喹喔啉并菲啰啉类热激活延迟荧光材料的合成及其发光性质  

Synthesis and Luminescent Properties of Thermally Activated Delayed Fluorescence Materials Based on Quinoxaline Phenanthroline

作　　者：夏晓雪 王达浩 曹远哲 袁国 胡英元 赵鑫[1] Xia Xiaoxue;Wang Dahao;Cao Yuanzhe;Yuan Guo;Hu Yingyuan;Zhao Xin(School of Chemistry and Life Sciences,Suzhou University of Science and Technology,Suzhou 215009,Jiangsu,China;Jiangsu Key Laboratory for Carbon-Based Functional Materials&Devices,Institute of Functional Nano&Soft Materials(FUNSOM),Soochow University,Suzhou 215123,Jiangsu,China)

机构地区：[1]苏州科技大学化学与生命科学学院,江苏苏州215009 [2]苏州大学功能纳米与软物质研究院江苏省碳基功能材料与器件重点实验室,江苏苏州215123

出　　处：《光学学报》2025年第1期177-185,共9页Acta Optica Sinica

基　　金：国家自然科学基金(21905048);江苏省研究生研究创新项目(KYCX24_3462)。

摘　　要：为了获得结构新颖的长波长热激活延迟荧光(TADF)材料,基于喹喔啉并菲啰啉(DPPZ),通过引入氰基或氰基苯合成了两种具有新颖受体的红光热激活延迟荧光材料:di TPA-DPPDC和di TPA-DPPDQ。研究发现,di TPA-DPPDC和di TPA-DPPDQ都具有典型的延迟荧光性质。相对于常见的供受体型TADF分子,它们具有较大的振子强度(分别为0.0682和0.0794)和小的单重态与三重态的能级差(ΔE_(ST)),在一定程度上实现了小的ΔE_(ST)与大的光致发光量子产率(PLQY)之间的平衡。两种材料皆以大位阻基团三苯胺(TPA)为供体,抑制了聚集诱导荧光猝灭(ACQ)现象。在di TPA-DPPDC中引入的氰基使得分子共轭程度增大,发光波长高达686 nm(深红光发射),但由于其振子强度相对较小(0.0682),故其PLQY较小。在di TPA-DPPDQ中引入的氰基苯,由于苯环扭曲使分子共轭程度不及前者,故发光波长为605 nm(红光发射),但因其相对较大的振子强度(0.0794),使其PLQY增大至62.8%,表现出良好的发光性能。Objective To develop novel long-wavelength red TADF materials,two compounds,di TPA-DPPDC and di TPA-DPPDQ,are synthesized using dipyrido[3,2-a:2',3'-c]phenazine (DPPZ) as the base receptor,modified with cyanide and cyanobenzene groups.Both materials exhibit characteristic delayed fluorescence properties,including small single-triplet energy differences (ΔE_(ST)) and relatively high oscillator strengths (0.0682 and 0.0794,respectively) compared to conventional donor-acceptor TADF molecules.This balance between smallΔE_(ST) and high photoluminescence quantum yield (PLQY) is achieved using triphenylamine (TPA) as a sterically hindered donor to suppress aggregation-induced fluorescence quenching (ACQ).Cyanide modification in di TPA-DPPDC enhances molecular conjugation,resulting in deep red emission at 686 nm,though its lower oscillator strength (0.0682) limits its PLQY.Conversely,the cyanobenzenemodified di TPA-DPPDQ emits red light at 605 nm,with a higher oscillator strength (0.0794),achieving a PLQY of62.8%,indicative of superior luminescence performance.Methods In this paper,we synthesize the di TPA-DPPDC and di TPA-DPPDQ materials via Buchwald?Hartwig and Suzuki coupling reactions.Their photophysical,delayed fluorescence,and thermal properties are investigated.Comparative analysis of their luminescent properties is conducted to evaluate their performance.Results and Discussions The structures of di TPA-DPPDC and di TPA-DPPDQ are confirmed by ~1H NMR,~(13)C NMR,and high-resolution mass spectrometry (HRMS).Density functional theory (DFT) calculations reveal twisted molecular structures due to TPA incorporation,which effectively suppresses ACQ and minimizesΔE_(ST )(Fig.3).di TPA-DPPDC exhibits deep red emission at 686 nm,while di TPA-DPPDQ emits red light at 605 nm due to the breaking of conjugation by the benzene ring[Fig.4(a)].Both compounds exhibit typical delayed fluorescence behavior (Fig.5).Fluorescence peaks of both materials red-shift with increasing solvent polarity,demonstrating intramolecular charge tr

关 键 词：材料 有机发光二极管 延迟荧光 喹喔啉并菲啰啉 光致发光 

分 类 号：O469[理学—凝聚态物理]