Multi-channel Non-radiative Dynamics to Reveal Δ E ST as the Key Efficiency Descriptor for Deep-Blue Pt(II) Phosphors

IF 4.5 2区化学 Q2 CHEMISTRY, PHYSICAL

The Journal of Physical Chemistry Letters Pub Date : 2026-10-16 DOI:10.1021/acs.jpclett.6c03198

Xiao Chen,Weitang Li,Wenjie Zhang,Yulong Li,Yaxin Wang,Zhigang Shuai

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引用次数: 0

Abstract

Abstract Tetradentate platinum(II) complexes are promising candidates for phosphorescent organic light-emitting diodes (OLEDs), combining deep-blue emission, high color purity, and potential for near-unity photoluminescence quantum yields (PLQYs). However, despite their rigid structures, which should suppress non-radiative decay, many of these complexes still show surprisingly low PLQYs, and the mechanism underlying this discrepancy has remained unclear. Here, through first-principle calculations of multi-channel transition rates for 25 tetradentate Pt(II) complexes, we show that this apparent paradox arises from a thermally activated S1 non-radiative channel (T1 → S1 → S0) that dominates the non-radiative decay. The rate of this channel depends exponentially on the singlet–triplet gap ΔEST, establishing ΔEST as a key descriptor for PLQY. Electronic structural analysis reveals that donors on the pyridine unit can delocalize LUMO, increase HOMO–LUMO overlap, and help enlarge ΔEST and PLQY. These results provide a unified mechanistic picture and a direct design rule for high-efficiency deep-blue Pt(II) emitters.

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多通道非辐射动力学揭示Δ E ST是深蓝色（II）荧光粉的关键效率描述符

四牙齿铂（II）配合物是磷光有机发光二极管（oled）的有希望的候选者，具有深蓝色发射，高色纯度和近单位光致发光量子产率（PLQYs）的潜力。然而，尽管它们的刚性结构应该抑制非辐射衰变，许多这些复合物仍然显示出令人惊讶的低PLQYs，并且这种差异的机制仍然不清楚。这里，通过对25个四牙齿Pt（II）配合物的多通道跃迁速率的第一性原理计算，我们表明这种明显的悖论是由热激活的S1非辐射通道（T1→S1→S0）引起的，该通道主导了非辐射衰变。该信道的速率以指数方式依赖于单重态-三重态间隙ΔEST，从而建立ΔEST作为PLQY的关键描述符。电子结构分析表明，吡啶单元上的给体可以使LUMO离域，增加HOMO-LUMO重叠，有助于增大ΔEST和PLQY。这些结果为高效深蓝Pt（II）发射体提供了一个统一的机理图和直接的设计规则。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

The Journal of Physical Chemistry Letters CHEMISTRY, PHYSICAL-NANOSCIENCE & NANOTECHNOLOGY

CiteScore

9.60

自引率

7.00%

发文量

1519

审稿时长

1.6 months

期刊介绍： The Journal of Physical Chemistry (JPC) Letters is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, chemical physicists, physicists, material scientists, and engineers. An important criterion for acceptance is that the paper reports a significant scientific advance and/or physical insight such that rapid publication is essential. Two issues of JPC Letters are published each month.