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

研究论文

空间电荷转移型热激活延迟荧光性能的理论研究

  • Wan Haobo ,
  • Xie Wenbin ,
  • Yang Lei ,
  • Ran Xueqin ,
  • Feng Quanyou ,
  • Xie ,
  • Linghai
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  • a南京邮电大学 柔性电子国家重点实验室 材料科学与工程学院 南京 中国 210023;
    b南京工业大学 柔性电子重点实验室 柔性电子学院 南京 中国 211816

收稿日期: 2026-04-20

  网络出版日期: 2026-06-25

基金资助

国家自然科学基金（21503114）、江苏省六大人才高峰项目（XCL-CXTD-009）、国家重点研发计划（2024YFB3612600）

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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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摘要

本研究基于密度泛函理论(DFT)和极化连续介质模型(PCM),以实验报道的高效分子3Ph-SPT为起点,通过理论设计构建了Ph2Ad-SPT、Ph2Ad-SDT与Ph2Ad-SST等一系列衍生分子以揭示中性基团工程与给体原子工程对TSCT-TADF材料性能的协同调控机制,系统分析了它们的几何结构、电子特性、吸收/发射行为、系间窜越(ISC/RISC)过程以及辐射/非辐射衰减动力学.结果表明,中性基团工程(以金刚烷苯基替换三联苯)可有效调控激发态能级与几何结构,将单重态-三重态能隙降至-0.007 eV,并抑制S1→S0的几何弛豫.进一步的给体原子工程呈现差异化影响：O→2(-CH₃)取代则因增大的ΔEST与减弱的SOC而导致性能下降;O→S取代则能协同优化自旋轨道耦合(SOC增至0.132 cm-1)并显著降低重组能,从而使RISC速率提升至2.10 × 10⁷ s-1,展现出超越原型分子的优越性能,而其在薄膜态初步研究也预期具有优异的TADF性能.本研究从理论上阐明了通过中性基团工程与给体原子工程来协同调控TSCT-TADF材料性能的微观机制,为理性设计兼具高激子利用率与高发光效率的非掺杂TADF材料提供了明确的理论指导.

关键词： 空间电荷转移; 热激活延迟荧光; 中性基团工程; 给体原子工程; 密度泛函理论; 激发态动力学

本文引用格式

Wan Haobo , Xie Wenbin , Yang Lei , Ran Xueqin , Feng Quanyou , Xie , Linghai . 空间电荷转移型热激活延迟荧光性能的理论研究[J]. 化学学报, 0 : 40128 -40128 . DOI: 10.6023/A26040128

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

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