三苯胺-吩噻嗪衍生物掺杂聚合物的光诱导室温磷光

doi:10.6023/cjoc202404016

有机化学 ›› 2024, Vol. 44 ›› Issue (8): 2487-2494.DOI: 10.6023/cjoc202404016 上一篇下一篇

研究论文

三苯胺-吩噻嗪衍生物掺杂聚合物的光诱导室温磷光

李楠^b, 王雲生^a^,^*(), 李振^a^,^b^,^c^,^*()

a 天津大学福州国际校区天津大学-新加坡国立大学福州联合学院福州 350207
b 天津大学分子聚集态科学研究院天津 300072
c 武汉大学化学与分子科学学院湖北省有机高分子光电功能材料重点实验室武汉 430072

收稿日期:2024-04-10 修回日期:2024-06-23 发布日期:2024-07-10
基金资助:
国家自然科学基金(22305172); 中国博士后科学基金(2023M732586); 中国博士后科学基金(2024T170640); 国家资助博士后研究人员计划(GZB20230509)

Photoinduced Room-Temperature Phosphorescence of Triphenylamine-Phenothiazine Derivative-Doped Polymers

Nan Li^b, Yunsheng Wang^a(), Zhen Li^a^,^b^,^c()

a Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Fuzhou 350207
b Institute of Molecular Aggregation Science, Tianjin University, Tianjin 300072
c Hubei Key Lab on Organic and Polymeric Opto-Electronic Materials, Department of Chemistry, Wuhan University, Wuhan 430072

Received:2024-04-10 Revised:2024-06-23 Published:2024-07-10
Contact: *E-mail: wangys_18@tju.edu.cn; lizhen@whu.edu.cn
Supported by:
National Natural Science Foundation of China(22305172); China Postdoctoral Science Foundation(2023M732586); China Postdoctoral Science Foundation(2024T170640); Postdoctoral Fellowship Program of China Postdoctoral Science Foundation (CPSF)(GZB20230509)

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摘要/Abstract

在刺激响应发光材料领域, 以光作为刺激源的光诱导室温磷光(RTP)材料因其非接触式读写和应用范围广而引起广泛关注. 然而, 这类材料目前仍相对稀少, 开发新型高效光响应RTP分子具有重要意义. 通过Buchwald-Hartwig C—N偶联反应成功合成了三个吩噻嗪衍生物TPA-PTZ、TPA-2PTZ和TPA-3PTZ. 将上述分子分别作为发色单元掺杂到聚甲基丙烯酸甲酯(PMMA)基质中, 制备了具有优异光诱导RTP性能的高分子薄膜. 其中, TPA-PTZ掺杂薄膜在持续的紫外线照射后, 量子产率增加了19倍, 达到了5.68%. 与此同时, 这些材料还具备优越的光稳定性和热稳定性, 在长时间的紫外线照射(365 nm, 500 μW•cm⁻², 时间>200 s)或温度高达75 ℃的情况下, 仍可以保持较高强度的磷光. 这些光诱导RTP材料的独特性质, 赋予它们在发光显示、防伪以及先进光学材料领域较大的应用潜力.

关键词: 刺激响应发光材料, 光诱导室温磷光, 吩噻嗪衍生物, 聚合物掺杂

Photo-responsive room-temperature phosphorescent (RTP) materials have garnered significant interest due to the advantages of rapid response, spatiotemporal control, and contactless precision manipulation. However, the development of such materials remains in its infancy, underscoring the importance of exploiting novel and efficient light-responsive RTP molecules. In this work, three phenothiazine derivatives of TPA-PTZ, TPA-2PTZ, and TPA-3PTZ were successfully synthesized via the Buchwald-Hartwig C—N coupling reaction. By embedding these molecules as RTP guests into polymethyl methacrylate (PMMA) matrix, photo-induced RTP properties were realized. Upon sustained UV irradiation, there was an enhancement of 19 times in the quantum yield to reach a value of 5.68%. Remarkably, these materials exhibit superior alongside robust light and thermal stability, maintaining high phosphorescence intensity even after prolonged UV exposure (irradiation for>200 s by a 365 nm UV lamp with the power of 500 µW•cm^－2) or at higher temperature up to 75 ℃. The outstanding properties of these photo-induced RTP materials make them promising candidates for applications in information encryption, anti-counterfeiting, and advanced optical materials.

Key words: stimuli-responsive luminescent materials, photo-induced room-temperature phosphorescence, phenothiazine deri- vatives, doped polymer

引用此文

李楠, 王雲生, 李振. 三苯胺-吩噻嗪衍生物掺杂聚合物的光诱导室温磷光[J]. 有机化学, 2024, 44(8): 2487-2494.

Nan Li, Yunsheng Wang, Zhen Li. Photoinduced Room-Temperature Phosphorescence of Triphenylamine-Phenothiazine Derivative-Doped Polymers[J]. Chinese Journal of Organic Chemistry, 2024, 44(8): 2487-2494.

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Figure 1. Schematic representation and demonstration of photo-induced RTP material used for optical information writing/erasing, and data storage (a) Illustrates the synthesis of RTP molecules TPA-PTZ, TPA-2PTZ, and TPA-3PTZ, and their subsequent doping into a PMMA matrix. (b) Depicts the localized activation of an RTP pattern by UV light through a mask. The bottom images show the phosphorescent output (TPA-3PTZ∶PMMA=1∶40, mass ratio, film size, 50 mm×50 mm×0.7 mm). (c) Erasable optical data storage device based on photo-induced RTP: high-density information storage and encryption (TPZ-2PTZp)

Figure 2. (a) Normalized steady-state PL spectra of TPA-PTZ, TPA-2PTZ, and TPA-3PTZ in DCM solution (c=1.0×10－5 mol?L－1) at room temperature and (b) 77 K; (c) phosphorescence decay profiles of TPA-PTZ, TPA-2PTZ, and TPA-3PTZ in DCM solution at 77 K (λem=510 nm); (d) steady-state photoluminescence (PL) spectra of TPA-PTZ, TPA-2PTZ, and TPA-3PTZ solutions from 77 to 298 K (λex=370 nm)

Figure 3. (a) In-suit monitoring of changed steady-state PL spectra of TPA-PTZ, TPA-2PTZ, and TPA-3PTZ doped films; (b) Phosphorescence decay profiles of TPA-PTZ, TPA-2PTZ, and TPA-3PTZ doped films at room temperature (λex=370 nm, λem=520 nm); (c) fluorescence decay profiles of TPA-PTZ, TPA-2PTZ, and TPA-3PTZ doped films at room temperature (λex=370 nm, λem=430 nm); (d) quantum yield (Φ) of TPA-PTZ, TPA-2PTZ, and TPA-3PTZ doped films before and after 365 nm UV irradiation (500 μW?cm－2)

Figure 4. Energy level diagrams and possible ISC channels from excited singlet state (S1) to excited triplet states (Tn) for (a) TPA-PTZ, (b) TPA-2PTZ, (c) TPA-3PTZ and the corresponding spin-orbit coupling (SOC) constants

Figure 5. In-suit monitoring of changed steady-state PL spectra of TPA-PTZ, TPA-2PTZ, and TPA-3PTZ doped films with different temperature (PL spectra were collected by QE65 Pro. Mode: high-speed scanning)

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三苯胺-吩噻嗪衍生物掺杂聚合物的光诱导室温磷光

Photoinduced Room-Temperature Phosphorescence of Triphenylamine-Phenothiazine Derivative-Doped Polymers

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