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DOI: https://doi.org/10.6023/A26040128

Article

Theoretical Study on the Performance of Through-Space Charge-Transfer Thermally Activated Delayed Fluorescence

  • 万浩波 ,
  • 谢文斌 ,
  • 杨磊 ,
  • 冉雪琴 ,
  • 冯全友 ,
  • 解令海
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  • aState Key Laboratory of Flexible Electronics (LoFE), College of Materials Science and Engineering, Nanjing University of Posts & Telecommunications (NJUPT), Nanjing 210023, China;
    bKey Laboratory of Flexible Electronics, College of Flexible Electronics, Nanjing Tech University Nanjing 211816, China

Received date: 2026-04-20

  Online published: 2026-06-25

Supported by

National Natural Science Foundation of China (Nos.21503114), and the Six Peak Talents Foundation of Jiangsu Province (XCL-CXTD-009), the National Key Research and Development Program of China （2024YFB3612600）

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Abstract

Through-space charge-transfer thermally activated delayed fluorescence (TSCT-TADF) materials have attracted considerable interest due to their considerable potential for high-performance, particularly non-doped organic light-emitting diodes (OLEDs). Introducing neutral bulky shielding groups into TSCT frameworks has been demonstrated as an effective strategy for developing efficient non-doped emitters; however, the precise molecular-level regulatory mechanisms remain to be fully elucidated. In this study, based on density functional theory (DFT) and the polarizable continuum model (PCM), starting from the experimentally reported high-efficiency molecule 3Ph-SPT, a series of derivative molecules including Ph2Ad-SPT, Ph2Ad-SDT, and Ph2Ad-SST were theoretically designed to elucidate the synergistic regulatory effects of "neutral group engineering" and "donor-atom engineering" on the performance of TSCT-TADF materials. A systematic analysis was conducted on their geometric structures, electronic properties, absorption/emission behaviors, intersystem crossing/reverse intersystem crossing (ISC/RISC) processes, as well as radiative and non-radiative decay dynamics. The results indicate that neutral group engineering—replacing the terphenyl unit with a diphenyladamantyl group—effectively tunes the excited-state energy levels and geometries, reducing the singlet-triplet energy gap to -0.007 eV and suppressing excessive S1→S0 geometric relaxation. Further donor-atom engineering exhibits distinct effects: O→2(-CH3) substitution degrades performance owing to an increased ΔEST and weakened spin-orbit coupling (SOC), whereas O→S substitution synergistically enhances SOC (to 0.132 cm-1) and markedly reduces the reorganization energy, thereby elevating the RISC rate to 2.10 × 10⁷ s-1and demonstrating superior performance over the prototype molecule, furthermore, preliminary investigations in the thin-film state also expect excellent TADF performance. This work theoretically clarifies the microscopic mechanism of synergistically regulating the performance of TSCT-TADF materials through neutral-group engineering and donor-atom engineering, providing clear theoretical guidance for the rational design of non-doped TADF materials that exhibit both high exciton utilization efficiency and high luminescent efficiency.

Key words： Through-space charge transfer; Thermally activated delayed fluorescence; Neutral-group engineering; Donor-atom engineering; Density functional theory; Excited-state dynamics

Cite this article

万浩波 , 谢文斌 , 杨磊 , 冉雪琴 , 冯全友 , 解令海 . Theoretical Study on the Performance of Through-Space Charge-Transfer Thermally Activated Delayed Fluorescence[J]. Acta Chimica Sinica, 0 : 40128 -40128 . DOI: 10.6023/A26040128

References

[1] Liu L, Chen X. Journal of Beijing Normal University Natural Science.2021, 57, 671-680.
[2] Wang H, Zhu Y, Xie F, Li Y, Tang J. Chinese Journal of Luminescence.2023, 44, 140-162.
[3] Zou J, Zhu G, Wang L, Xu M, Wu W, Peng J. Chinese Journal of Luminescence.2023, 44, 198-217.
[4] Zhang N, Han S R, Ma H W, Chen P K. Acta Chimica Sinica.2025, 83, 10-16
(in Chinese). (张大杰, 张妞, 韩书冉, 马宏伟, 陈磅宽, 化学学报,2025, 83, 10-16.)
[5] Uoyama H, Goushi K, Shizu K, Nomura H, Adachi C. Nature.2012, 492, 234-238.
[6] Lee J, Shizu K, Tanaka H, Nomura H, Yasuda T, Adachi C. Journal of Materials Chemistry C.2013, 1, 4599-4604.
[7] Shao S, Hu J, Wang X, Wang L, Jing X, Wang F. Journal of the American Chemical Society.2017, 139, 17739-17742.
[8] Fang S Q, Tong K N, Chen S H, Zhang Q F, Tong B H, Fung M, Kong H. Acta Chimica Sinica.2025, 83, 471-478
(in Chinese). (方素琴, 童恺宁, 陈思浛, 张千峰, 童碧海, 冯敏强, 孔辉, 化学学报, 2025, 83, 471-478.)
[9] Ma J Z, Li Y, Gao S, Zhao Y, Ding L, Zhou D Y, Fan J. Acta Chimica Sinica.2025, 83, 17-24
(in Chinese). (马金珠, 李阳, 高珊, 赵越, 丁磊, 周东营, 樊健, 化学学报, 2025, 83 ,17-24.)
[10] Zhang D C, Jia J H, Liang D, Cai X B, Zhao Y Q, Hu K L, Jiang Y B, Lu C Z. Acta Chimica Sinica.2024, 82, 887-893
(in Chinese). (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, 887-893.)
[11] Puttock E V, Ranasinghe C S K, Babazadeh M, Jang J, Huang D M, Tsuchiya Y, Adachi C, Burn P L, Shaw P E. Macromolecules.2020, 53, 10375-10385.
[12] Li J, Tian T, Guo D, Li T, Zhang M, Zhang H. Journal of Materials Chemistry C.2023, 11, 6119-6129.
[13] Song X, Xu H. Journal of Information Display.2020, 21, 149-172.
[14] Kim H J, Yasuda T. Advanced Optical Materials.2022, 10, 2270086.
[15] Wang Y, Shao S, Wang L. Acta Chimica Sinica.2023, 81, 1202-1214
(in Chinese). (王一诺, 邵世洋, 王利祥, 化学学报,2023, 81, 1202-1214.)
[16] Chen G, Wang J, Chen W-C, Gong Y, Zhuang N, Liang H, Xing L, Liu Y, Ji S, Zhang H-L, Zhao Z, Huo Y, Tang B Z. Advanced Functional Materials.2023, 33, 2211893.
[17] Wang Y-K, Wu S-F, Yuan Y, Li S-H, Fung M-K, Liao L-S, Jiang Z-Q. Organic Letters. 2017, 19, 3155-3158.
[18] Tang X, Cui L-S, Li H-C, Gillett A J, Auras F, Qu Y-K, Zhong C, Jones S T E, Jiang Z-Q, Friend R H, Liao L-S. Nature Materials. 2020, 19, 1332-+.
[19] Tsujimoto H, Ha D-G, Markopoulos G, Chae H S, Baldo M A, Swager T M. Journal of the American Chemical Society.2017, 139, 4894-4900.
[20] Chen X-L, Jia J-H, Yu R, Liao J-Z, Yang M-X, Lu C-Z. Angewandte Chemie-International Edition.2017, 56, 15006-15009.
[21] Cha J-R, Lee C W, Lee J Y, Gong M-S. Dyes and Pigments. 2016, 134, 562-568.
[22] Spuling E, Sharma N, Samuel I D W, Zysman-Colman E, Braese S. Chemical Communications. 2018, 54, 9278-9281.
[23] Wang X, Wang S, Lv J, Shao S, Wang L, Jing X, Wang F. Chemical Science. 2019, 10, 2915-2923.
[24] Wang T, Cheng Y X, Yang C L. Progress in Polymer Science.2024, 158, 101892.
[25] Yan X Y, Song S Y, Liang S C, Liu K K, Liu X T, Lu C. Chemical Science. 2025, 16, 16770-16779.
[26] Wang J S, Niu Y D, Jiang Y, Yao C, Dai Z X, Deng Y H, Zhang J F. Chemical Engineering Journal.2025, 524, 169199.
[27] Jing Y-Y, Tao X-D, Yang M-X, Chen X-L, Lu C-Z. Chemical Engineering Journal.2021, 413, 127418.
[28] Zhan Q, Cao C, Huang T, Zhou C, Xie Z, Zou Y, Lee C-S, Yang C. Advanced Optical Materials.2021, 9, 2100273.
[29] Wang H-Y, Xie F-M, Li H-Z, Zhang K, Zou J, Li Y-Q, Tang J-X. Chemical Engineering Journal.2024, 495, 153511.
[30] Li J, Zhao F, Chen Y, Zhang M, Li T, Zhang H. Journal of Materials Chemistry C.2021, 9, 15309-15320.
[31] An L, Su R, Sun Y, Song C, Wang Q. Computational and Theoretical Chemistry. 2023, 1228, 114277.
[32] Cossi M, Scalmani G, Rega N, Barone V. Journal of Chemical Physics.2002, 117, 43-54.
[33] Cossi M, Barone V, Cammi R, Tomasi J. Chemical Physics Letters.1996, 255, 327-335.
[34] Tirado-Rives J, Jorgensen W L. Journal of Chemical Theory and Computation. 2008, 4, 297-306.
[35] Adamo C, Barone V. Journal of Chemical Physics.1999, 110, 6158-6170.
[36] Zhao Y, Truhlar D G. Accounts of Chemical Research.2008, 41, 157-167.
[37] Hohenstein E G, Chill S T, Sherrill C D.Journal of Chemical Theory and Computation. 2008, 4, 1996-2000.
[38] Chai J-D, Head-Gordon M. Journal of Chemical Physics.2008, 128.
[39] Yanai T, Tew D P, Handy N C. Chemical Physics Letters.2004, 393, 51-57.
[40] Frisch M J, Trucks G W, Schlegel H B, Scuseria G E, Robb M A, Cheeseman J R, Scalmani G, Barone V, Petersson G A, Nakatsuji H, Li X, Caricato M, Marenich A V, Bloino J, Janesko B G, Gomperts R, Mennucci B, Hratchian H P, Ortiz J V, Izmaylov A F, Sonnenberg J L, Williams, Ding F, Lipparini F, Egidi F, Goings J, Peng B, Petrone A, Henderson T, Ranasinghe D, Zakrzewski V G, Gao J, Rega N, Zheng G, Liang W, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Throssell K, Montgomery Jr. J A, Peralta J E, Ogliaro F, Bearpark M J, Heyd J J, Brothers E N, Kudin K N, Staroverov V N, Keith T A, Kobayashi R, Normand J, Raghavachari K, Rendell A P, Burant J C, Iyengar S S, Tomasi J, Cossi M, Millam J M, Klene M, Adamo C, Cammi R, Ochterski J W, Martin R L, Morokuma K, Farkas O, Foresman J B, Fox D J. Gaussian 16 Rev. C.01[Z]. Wallingford, CT. 2016.
[41] Park I S, Matsuo K, Aizawa N, Yasuda T. Advanced Functional Materials.2018, 28, 1802031.
[42] Cui L-S, Gillett A J, Zhang S-F, Ye H, Liu Y, Chen X-K, Lin Z-S, Evans E W, Myers W K, Ronson T K, Nakanotani H, Reineke S, Bredas J-L, Adachi C, Friend R H. Nature Photonics.2020, 14, 636-+.
[43] Lawetz V, Orlandi G, Siebrand W. The Journal of Chemical Physics.1972, 56, 4058-4072.
[44] Neese F. Wiley Interdisciplinary Reviews-Computational Molecular Science.2018, 8, e1327.
[45] Neese F. Wiley Interdisciplinary Reviews-Computational Molecular Science.2012, 2, 73-78.
[46] Neese F. Wiley Interdisciplinary Reviews-Computational Molecular Science.2022, 12, e1606.
[47] Nelsen S F, Blackstock S C, Kim Y. Journal of the American Chemical Society.1987, 109, 677-682.
[48] Hilborn R C. American Journal of Physics.1982, 50, 982-986.
[49] Liu Z, Lu T, Chen Q. Carbon.2020, 165, 461-467.
[50] Lu T, Chen F. Journal of Computational Chemistry.2012, 33, 580-592.
[51] Lu T, Chen F. Journal of Molecular Graphics & Modelling.2012, 38, 314-323.
[52] Lu T. Journal of Chemical Physics.2024, 161.
[53] Zhuang C, Yue H, Zhang H. Plastics.2010, 39, 81-84.
[54] Wang X F, Wu Z M, Li R, Li X F, Song Y Z, Fan J Z, Wang C K, Lin L L. Journal of Physical Chemistry A.2024, 128, 3241-3252.
[55] Humphrey W, Dalke A, Schulten K. Journal of Molecular Graphics & Modelling.1996, 14, 33-38.
[56] Li P, Zhou C F, Li W J, Zhang Y W, Yuan J, Chen R F. Science China-Materials.2023, 66, 3958-3967.
[57] Lee Y N, Kim J, Lee S H Y, Sim E, Hong J I. Chemical Engineering Journal.2023, 476, 146659.
[58] Gan L, Xu Z D, Wang Z H, Li B B, Li W, Cai X Y, Liu K K, Liang Q M, Su S J. Advanced Functional Materials.2019, 29, 1808088.
[59] Mei Y Q, Liu D, Li J Y, Li H T, Wei W K. Journal of Materials Chemistry C.2021, 9, 5885-5892.
[60] Tang X, Cui L S, Li H C, Gillett A J, Auras F, Qu Y K, Zhong C, Jones S T E, Jiang Z Q, Friend R H, Liao L S. Nature Materials.2020, 19, 1332-1338.
[61] Chen R, Tang Y, Wan Y, Chen T, Zheng C, Qi Y, Cheng Y, Huang W. Scientific Reports. 2017, 7, 6225.
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