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

doi:10.6023/A23040157

Acta Chimica Sinica ›› 2023, Vol. 81 ›› Issue (9): 1129-1134.DOI: 10.6023/A23040157 Previous Articles Next Articles

Special Issue: 庆祝《化学学报》创刊90周年合辑

Article

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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Abstract

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

Cite this article

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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Fig. & Tab. 6

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

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

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

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

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

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^★