苯二甲酸衍生物修饰聚合物的超长有机室温磷光★

doi:10.6023/A23040157

化学学报 ›› 2023, Vol. 81 ›› Issue (9): 1129-1134.DOI: 10.6023/A23040157 上一篇下一篇

所属专题：庆祝《化学学报》创刊90周年合辑

研究论文

苯二甲酸衍生物修饰聚合物的超长有机室温磷光^★

田野^a^,^b, 司端惠^a^,^b, 高水英^a^,^b^,^*(), 曹荣^a^,^b^,^*()

a 中国科学院福建物质结构研究所结构化学国家重点实验室福建福州 350002
b 中国科学院大学北京 100049

投稿日期:2023-04-22 发布日期:2023-08-24
作者简介:
^★庆祝《化学学报》创刊90周年.
基金资助:
科技部国家重点研发计划重点专项(2021YFA1501500); 国家自然科学基金(22033008); 国家自然科学基金(22220102005); 国家自然科学基金(22201286); 国家自然科学基金(22171265); 中国福建光电信息科学与技术创新实验室(2021ZZ103)

Ultra-Long Organic Room Temperature Phosphorescence of Phthalic Acid Derivative Modified Polymer^★

Ye Tian^a^,^b, Duanhui Si^a^,^b, Shuiying Gao^a^,^b(), Rong Cao^a^,^b()

a State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, China
b University of the Chinese Academy of Sciences, Beijing 100049, China

Received:2023-04-22 Published:2023-08-24
Contact: *E-mail: gaosy@fjirsm.ac.cn; rcao@fjirsm.ac.cn
About author:
^★Dedicated to the 90th anniversary of Acta Chimica Sinica.
Supported by:
The National Key Research and Development Program of China(2021YFA1501500); The National Natural Science Foundation of China(22033008); The National Natural Science Foundation of China(22220102005); The National Natural Science Foundation of China(22201286); The National Natural Science Foundation of China(22171265); Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China(2021ZZ103)

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摘要/Abstract

超长有机室温磷光材料(UORTP)由于其独特的长寿命、丰富的激发态等优点, 在成像、防伪、信息加密等领域受到了越来越多的关注. 具有UORTP的聚合物材料则因其可加工性、透明度和柔韧性等特性渐渐走入人们的视野. 本工作利用苯二甲酸衍生物作为磷光体, 通过酰胺键将苯二甲酸分子修饰在聚乙烯亚胺分子链上, 合成了一系列具有超长有机室温磷光性能的聚合物. 密度泛函理论(DFT)计算证明苯二甲酸和聚乙烯亚胺之间存在能量转移效应, 阐释了长寿命磷光的产生途径. 同时, 通过调控磷光小分子的含量, 这些聚合物可获得达1.51 s的超长寿命和6 s可见余辉. 这是因为随着磷光分子含量的增加, 逐渐增强的分子内氢键构建的刚性环境限制了其非辐射跃迁. 基于材料磷光强度随温度变化的特性, 进一步开发了其在温度传感领域的应用. 这项工作为设计具有长寿命室温磷光和可调余辉的智能发光聚合物提供了一种新的方法.

关键词: 有机室温磷光, 聚合物, 超长寿命, 可见余辉, 温度传感

Ultra-long organic room temperature phosphorescent materials (UORTP) have attracted more and more attention in the fields of imaging, anti-counterfeiting and information encryption due to their unique long life and abundant excited state characteristics. Polymer materials with UORTP are gradually coming into people's eyes because of their machinability, transparency and flexibility. In this work, a series of polymers with UORTP phosphorescent properties were synthesized by modifying phthalic acid molecules on polyethylenimide (PEI) molecular chains through amide bonds using phthalic acid derivatives (isophthalic acid, IPA/terephthalic acid, TPA/phthalic acid, PA) as phosphorescent units. Fourier transform infrared spectrum and X-ray photoelectron spectroscopy demonstrated that the phthalic acid molecules were successfully modified on polyethylenimide. ¹³C Nuclear magnetic resonance illustrates the structure of the phthalic acid remained. Density functional theory (DFT) calculation proved the existence of energy transfer effect between phthalic acid and polyethylenimide, which explained the mechanism of long life phosphorescence. By changing the content of phthalic acid molecules, these polymers can achieve a long-lived lifetime of 1.51 s and an afterglow of 6 s. This is because the rigid environment constructed by the increasing intramolecular hydrogen bond limits the non-radiative transition with the increase of phosphor molecule content. The maximum lifetimes of IPA-PEI, TPA-PEI and PA-PEI were 1.51 s, 0.27 s and 0.03 s, which were 1.5 times, 13.8 times and 47.6 times longer than those of IPA (1 s), TPA (19.6 ms) and PA (0.63 ms), respectively. Thermogravimetry confirmed that the polymers have good thermal stability and the cyclic variable-temperature curves of phosphorescence intensity and cyclic variable-temperature curves of phosphorescent lifetime also illustrate the polymers’ thermal stability. In addition, we further developed application of these polymers in the field of temperature sensing based on the change of phosphorescence intensity with temperature, which the relative sensitivity is up to 1.5%•K^-1. This work provides a novel way for designing smart luminescent polymers with long-lived room temperature phosphorescence and adjustable afterglow.

Key words: organic room-temperature phosphorescence, polymers, ultra-long lifetime, afterglow, temperature sensing

引用此文

田野, 司端惠, 高水英, 曹荣. 苯二甲酸衍生物修饰聚合物的超长有机室温磷光^★[J]. 化学学报, 2023, 81(9): 1129-1134.

Ye Tian, Duanhui Si, Shuiying Gao, Rong Cao. Ultra-Long Organic Room Temperature Phosphorescence of Phthalic Acid Derivative Modified Polymer^★[J]. Acta Chimica Sinica, 2023, 81(9): 1129-1134.

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图/表 6

图1. (a) PEI、PA、IPA和TPA的结构式, 以及所制备的聚合物的荧光照片. (b) UORTP的机制: 持续的激发能量从供体向受体转移, 从而延长RTP的寿命. (c) 苯二甲酸衍生物修饰PEI聚合物的结构图

Figure 1. (a) The structural formula of PEI, PA, IPA, and TPA, and the fluorescence images of the as-prepared polymers. (b) The proposed mechanism for UORTP: the persistent excited energy transfer from donor to acceptor, thus enhancing the lifetime of RTP. (c) Structure diagram of PEI polymer modified by phthalic acid derivatives

图2. 计算得到的PEI和IPA的LUMO和HOMO能级图

Figure 2. The calculated LUMO and HOMO diagrams of PEI and IPA

图3. 三种聚合物的(a)稳态光致发光光谱(蓝线)和延迟光致发光光谱; (b)时间分辨衰减曲线和拟合曲线(分别在521、552和545 nm处的发射)

Figure 3. (a) Steady state (navy blue line) and delayed photoluminescence spectra for the three polymers; (b) time-resolved PL-decay profiles and fitted curves of three polymers at 521, 552 and 545 nm, respectively

图4. 紫外激发后的室温磷光比较. (a) IPA-PEI; (b) TPA-PEI; (c) PA-PEI. 注: 所有照片皆使用手机相机拍摄

Figure 4. Comparison of RTP under UV light irradiation. (a) IPA-PEI; (b) TPA-PEI; (c) PA-PEI. Note the photographs obtained by cell phone camera

图5. (a) IPA-PEI在–100 ℃和25 ℃的稳态光致发光光谱; (b) IPA-PEI在–100 ℃和25 ℃的时间分辨衰减曲线; (c) 磷光强度的变温循环曲线; (d) 磷光寿命的变温循环曲线

Figure 5. (a) Steady-state photoluminescence spectra of IPA-PEI at –100 ℃ and 25 ℃; (b) time-resolved attenuation curves of IPA-PEI at –100 ℃ and 25 ℃; (c) variable temperature cycle curve of phosphorescence intensity; (d) variable temperature cyclic curve of phosphorescent lifetime

图6. (a) IPA-PEI变温稳态光致发光光谱; (b) 最大发射强度随温度变化拟合曲线(红线)和相对灵敏度曲线(黑线)

Figure 6. (a) Variable-temperature steady-state photoluminescence spectra; (b) the fitting curve of the maximum phosphor emission intensity varies with temperature (red line) and relative sensitivity curve (black line)

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苯二甲酸衍生物修饰聚合物的超长有机室温磷光^★

Ultra-Long Organic Room Temperature Phosphorescence of Phthalic Acid Derivative Modified Polymer^★

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苯二甲酸衍生物修饰聚合物的超长有机室温磷光★

Ultra-Long Organic Room Temperature Phosphorescence of Phthalic Acid Derivative Modified Polymer★

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苯二甲酸衍生物修饰聚合物的超长有机室温磷光^★

Ultra-Long Organic Room Temperature Phosphorescence of Phthalic Acid Derivative Modified Polymer^★