Scholarlink

<p>This study systematically investigated the structure-property relationship of Cu(I) carbene-metal-amide (CMA) complexes using density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations. Potential energy surface analysis revealed that planar geometry represents the most stable configuration for both ground and excited states. By modulating ligand structures, we not only elucidated the luminescence mechanism in solution phase but also demonstrated that the synergistic effect of small singlet-triplet energy gap (Δ<i>E</i><sub>ST</sub>) and low reorganization energy (<i>λ</i>) can facilitate rapid reverse intersystem crossing (RISC) despite weak spin-orbit coupling (SOC). Comparative studies between solution and solid phases showed that molecular packing in crystalline state effectively suppresses structural distortion, significantly enhancing radiative transition efficiency by reducing non-radiative decay. The planar geometry-enabled fast ISC/RISC cycling ensures efficient triplet exciton utilization, leading to high-performance thermally activated delayed fluorescence (TADF). Our work provides molecular-level insights into the TADF mechanism of Cu-CMA systems, particularly revealing a non-conventional exciton conversion mechanism governed by the “weak SOC-small Δ<i>E</i><sub>ST</sub>-low <i>λ″</i> synergy, which offers new design principles for developing cost-effective, high-efficiency copper-based TADF materials.</p>

错误：搜索内容不能为空，请输入英文关键词
错误：关键词超出字数限制，请精简
高级检索

Overcoming the Spin-Orbit Coupling Limitation: Cooperative Singlet-Triplet Energy Gap and Reorganization Energy Engineering for High-Efficiency Thermally Activated Delayed Fluorescence in Carbene-Cu(I)-Amide Systems

  • 期刊论文

  • 发表日期：

    2025年9月9日

查看全文
  • Tengfei He,
  • Zihan Zhang,
  • Lifang Yin,
  • Yi Zhao,
  • Mengnan Zhao,
  • Qiang Gao,
  • Yajun Yin,
  • Yufei Yang,
  • Tongshun Wu,
  • Luyi Zou

摘要

This study systematically investigated the structure-property relationship of Cu(I) carbene-metal-amide (CMA) complexes using density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations. Potential energy surface analysis revealed that planar geometry represents the most stable configuration for both ground and excited states. By modulating ligand structures, we not only elucidated the luminescence mechanism in solution phase but also demonstrated that the synergistic effect of small singlet-triplet energy gap (ΔEST) and low reorganization energy (λ) can facilitate rapid reverse intersystem crossing (RISC) despite weak spin-orbit coupling (SOC). Comparative studies between solution and solid phases showed that molecular packing in crystalline state effectively suppresses structural distortion, significantly enhancing radiative transition efficiency by reducing non-radiative decay. The planar geometry-enabled fast ISC/RISC cycling ensures efficient triplet exciton utilization, leading to high-performance thermally activated delayed fluorescence (TADF). Our work provides molecular-level insights into the TADF mechanism of Cu-CMA systems, particularly revealing a non-conventional exciton conversion mechanism governed by the “weak SOC-small ΔEST-low λ″ synergy, which offers new design principles for developing cost-effective, high-efficiency copper-based TADF materials.