键词: 化学键锁, 分子内旋转, 超长余辉, 磷光聚合物

Internal rotation of conjugated organic backbone seriously impaired room temperature phosphorescence (RTP), leading to rare realization of ultra-long afterglows with RTP lifetimes over 2 s in non-bibulous polymers. Herein, N-(bromo- phenyl)carbazoles are cyclized to lock up phenyl-carbazol internal rotation in advance and the fused nitrogen hetero-cyclic compounds are doped into poly(methyl methacrylate) (PMMA). The results show that locking up the molecular internal rotation can achieve ultra-long RTP polymers with lifetimes over 2 s, in contrast, the unlocked molecules hardly emit RTP in PMMA. The high-lying triplet excitons can transfer the energy to low-lying organic fluorescent dyes, and the persistent multi- color afterglows including white emission can be readily modulated. This work discloses an effective and extendable dopant molecular strategy for developing high-performance ultra-long organic RTP polymers.

Key words: chemical locking, internal rotation, ultra-long afterglows, room temperature phosphorescence (RTP) polymer

引用此文

张念双, 秦玉静, 王硕博, 梁于, 杨文君, 孙其坤, 薛善锋. 键锁N-苯基咔唑分子内旋转制备超长室温磷光聚合物[J]. 有机化学, 2025, 45(11): 4178-4184.

Nianshuang Zhang, Yujing Qin, Shuobo Wang, Yu Liang, Wenjun Yang, Qikun Sun, Shanfeng Xue. Locking up Internal Rotation of N-Phenylcarbazole in Advance to Endow Ultralong Room Temperature Phosphorescence (RTP) Afterglows in Polymers[J]. Chinese Journal of Organic Chemistry, 2025, 45(11): 4178-4184.

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图/表 4

Figure 1. Molecular structures before and after chemical locking and the generation mechanism of organic afterglow before and after chemical locking are included

Figure 2. (a) PL photographs of thermoplasticized 0.1% ICz-pCN and 0.1% ICz doped into PMMA sheets before and after removing 365 nm light excitation; (b) Prompt and delayed PL spectra of 0.1% ICz-pCN and 0.1% ICz in PMMA at 365 nm in film state at 298 K; (c) Time-resolved RTP decay curves and fitted long-component lifetimes of photo-activated thermoplasticized PMMA doped sheets under 365 nm light excitation; (d) RTP efficiency calculated by differential method, and average lifetimes (All the samples are sustainably photo-activated by 365 nm lamp (0.3 mW/cm2) for 10 s before measurements)

Figure 3. (a) Natural transition orbitals for ICz-pCN and 2X4Q molecules in crystals; (b) Single-crystal structure and dihedral angle of ICz-pCN and 2X4Q: (c) Excited state energy level diagram of ICz-pCN and 2X4Q molecules (The blue dotted arrow indicates the possible ISC channel (ES1±0.3 eV)); (d) Low temperature phosphorescence photo of 0.1% 2X4Q and 0.1% ICz-pCN doped into PMMA sheets (The samples are sustainably photo-activated by 365 nm lamp (0.3 mW/cm2) for 5 s before measurements)

Figure 4. (a) Phosphorescence emission of ICz-pCN-PMMA overlaps with the absorption characteristics of OFD and RFD; (b) Afterglow photos of 0.1% ICz-pCN and different mass fractions of OFD doped in PMMA at 365 nm film state at 298 K; (c) Commission International de l’Eclairage (CIE) color coordinates and delayed PL spectra of PMMA doped with 0.1% ICz-pCN and different mass fractions of OFD; (d) Time-resolved RTP decay curves and fitted long-component lifetimes of photo-activated thermoplasticized OFD/ICz- pCN-PMMA doped sheets under 365 nm light excitation; (e) Afterglow photos of 0.1% ICz-pCN and different mass fractions of RFD doped in PMMA at 365 nm film state at 298 K; (f) Delayed PL spectra of 0.1% ICz-pCN-0.1% RFD in PMMA at 365 nm in film state at 298 K

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键锁N-苯基咔唑分子内旋转制备超长室温磷光聚合物

Locking up Internal Rotation of N-Phenylcarbazole in Advance to Endow Ultralong Room Temperature Phosphorescence (RTP) Afterglows in Polymers

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