Wang Yi, Wu Shengxiu, Xu Shipan, Du Xuyang, Sun Yuanhui, Yan An, Zhou Guijiang, Yang Xiaolong
School of Chemistry, Xi'an Key Laboratory of Sustainable Energy Material Chemistry, Engineering Research Center of Energy Storage Materials and Devices, Ministry of Education, Xi'an Jiaotong University, Xi'an 710049, China.
Molecules. 2024 Dec 9;29(23):5807. doi: 10.3390/molecules29235807.
Triarylamine groups have been widely utilized in the development of high-performance charge-transporting or luminescent materials for fabricating organic light-emitting diodes (OLEDs). In this study, atmospheric pressure chemical ionization (APCI) Q-Orbitrap mass spectrometry was adopted to investigate the dissociation behaviors of these triarylamine derivatives. Specifically, taking [M+H] as the precursor ion, high-energy collision dissociation (HCD) experiments within the energy range from 0 to 80 eV were carried out. The results showed that triarylamine derivatives with specific structures exhibited distinct fragmentation patterns. For diarylamine, the formation of odd-electron ions was ascribed to the single-electron transfer (SET) reaction mediated by ion-neutral complexes (INCs). In the low-energy range (below 40 eV), proton transfer served as the predominant mechanism for generating even-electron ions. Conversely, in the high-energy range (60 eV and above), the INC-SET reaction dominated. The precursor ion's structure affects compliance with the "even-electron rule", which has exceptions. Here, even-electron ion fragmentation was energy-dependent and could deviate from the rule, yet did not conflict with its concept, reflecting dissociation complexity. This research provides insights for triarylamine-based OLED materials, facilitating analysis and identification, and is expected to aid OLED material development.
三芳基胺基团已被广泛应用于开发用于制造有机发光二极管（OLED）的高性能电荷传输或发光材料。在本研究中，采用大气压化学电离（APCI）Q-轨道阱质谱法研究了这些三芳基胺衍生物的解离行为。具体而言，以[M+H]作为前体离子，在0至80 eV的能量范围内进行了高能碰撞解离（HCD）实验。结果表明，具有特定结构的三芳基胺衍生物表现出不同的碎裂模式。对于二芳基胺，奇电子离子的形成归因于离子-中性复合物（INC）介导的单电子转移（SET）反应。在低能量范围（低于40 eV），质子转移是产生偶电子离子的主要机制。相反，在高能量范围（60 eV及以上），INC-SET反应占主导。前体离子的结构影响对“偶电子规则”的遵循情况，该规则存在例外。在此，偶电子离子碎裂与能量有关，可能偏离该规则，但与其概念不冲突，反映了解离的复杂性。本研究为基于三芳基胺的OLED材料提供了见解，有助于分析和鉴定，有望助力OLED材料的开发。
