基于分子内电荷转移技术构建高效热激活延迟荧光型有机余辉材料

doi:10.6023/cjoc202503027

摘要/Abstract

报道了基于热激活延迟荧光(TADF)机制的高效可见光激发余辉材料的构筑, 采用分子内电荷转移技术, 所得的TADF型余辉材料展示了数百毫秒的发射寿命和50%左右的光致发光量子产率, 表现出显著的温度响应特性. 通过在给体-受体(D-A)型二氟化硼β-二酮(BF₂bdk)分子中引入额外的电子供体基团, 设计了给体-受体-给体(D-A-D)型化合物, 所得化合物表现出适度的反向系间窜越速率, 促进了BF₂bdk在刚性晶体基质中的TADF型余辉的出现. 此外, D-A-D设计方法提高了最高占据分子轨道能级, 从而实现了在可见光激发下的TADF型余辉发射. 研究结果表明分子内电荷转移技术在推进高性能有机TADF型余辉材料设计中的重要性.

关键词: 二氟化硼β-二酮, 热激活延迟荧光, 有机余辉, 室温磷光, 分子内电荷转移

The construction of highly efficient visible-light-excitable afterglow materials based on thermally activated delayed fluorescence (TADF) mechanism is reported, employing an intramolecular charge transfer technology. The resulting TADF- type afterglow materials exhibit emission lifetimes in the range of hundreds of milliseconds and photoluminescence quantum yields of approximately 50%, demonstrating remarkable temperature-responsive properties. By introducing additional electron- donating groups into the donor-acceptor (D-A)-type difluoroboron β-diketonate (BF₂bdk) molecules, donor-acceptor-donor (D-A-D)-type compounds were designed. These compounds exhibit a moderate rate of reverse intersystem crossing (RISC), thereby promoting the emergence of TADF-type afterglow within a rigid crystalline matrix. Furthermore, the D-A-D design approach elevates the highest occupied molecular orbital (HOMO) energy level, enabling TADF-type afterglow emission under visible light excitation. The research findings highlight the significance of intramolecular charge transfer technology in advancing the design of high-performance organic TADF-type afterglow materials.

Key words: difluoroboron β-diketonate, thermally activated delayed fluorescence, organic afterglow, room-temperature phos- phorescence, intramolecular charge transfer

引用此文

罗婷, 肖宇峰, 李珣, 夏雯, 张卡卡. 基于分子内电荷转移技术构建高效热激活延迟荧光型有机余辉材料[J]. 有机化学, 2025, 45(11): 4202-4209.

Ting Luo, Yufeng Xiao, Xun Li, Wen Xia, Kaka Zhang. Fabrication of Highly-Efficient Thermally Activated Delayed Fluorescence-Type Organic Afterglow Materials Based on Intramolecular Charge Transfer Technology[J]. Chinese Journal of Organic Chemistry, 2025, 45(11): 4202-4209.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 5

图1. (a) BF2bdk化合物; (b) D-A-D型BF2bdk化合物的合成方法; (c)本研究中使用的BF2bdk化合物的化学结构

Figure 1. (a) BF2bdk compound; (b) Synthesis method of D-A-D type BF2bdk compound; (c) Chemical structures of the BF2bdk compounds used in this study

图2. (a~c)掺杂浓度为0.001%、0.01%、0.1%的1-MeOBP在365 nm激发下的室温稳态和延迟发光(延迟1 ms)谱图以及材料在365 nm紫外灯下和移除紫外灯后的照片; (d~f)掺杂浓度为0.001%、0.01%、0.1%的1-MeOBP的室温发光衰减曲线

Figure 2. (a~c) Room temperature steady-state and delayed emission (1 ms delay) spectra of 1-MeOBP with doping concentrations of 0.001%, 0.01%, 0.1% excited at 365 nm and photographs of the material under 365 nm UV lamp and after removing the UV lamp; (d~f) Room temperature emission decay curves of 1-MeOBP with doping concentrations of 0.001%, 0.01%, 0.1%

图3. (a)不同温度下1-MeOBP-0.001%的延迟发光(延迟1 ms)谱图; (b)不同温度下1-MeOBP-0.001%的发光衰减曲线(监测波长为470 nm); (c) 1-MeOBP-0.001%的ln(kRISC)和1/T的拟合直线图, 其斜率与△EST相关; (d) BF2bdk-MeOBP体系中TADF型有机余辉机制示意图

Figure 3. (a) Delay emission spectra (1 ms delay) of 1-MeOBP-0.001% at different temperatures; (b) Emission decay curves of 1-MeOBP-0.001% at different temperatures monitored at 470 nm; (c) Fitted line plot of 1-MeOBP-0.001% ln(kRISC) and 1/T with slope associated with △EST; (d) Schematic illustration of TADF-type organic afterglow mechanism in BF2bdk-MeOBP system

图4. 化合物1的单重态和三重态激发态的电子-空穴密度差等值面图、激发能、振子强度和SOCME值

Figure 4. Iso-surface map of electron hole density difference, excitation energy, oscillator strength and SOCME value for the singlet and triplet excited states of compound 1

Entry	λ_F/nm	λ_AG/nm	τ_AG/ms	PLQY/%
1-MeOBP-0.001%	470	470	211	55.1
2-MeOBP-0.001%	470	470	182	52.9
3-MeOBP-0.001%	470	470	248	47.8
4-MeOBP-0.001%	480	480	161	50.3

表1. 余辉材料的光物理性质

Table 1. Photophysical properties of afterglow materials

参考文献 66

[1]	Yam, V. W.-W.; Au, V. K.-M.; Leung, S. Y.-L. Chem. Rev. 2015, 115, 7589. doi: 10.1021/acs.chemrev.5b00074
[2]	Zhao, W.; He, Z.; Tang, B. Z. Nat. Rev. Mater. 2020, 5, 869. doi: 10.1038/s41578-020-0223-z
[3]	Gan, N.; Shi, H.; An, Z.; Huang, W. Adv. Funct. Mater. 2018, 28, 1802657. doi: 10.1002/adfm.v28.51
[4]	Ma, X.; Wang, J.; Tian, H. Acc. Chem. Res. 2019, 52, 738. doi: 10.1021/acs.accounts.8b00620
[5]	Hirata, S. Adv. Opt. Mater. 2017, 5, 1700116. doi: 10.1002/adom.v5.17
[6]	Forni, A.; Lucenti, E.; Botta, C.; Cariati, E. J. Mater. Chem. C 2018, 6, 4603. doi: 10.1039/C8TC01007B
[7]	Kenry; Chen, C.; Liu, B. Nat. Commun. 2019, 10, 2111. doi: 10.1038/s41467-019-10033-2 pmid: 31068598
[8]	Zhang, T.; Ma, X.; Wu, H.; Zhu, L.; Zhao, Y.; Tian, H. Angew. Chem., Int. Ed. 2020, 59, 11206. doi: 10.1002/anie.v59.28
[9]	Li, Q.; Li, Z. Acc. Chem. Res. 2020, 53, 962. doi: 10.1021/acs.accounts.0c00060
[10]	Zhou, Q.; Yang, C.; Zhao, Y. Chem 2023, 9, 2446. doi: 10.1016/j.chempr.2023.05.023
[11]	Guo, S.; Dai, W.; Chen, X.; Lei, Y.; Shi, J.; Tong, B.; Cai, Z.; Dong, Y. ACS Mater. Lett. 2021, 3, 379.
[12]	Yan, X.; Peng, H.; Xiang, Y.; Wang, J.; Yu, L.; Tao, Y.; Li, H.; Huang, W.; Chen, R. Small 2022, 18, 2104073. doi: 10.1002/smll.v18.1
[13]	Singh, M.; Liu, K.; Qu, S.; Ma, H.; Shi, H.; An, Z.; Huang, W. Adv. Opt. Mater. 2021, 9, 2002197. doi: 10.1002/adom.v9.10
[14]	Dai, X.-Y.; Huo, M.; Liu, Y. Nat. Rev. Chem. 2023, 7, 854. doi: 10.1038/s41570-023-00555-1
[15]	Ding, B.; Ma, X.; Tian, H. Acc. Mater. Res. 2023, 4, 827. doi: 10.1021/accountsmr.3c00090
[16]	Wu, H.; Chi, W.; Chen, Z.; Liu, G.; Gu, L.; Bindra, A. K.; Yang, G.; Liu, X.; Zhao, Y. Adv. Funct. Mater. 2019, 29, 1807243. doi: 10.1002/adfm.v29.10
[17]	Zhang, G.; Palmer, G. M.; Dewhirst, M. W.; Fraser, C. L. Nat. Mater. 2009, 8, 747. doi: 10.1038/nmat2509
[18]	Yang, J.; Wu, X.; Shi, J.; Tong, B.; Lei, Y.; Cai, Z.; Dong, Y. Angew. Chem., Int. Ed. 2020, 59, 16054. doi: 10.1002/anie.v59.37
[19]	Ma, X.-K.; Zhang, W.; Liu, Z.; Zhang, H.; Zhang, B.; Liu, Y. Angew. Chem., Int. Ed. 2019, 58, 6028. doi: 10.1002/anie.v58.18
[20]	Ward, J. S.; Nobuyasu, R. S.; Batsanov, A. S.; Data, P.; Monkman, A. P.; Dias, F. B.; Bryce, M. R. Chem. Commun. 2016, 52, 2612. doi: 10.1039/C5CC09645F
[21]	Kabe, R.; Adachi, C. Nature 2017, 550, 384. doi: 10.1038/nature24010
[22]	Li, W.; Li, Z.; Si, C.; Wong, M. Y.; Jinnai, K.; Gupta, A. K.; Kabe, R.; Adachi, C.; Huang, W.; Zysman‐Colman, E.; Samuel, I. D. W. Adv. Mater. 2020, 32, 2003911. doi: 10.1002/adma.v32.45
[23]	Liang, X.; Zheng, Y.; Zuo, J. Angew. Chem., Int. Ed. 2021, 60, 16984. doi: 10.1002/anie.v60.31
[24]	Jinnai, K.; Kabe, R.; Lin, Z.; Adachi, C. Nat. Mater. 2022, 21, 338. doi: 10.1038/s41563-021-01150-9
[25]	Alam, P.; Leung, N. L. C.; Liu, J.; Cheung, T. S.; Zhang, X.; He, Z.; Kwok, R. T. K.; Lam, J. W. Y.; Sung, H. H. Y.; Williams, I. D.; Chan, C. C. S.; Wong, K. S.; Peng, Q.; Tang, B. Z. Adv. Mater. 2020, 32, 2001026. doi: 10.1002/adma.v32.22
[26]	Wang, Y.; Gao, H.; Yang, J.; Fang, M.; Ding, D.; Tang, B. Z.; Li, Z. Adv. Mater. 2021, 33, 2007811. doi: 10.1002/adma.v33.18
[27]	Wang, G.; Chen, X.; Zeng, Y.; Li, X.; Wang, X.; Zhang, K. J. Am. Chem. Soc. 2024, 146, 24871. doi: 10.1021/jacs.4c05531
[28]	Wang, X.; Sun, Y.; Wang, G.; Li, J.; Li, X.; Zhang, K. Angew. Chem., Int. Ed. 2021, 60, 17138. doi: 10.1002/anie.v60.31
[29]	Pan, Y.; Li, J.; Wang, X.; Sun, Y.; Li, J.; Wang, B.; Zhang, K. Adv. Funct. Mater. 2022, 32, 2110207. doi: 10.1002/adfm.v32.14
[30]	Chen, X.; Wang, G.; Piao, X.; Zhang, K. Chem.-Eur. J. 2024, 30, e202303834.
[31]	Yang, Y.; Liang, Y.; Zheng, Y.; Li, J.; Wu, S.; Zhang, H.; Huang, T.; Luo, S.; Liu, C.; Shi, G.; Sun, F.; Chi, Z.; Xu, B. Angew. Chem., Int. Ed. 2022, 61, e202201820.
[32]	Wang, G.; Ding, S.; Li, J.; Li, X.; Xia, W.; Chen, X.; Yao, H.; Ye, Z.; Zhang, K. Chem. Mater. 2024, 36, 3000. doi: 10.1021/acs.chemmater.4c00161
[33]	Ye, Z.; Li, J.; Li, X.; Wang, G.; Zhang, K. Org. Electron. 2024, 134, 107128. doi: 10.1016/j.orgel.2024.107128
[34]	Wang, J.; Yang, Y.; Li, K.; Zhang, L.; Li, Z. Angew. Chem., Int. Ed. 2023, 62, e202304020.
[35]	Yuan, W. Z.; Shen, X. Y.; Zhao, H.; Lam, J. W. Y.; Tang, L.; Lu, P.; Wang, C.; Liu, Y.; Wang, Z.; Zheng, Q.; Sun, J. Z.; Ma, Y.; Tang, B. Z. J. Phys. Chem. C 2010, 114, 6090. doi: 10.1021/jp909388y
[36]	Bolton, O.; Lee, K.; Kim, H.-J.; Lin, K. Y.; Kim, J. Nat. Chem. 2011, 3, 205. doi: 10.1038/nchem.984 pmid: 21336325
[37]	Yang, Z.; Xu, C.; Li, W.; Mao, Z.; Ge, X.; Huang, Q.; Deng, H.; Zhao, J.; Gu, F. L.; Zhang, Y.; Chi, Z. Angew. Chem., In. Ed. 2020, 59, 17451.
[38]	Chen, H.; Ma, X.; Wu, S.; Tian, H. Angew. Chem., Int. Ed. 2014, 53, 14149. doi: 10.1002/anie.v53.51
[39]	Zhao, W.; He, Z.; Lam, J. W. Y.; Peng, Q.; Ma, H.; Shuai, Z.; Bai, G.; Hao, J.; Tang, B. Z. Chem 2016, 1, 592. doi: 10.1016/j.chempr.2016.08.010
[40]	Ma, H.; Peng, Q.; An, Z.; Huang, W.; Shuai, Z. J. Am. Chem. Soc. 2019, 141, 1010. doi: 10.1021/jacs.8b11224
[41]	Su, Y.; Wu, M.; Wang, G.; Li, J.; Chen, X.; Li, X.; Wang, G.; Zhang, K. Chem. Commun. 2023, 59, 1525. doi: 10.1039/D2CC06601G
[42]	Englman, R.; Jortner, J. J. Lumin. 1970, 1-2, 134. doi: 10.1016/0022-2313(70)90029-3
[43]	Bixon, M.; Jortner, J.; Cortes, J.; Heitele, H.; Michel-Beyerle, M. E. J. Phys. Chem. 1994, 98, 7289.
[44]	Lower, S. K.; El-Sayed, M. A. Chem. Rev. 1966, 66, 199. doi: 10.1021/cr60240a004
[45]	El-Sayed, M. A. Acc. Chem. Res. 1968, 1, 8. doi: 10.1021/ar50001a002
[46]	Hirata, S.; Totani, K.; Zhang, J.; Yamashita, T.; Kaji, H.; Marder, S. R.; Watanabe, T.; Adachi, C. Adv. Funct. Mater. 2013, 23, 3386. doi: 10.1002/adfm.v23.27
[47]	Louis, M.; Thomas, H.; Gmelch, M.; Haft, A.; Fries, F.; Reineke, S. Adv. Mater. 2019, 31, 1807887. doi: 10.1002/adma.v31.12
[48]	Li, D.; Yang, Y.; Yang, J.; Fang, M.; Tang, B. Z.; Li, Z. Nat. Commun. 2022, 13, 347. doi: 10.1038/s41467-022-28011-6
[49]	Zhang, Y.; Su, Y.; Wu, H.; Wang, Z.; Wang, C.; Zheng, Y.; Zheng, X.; Gao, L.; Zhou, Q.; Yang, Y.; Chen, X.; Yang, C.; Zhao, Y. J. Am. Chem. Soc. 2021, 143, 13675. doi: 10.1021/jacs.1c05213
[50]	Qian, C.; Ma, Z.; Fu, X.; Zhang, X.; Li, Z.; Jin, H.; Chen, M.; Jiang, H.; Jia, X.; Ma, Z. Adv. Mater. 2022, 2200544.
[51]	Li, X.; Wang, G.; Li, J.; Sun, Y.; Deng, X.; Zhang, K. ACS Appl. Mater. Interfaces 2022, 14, 1587. doi: 10.1021/acsami.1c20331
[52]	Sun, Y.; Liu, J.; Li, J.; Li, X.; Wang, X.; Wang, G.; Zhang, K. Adv. Opt. Mater. 2022, 10, 2101909. doi: 10.1002/adom.v10.4
[53]	Li, J.; Li, X.; Wang, G.; Wang, X.; Wu, M.; Liu, J.; Zhang, K. Nat. Commun. 2023, 14, 1987. doi: 10.1038/s41467-023-37662-y
[54]	Ding, S.; Wang, X.; Wang, G.; Wu, M.; Li, J.; Zhao, X.; Li, H.; Ren, S.; Zhang, K. Adv. Opt. Mater. 2022, 2202540.
[55]	Wang, J.-X.; Zhang, H.; Niu, L.-Y.; Zhu, X.; Kang, Y.-F.; Boulatov, R.; Yang, Q.-Z. CCS Chem. 2020, 2, 1391. doi: 10.31635/ccschem.020.202000158
[56]	Chen, C.; Chi, Z.; Chong, K. C.; Batsanov, A. S.; Yang, Z.; Mao, Z.; Yang, Z.; Liu, B. Nat. Mater. 2021, 20, 175. doi: 10.1038/s41563-020-0797-2
[57]	Jinnai, K.; Kabe, R.; Adachi, C. Adv. Mater. 2018, 30, 1800365. doi: 10.1002/adma.v30.38
[58]	Ma, L.; Xu, Q.; Sun, S.; Ding, B.; Huang, Z.; Ma, X.; Tian, H. Angew. Chem., Int. Ed. 2022, 61, e202115748.
[59]	Noda, H.; Chen, X. K.; Nakanotani, H.; Hosokai, T.; Miyajima, M.; Notsuka, N.; Kashima, Y.; Brédas, J. L.; Adachi, C. Nat. Mater. 2019, 18, 1084. doi: 10.1038/s41563-019-0465-6
[60]	Kondakov, D. Y.; Pawlik, T. D.; Hatwar, T. K.; Spindler, J. P. J. Appl. Phys. 2009, 106, 124510. doi: 10.1063/1.3273407
[61]	Suresh, S. M.; Duda, E.; Hall, D.; Yao, Z.; Bagnich, S.; Slawin, A. M. Z.; Bässler, H.; Beljonne, D.; Buck, M.; Olivier, Y.; Köhler, A.; Zysman-Colman, E. J. Am. Chem. Soc. 2020, 142, 6588. doi: 10.1021/jacs.9b13704
[62]	Wang, Y. N.; Shao, S. Y.; Wang, L. X. Acta Chim. Sinica 2023, 81, 1202 (in Chinese). doi: 10.6023/A23040186
	(王一诺, 邵世洋, 王利祥, 化学学报, 2023, 81, 1202.) doi: 10.6023/A23040186
[63]	Liu, Z. Y.; Rao, J. F.; Zhu, S. J.; Wang, B. Y.; Yu, F.; Feng, Q. Y.; Xie, L. H. Acta Chim. Sinica 2023, 81, 820 (in Chinese). doi: 10.6023/A23040119
	(刘振宇, 饶俊峰, 祝守加, 王兵洋, 余帆, 冯全友, 解令海, 化学学报, 2023, 81, 820.) doi: 10.6023/A23040119
[64]	Wang, Y. F.; Li, M.; Chen, C. F. Acta Chim. Sinica 2023, 81, 588 (in Chinese). doi: 10.6023/A23040153
	(王银凤, 李猛, 陈传峰, 化学学报, 2023, 81, 588.) doi: 10.6023/A23040153
[65]	Zhang, D. C.; Jia, J. H.; Liang, D.; Cai, X. B.; Zhao, Y. Q.; Hu, X. L.; Jiang, Y. B.; Lu, C. Z. Acta Chim. Sinica 2024, 82, 887 (in Chinese). doi: 10.6023/A24040148
	(张登朝, 贾吉慧, 梁栋, 蔡显宝, 赵雨晴, 胡祥龙, 江钰冰, 卢灿忠, 化学学报, 2024, 82, 887.) doi: 10.6023/A24040148
[66]	Samanta, P. K.; Kim, D.; Coropceanu, V.; Bredas, J. L. J. Am. Chem. Soc. 2017, 139, 4042. doi: 10.1021/jacs.6b12124 pmid: 28244314