Effect of tert-Butylation on the Photophysics of Thermally Activated Delayed Fluorescence Emitters

IF 3.7 Q2 MATERIALS SCIENCE, MULTIDISCIPLINARY
Kalyani Thakur, Bas van der Zee, Oskar Sachnik, Constantin Haese, Robert Graf, Jasper J. Michels, Gert-Jan A. H. Wetzelaer, Charusheela Ramanan, Paul W. M. Blom
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Abstract

Thermally activated delayed fluorescence (TADF) emitters potentially can provide organic light-emitting diodes with 100% internal quantum efficiency by harvesting triplet excitons. Generally, TADF emitters are small molecules that are not applicable for solution processability. The addition of tert-butyl groups to the periphery of TADF emitters has proven to improve their solubility in various organic solvents, reduce aggregation-induced quenching, and enhance the photoluminescence quantum yield (PLQY). This article studies the photophysical influence of the tert-butyl group attached to an emitter with a carbazole acceptor and a triazine donor. The resulting t3CzTrz-F is a blue–green TADF emitter, in which the addition of a tert-butyl group increases the rate of reverse intersystem crossing (rISC), while simultaneously decreasing the nonradiative decay rate substantially. In addition, dilution of t3CzTrz-F in a host matrix in film results in an enhanced PLQY, which is associated with a decrease in the nonradiative decay constant, while there is no change in the rISC rate. Through a solid-state NMR study, the change in rISC and nonradiative rate upon tert-butylation by enlarged intermolecular spacing and reduced vibrational and rotational freedom is rationalized, resulting in improved photophysical performance.

叔丁基化对热激活延迟荧光发射器光物理学的影响
热激活延迟荧光(TADF)发射器通过收集三重激子,有可能为有机发光二极管提供 100% 的内部量子效率。一般来说,TADF 发射器都是小分子,不适用于溶液加工。事实证明,在 TADF 发射器的外围添加叔丁基可以提高它们在各种有机溶剂中的溶解度,减少聚集诱发的淬灭,并提高光致发光量子产率(PLQY)。本文研究了带有咔唑受体和三嗪供体的发射体上所附叔丁基的光物理影响。所得到的 t3CzTrz-F 是一种蓝绿色 TADF 发射器,其中添加的叔丁基增加了反向系统间交叉(rISC)的速率,同时大大降低了非辐射衰减速率。此外,稀释薄膜中主基质中的 t3CzTrz-F 会提高 PLQY,这与非辐射衰变常数的降低有关,而 rISC 速率没有变化。通过固态核磁共振研究,合理解释了分子间距增大、振动和旋转自由度降低导致叔丁基化时 rISC 和非辐射速率的变化,从而改善了光物理性能。
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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