Organic Phosphorescent System and Its Research Progress

doi:10.3969/j.issn.1672-6952.2022.01.006

Abstract

Abstract:

In recent years, light?emitting organics have attracted widespread attention due to their unique functions. Among them, room temperature phosphorescent organics have the characteristics of longer wavelength and long life due to their triplet excitons and relatively slow decay rate, resulting in a wide range of application prospects in optical devices, photocatalytic reactions and other fields. At present, the construction of room temperature phosphorescent organic system is mainly accomplished by promoting spin?orbit coupling and suppressing the non?radiative decay process from the triplet state to the ground state. This article summarized the development of room temperature phosphorescent organic system in recent years. According to how to design room temperature phosphorescent organic system, several methods were proposed and their principles were analyzed, and the future development and application of room temperature phosphorescence organic system were prospected.

Key words: Room temperature phosphorescence, Coupling, Non?radiative decay

摘要：

室温磷光性有机物由于三重态激子的参与和相对较慢的衰变速率，使其具有较长波长及长寿命的特性，让该类型化合物在光学器件、光催化反应、生物成像等领域中具有广泛的应用前景。目前构筑室温磷光有机体系主要是通过促进自旋轨道耦合和抑制三重态到基态的非辐射衰变来完成。对近年来室温磷光有机体系的发展进行归纳和总结，针对如何设计室温磷光有机体系提出了几种方法，并分析其原理，对未来室温磷光有机体系的发展与应用进行了展望。

关键词: 室温磷光, 耦合, 非辐射衰变

CLC Number:

TE09

Wangbin Chen, Shijia Zhou, Xiaozhen Zhang, Yuhan Yin, Shuyu Cang, Xian Ou, Guangfu Dai, Xiaorong Wang. Organic Phosphorescent System and Its Research Progress[J]. Journal of Liaoning Petrochemical University, 2022, 42(1): 28-34.

陈望彬, 周世嘉, 张晓朕, 尹禹翰, 苍书宇, 欧贤, 代广福, 王晓蓉. 有机磷光体系及其研究进展[J]. 辽宁石油化工大学学报, 2022, 42(1): 28-34.

Figures/Tables 5

References 47

1	Mukherjee S， Thilagar P. Recent advances in purely organic phosphorescent materials［J］. Chemical Communications， 2015， 51（55）： 10988⁃11003.
2	Hirata S. Recent advances in materials with room‐temperature phosphorescence： Photophysics for triplet exciton stabilization［J］. Advanced Optical Materials， 2017， 5（17）： 1700116.
3	Xu S， Chen R， Zheng C. Excited state modulation for organic afterglow： Materials and applications［J］. Advanced Materials， 2016， 28（45）： 9920⁃9940.
4	Ryota K， Naoto N， Kou Y， et al. Afterglow organic light⁃emitting diode［J］. Advanced Materials， 2016， 28（4）：655⁃660.
5	Yang J， Zhen X， Wang B， et al. The influence of the molecular packing on the room temperature phosphorescence of purely organic luminogens［J］. Nature Communications， 2018， 9（1）： 840.
6	Yang J， Gao X， Xie Z， et al. Elucidating the excited state of mechanoluminescence in organic luminogens with room⁃temperature phosphorescence［J］. Angewandte Chemie International Edition， 2017， 129（48）： 15501⁃15505.
7	Chai Z F， Wang C， Wang J F， et al. Abnormal room temperature phosphorescence of purely organic boron⁃containing compounds： The relationship between the emissive behavior and the molecular packing， and the potential related applications［J］. Chemical Science， 2017， 8（12）： 8336⁃8344.
8	Xie Y J， Ge Y W， Peng Q， et al. How the molecular packing affects the room temperature phosphorescence in pure organic compounds： Ingenious molecular design， detailed crystal analysis， and rational theoretical calculations［J］. Advanced Materials， 2017， 29（17）： 1606829.
9	Xie Y J， Li Z. Thermally activated delayed fluorescent polymers［J］. Journal of Polymer Science Part A： Polymer Chemistry， 2017， 55（4）： 575⁃584.
10	Fang X Y， Yan D P. White⁃light emission and tunable room temperature phosphorescence of dibenzothiophene［J］. Science China Chemistry， 2018， 61（4）： 397⁃401.
11	Li K X， Zhao L F， Gong Y Y，et al. A gelable pure organic luminogen with fluorescence⁃phosphorescence dual emission［J］. Science China Chemistry， 2017， 60（6）： 136⁃142.
12	Kimura T， Watanabe S， Sawada S I， et al. Preparation and optical properties of polyimide films linked with porphyrinato Pd （II） and Pt （II） complexes through a triazine ring and application toward oxygen sensors［J］. Journal of Polymer Science Part A： Polymer Chemistry， 2017， 55（6）： 1086⁃1094.
13	Liu H C， Gao Y， Cao J G， et al. Efficient room⁃temperature phosphorescence based on pure organic sulfur⁃containing heterocycle： Folding⁃induced spin⁃orbit coupling enhancement［J］. Materials Chemistry Frontiers， 2018， 2（10）： 1853⁃1858.
14	Tao S Y， Lu S Y， Geng Y J， et al. Design of metal⁃free polymer carbon dots： A new class of room⁃temperature phosphorescent materials［J］. Angewandte Chemie International Edition， 2018， 57（9）： 2393⁃2398.
15	Ma X， Xu C， Wang J， et al. Amorphous pure organic polymers for heavy⁃atom⁃free efficient room⁃temperature phosphorescence emission［J］. Angewandte Chemie International Edition， 2018， 130（34）： 10854⁃10858.
16	Kautsky H. Energie⁃umwandlungen an grenzflächen， VIII. mitteil.： H. Kautsky， A. Hirsch und W. Flesch： Die bedeutung metastabiler zustände für sensibilisierte photo⁃oxydationen［J］. Berichte Der Deutschen Chemischen Gesellschaft， 1935， 68（1）： 152⁃162.
17	Lewis G N， Kasha M. Phosphorescence and the triplet state［J］. Journal of the American Chemical Society， 1944， 66（12）： 2100⁃2116.
18	Seybold P G， White W. Room temperature phosphorescence analysis. Use of the external heavy⁃atom effect［J］. Analytical Chemistry， 1975， 47（7）： 1199⁃1200.
19	Winnik M A， Lemire A， Saunders D S， et al. Phosphorescence of substituted benzophenones in solution. Probes for the conformation of hydrocarbon chains in polar and proticsolvents［J］. Journal of the American Chemical Society， 1976， 98（7）： 2000⁃2002.
20	Winnik M A， Basu S N， Lee C K， et al. Phosphorescence of substituted benzophenones in solution. A probe of hydrocarbon chain conformation in three nonpolar solvents［J］. Journal of the American Chemical Society， 1976， 98（10）： 2928⁃2935.
21	Schulman E M， Parker R T. Room temperature phosphorescence of organic compounds. The effects of moisture， oxygen， and the nature of the support⁃phosphor interaction［J］. The Journal of Physical Chemistry， 1977， 81（20）： 1932⁃1939.
22	Boduszynski M M， Hurtubise R J， Allen T W. Liquid chromatography/field ionization mass spectrometry in the analysis of high⁃boiling and nondistillable coal liquids for hydrocarbons［J］. Analytical Chemistry， 1983， 55（2）： 225⁃231.
23	Saviotti M L， Galley W C. Room temperature phosphorescence and the dynamic aspects of protein structure［J］. Proceedings of the National Academy of Sciences， 1974， 71（10）： 4154⁃4158.
24	Kalyanasundaram K， Grieser F， Thomas J K. Room temperature phosphorescence of aromatic hydrocarbons in aqueous micellar solutions［J］. Chemical Physics Letters， 1977， 51（3）： 501⁃505.
25	Scypinski S， Love L J C. Room temperature phosphorescence of polynuclear aromatic hydrocarbons in cyclodextrins［J］. Analytical Chemistry， 1984， 56（3）： 322⁃327.
26	Itoh T. The evidence showing that the intersystem crossing yield of benzaldehydevapour is unity［J］. Chemical Physics Letters， 1988， 151（1⁃2）： 166⁃168.
27	Yuan W Z， Shen X Y， Zhao H. Crystallization⁃induced phosphorescence of pure organic luminogens at room temperature［J］. Journal of Physical Chemistry C， 2010， 114（13）： 6090⁃6099.
28	Gong Y Y， Tan Y Q， Mei J， et al. Room temperature phosphorescence from natural products： Crystallization matters［J］. Science China Chemistry， 2013，56（9）： 1178⁃1182.
29	Gong Y Y， Chen G， Peng Q，et al. Achieving persistent room temperature phosphorescence and remarkable mechanochromism from pure organic luminogens［J］. Advanced Materials， 2015， 27（40）：6195⁃6201.
30	Gong Y Y， Zhao L， Peng Q，et al. Crystallization⁃induced dual emission from metal⁃ and heavy atom⁃free aromatic acids and esters［J］. Chemical Science， 2015， 6（8）： 4438⁃4444.
31	Li J， Jiang Y， Cheng J. Tuning the singlet⁃triplet energy gap of AIE luminogens： Crystallization⁃induced room temperature phosphorescence and delay fluorescence， tunable temperature response， highly efficient non⁃doped organic light⁃emitting diodes［J］. Physical Chemistry Chemical Physics： PCCP， 2015， 17（2）： 1134⁃1141.
32	唐亮亮. 具有刺激响应行为的有机材料合成与性质研究［D］. 青岛：青岛科技大学， 2019.
33	Gong Y Y， Zhao L， Peng Q. Crystallization⁃induced dual emission from metal⁃ and heavy atom⁃free aromatic acids and esters［J］. Chemical Science， 2015， 6（8）： 4438⁃4444.
34	Xue P C. Luminescence switching of a persistent room⁃temperature phosphorescent pure organic molecule in response to external stimuli［J］. Chemical Communications， 2015， 51（52）： 10381⁃10384.
35	张振振. 基于咔唑的纯有机室温磷光材料的设计合成及光学性质研究［D］. 青岛：青岛科技大学，2019.
36	Bolton O， Lee K， Kim H J， et al. Activating efficient phosphorescence from purely organic materials by crystal design［J］. Nature Chemistry， 2011， 3（3）： 207⁃212.
37	Gao H Y， Shen Q J， Zhao X R， et al. Phosphorescent co⁃crystal assembled by 1，4⁃diiodotetrafluorobenzene with carbazole based on C–I···π halogen bonding［J］. Journal of Materials Chemistry， 2012， 22（12）： 5336.
38	Pang X， Wang H， Zhao X R， et al. Co⁃crystallization turned on the phosphorescence of phenanthrene by C-Br···π halogen bonding， π⁃hole···π bonding and other assisting interactions［J］. CrystEngComm， 2013， 15（14）： 2722⁃2730.
39	Gan N， Shi H F， An Z F， et al. Recent advances in polymer‐based metal‐free room‐temperature phosphorescent materials［J］. Advanced Functional Materials， 2018， 28（51）： 1802657.
40	Wu W B， Tang R L， Li Q Q， et al. Functional hyperbranched polymers with advanced optical， electrical and magnetic properties［J］. Chemical Society Reviews， 2015， 44（12）： 3997⁃4022.
41	Min S K， Lee D， Seo S， et al. Tailoring intermolecular interactions for efficient room⁃temperature phosphorescence from purely organic materials in amorphous polymer matrices［J］. Angewandte Chemie， 2014， 126（42）： 11177⁃11181.
42	Su Y， Phua S Z F， Li Y B， et al. Ultralong room temperature phosphorescence from amorphous organic materials toward confidential information encryption and decryption［J］. Science Advances， 2018， 4（5）： eaas9732.
43	Jinnai K， Kabe R， Adachi C. Wide⁃Range tuning and enhancement of organic long⁃persistent luminescence using emitter dopants［J］. Advanced Materials， 2018， 30（38）： 1800365.
44	Zhang G Q， Chen J B， Sarah J P， et al. Multi⁃emissive difluoroboron dibenzoylmethane polylactide exhibiting intense fluorescence and oxygen⁃sensitive room⁃temperature phosphorescence［J］. Journal of the American Chemical Society， 2007， 129（29）： 8942⁃8943.
45	DeRosa C A， Kerr C， Fan Z， et al. Tailoring oxygen sensitivity with halide substitution in difluoroboron dibenzoylmethane polylactide materials［J］. ACS Applied Materials & Interfaces， 2015， 7（42）： 23633⁃23643.
46	Chen H， Yao X Y， Ma X， et al. Amorphous， efficient， room⁃temperature phosphorescent metal⁃free polymers and their applications as encryption ink［J］. Advanced Optical Materials， 2016， 4（9）： 1397⁃1401.
47	Zhou C， Xie T Q， Zhou R， et al. Waterborne polyurethanes with tunable fluorescence and room⁃temperature phosphorescence［J］. ACS Applied Materials & Interfaces， 2015， 7（31）： 17209⁃17216.

[1]	Heng QU, Zhonghu WU. Numerical Simulation of Mechanical Properties and Damage Modes of Shales with Cross⁃Fractures under Triaxial Stress [J]. Journal of Liaoning Petrochemical University, 2024, 44(2): 42-49.
[2]	Jiajun Yu, Shuang Zhao, Xiao Feng. Research Progress of Membrane Separation Technology in Salt Lake Lithium Extraction [J]. Journal of Liaoning Petrochemical University, 2023, 43(4): 30-35.
[3]	Mengyuan Dong, Jianmin Ren, Xiangzhe Zhu. Analysis of the Influence of Modeling Method on the Dynamic Characteristics of Machine Tool Spindle⁃Tool Coupling System [J]. Journal of Liaoning Petrochemical University, 2023, 43(3): 69-74.
[4]	Chaofan Zhu, Rui Wang, Yunrong Chen. Synthesis of 2⁃Ethyl⁃2⁃Aryl⁃Dihydroquinoline Derivatives [J]. Journal of Liaoning Petrochemical University, 2022, 42(5): 18-25.
[5]	Hongzhi Sun, Wei Sun, Bo Zhao, Huaihong Guo. Theoretical Study on Double Resonant Raman Scattering in Janus MoSSe Monolayer [J]. Journal of Liaoning Petrochemical University, 2022, 42(3): 30-36.
[6]	Chengbin Wang, Yili Duo, Tie Sun, Songyu Yang. High Temperature Bolted Flange Connection Structure and Risk Analysis [J]. Journal of Liaoning Petrochemical University, 2022, 42(2): 67-72.
[7]	Zhigang Duan, Zhi Wang, Minglai Chu, Xiantao Liao, Zhimei Si, Liao Wang. Analysis of the Movement Law of the Valve Ball in the Oil Well Pump Based on the Ellipse Rate Drive [J]. Journal of Liaoning Petrochemical University, 2021, 41(5): 50-54.
[8]	Yuke Liu, Fei Yan, Jing Sun, Mingdong Zhou. Copper⁃Catalyzed Synthesis of a Long Alkyl Branched Fatty Alcohol [J]. Journal of Liaoning Petrochemical University, 2021, 41(4): 17-21.
[9]	Zhu Liming， Yu Fang. Synthesis of Various Novel Chiral Phosphoric Acid Catalysts [J]. Journal of Liaoning Petrochemical University, 2021, 41(2): 13-16.
[10]	Zhang Yuanyuan， Zhang Juwei， Liu Xiaopei. Proposition and Application of Nonlinear Multi Factor Coupling Accident Cause Model [J]. Journal of Liaoning Petrochemical University, 2021, 41(2): 73-78.
[11]	Zhai Chunyan, Meng Xiangxue, Wang Guoliang. The Stability of Nonlinear Complex Networks with Coupling Matrix Failures [J]. Journal of Liaoning Petrochemical University, 2020, 40(1): 84-90.
[12]	Liang Jiling，Wang Liqun，Liu Lijuan，Tian Li，Zhang Lunqiu，Wang Weiqiang. The Modification of Fe3O4@SiO2 by Silane Coupling Agent and Performance [J]. Journal of Liaoning Petrochemical University, 2019, 39(6): 21-26.
[13]	Zhou Jie，Zhang Fenghua，Ding Xiaoguang，Yu Fang. CuCl⁃Promoted C-O Cross Coupling of p⁃Methyl Bromobenzene and Phenol [J]. Journal of Liaoning Petrochemical University, 2019, 39(5): 21-25.
[14]	Jiang Xiuxiu， Wu Ming， Zhao Ling， Liu Guangxin， Wang Jidong. Factors Decomposition of Industrial Carbon Emission and the  Analysis of Its Decoupling Efforts in Liaoning Province [J]. Journal of Liaoning Petrochemical University, 2017, 37(4): 70-74.
[15]	Han Zhen,Zhang Deqi,Wu Qiang,Zheng Xuhui. Improvement on the Coupling Method for Rock Ultrasonic Probetoa Test Piece [J]. Journal of Liaoning Petrochemical University, 2017, 37(3): 51-53.