基于ESIPT的水杨醛吡啶衍生物发光调控机制的理论研究  

Theoretical Study on the Luminescence Regulation Mechanism of Salicylaldehyde Pyridine Derivatives Based on ESIPT

作　　者：赵建丽 郭臻 杨文静 陈雪波[2] ZHAO Jianli;GUO Zhen;YANG Wenjing;CHEN Xuebo(College of Materials Science and Engineering,Taiyuan University of Technology,Taiyuan 030024,China;Key Laboratory of Theoretical and Computational Photochemistry,Beijing Normal University,Beijing 100875,China)

机构地区：[1]太原理工大学材料科学与工程学院,山西太原030024 [2]北京师范大学理论计算光化学重点实验室,北京100875

出　　处：《山西大学学报（自然科学版）》2023年第3期699-707,共9页Journal of Shanxi University(Natural Science Edition)

基　　金：国家自然科学基金(21903059)。

摘　　要：本文运用完全活化空间自洽场(CASSCF)和完全活化空间二阶微扰(CASPT2)方法,结合激发态辐射速率公式,探索了两种水杨醛-4,6-(二甲基氨基)-吡啶(SDP)衍生物,即SDP吡啶环亚胺基对位单取代氯原子(R-SDP-Cl)和苯环羟基对位单取代氯原子(L-SDP-Cl),在气相、水、二甲亚砜、四氢呋喃和甲苯溶液中发生激发态分子内质子迁移(ESIPT)反应的机制,双荧光发射特性以及发光范围。研究结果表明,在吡啶环亚胺基和苯环羟基对位分别引入氯原子后,共轭体系的电荷发生重排,但其ESIPT反应能垒接近,因此该取代基对ESIPT反应能垒几乎没有影响。根据两种色光的发光二极管的配色原理,将荧光速率比类比于亮度比,近似评估两种衍生物的发光范围,R-SDP-Cl的发光范围为CIE(0.138,0.083)~CIE(0.139,0.086),而L-SDP-Cl的发光范围为CIE(0.142,0.090)~CIE(0.145,0.095),可以发现L-SDP-Cl对发光范围的拓展效果更好。这些理论预测可以为有机发光二极管(OLED)材料分子的设计和优化提供合理化方案。In this paper,the Complete active space self consistent field(CASSCF)and Complete active space second-order perturbation(CASPT2)methods,combined with the excited state radiation rate formula,were used to explore two salicylaldehyde 4,6-(dimethylamino)pyridine(SDP)derivatives,namely,SDP pyridine ring imino group para monosubstituted chlorine atom(R-SDP-Cl)and benzene ring hydroxyl group para monosubstituted chlorine atom(L-SDP-Cl),in the gas phase,water,dimethyl sulfoxide,tetrahydrofuran and toluene,the mechanism of excited state intramolecular proton transfer(ESIPT)reaction,double fluorescence emission characteristics and luminous range.The results show that the charge of the conjugated system rearranges after the introduction of chlorine atoms into the pyridine ring imino group and the benzene ring hydroxy group respectively,but the ESIPT reaction energy barrier is close,so the substituent has little effect on the ESIPT reaction energy barrier.At the same time,according to the color matching principle of light-emitting diodes with two colors of light,the fluorescence rate ratio is comparable to the brightness ratio to approximately evaluate the luminous range of the two derivatives.The luminous range of R-SDP-Cl is CIE(0.138,0.083)-CIE(0.139,0.086),while the luminous range of L-SDP-Cl is CIE(0.142,0.090)-CIE(0.145,0.095).It can be found that L-SDP-Cl has a better effect on expanding the luminous range.These theoretical predictions can provide a rationalization scheme for the design and optimization of OLED materials.

关 键 词：水杨醛吡啶衍生物 ESIPT CASSCF CASPT2 激发态辐射速率公式 

分 类 号：O436[机械工程—光学工程]