基于9,9'-螺二芴和萘的纯碳氢主体材料

doi:10.6023/cjoc202108017

摘要/Abstract

利用磷光有机发光二极管的主客体掺杂结构有助于避免三重态激子浓度猝灭, 从而提高器件性能. 9,9'-螺二芴(SBF)及其衍生物具有独特的正交构型和刚性骨架, 具有高玻璃化转变温度、高三线态能级和用作主体材料的潜力. 通过引入萘环合成并表征了两种基于SBF的纯碳氢化合物(PHC)磷光发光器件的主体材料, 命名为1,4-SBF-Nap和1,8-Oct-Nap. 其中, 1,8-Oct-Nap分子存在一个有趣的环化反应, 形成八原子环结构而不是一般的SBF. 以Ir(MDQ)₂(acac)为客体, 成功制备了基于这两种主体的红光器件, 最大外量子效率(EQE)分别为15.0%和13.7%, 证明PHC主体材料在设计上的多样性.

关键词: 有机发光二极管, 主体材料, 9,9'-螺二芴, 萘, 八元环

The utilization of host-guest doped structure of phosphorescent organic light-emitting diodes helps avoid the triplet exciton concentration quenching, thus improve the device performance. 9,9'-Spirobifluorene (SBF) and its derivatives with a unique orthogonal configuration and rigid framework, exhibit high glass transition temperature, high triplet energy levels, and potential to be used as host materials. In this work, two types of SBF-based pure hydrocarbon (PHC) phosphorescent light-emitting device host materials were synthesized and characterized by introducing naphthalene, named 1,4-SBF-Nap and 1,8-Oct-Nap. 1,8-Oct-Nap has an interestingly cyclized cites and resulting in an octatomic ring structure instead of normal SBF. Co-evaporating with bis(2-methyldibenzo[f,h]quinoxaline)(acetylacetonate)iridium(III) (Ir(MDQ)₂(acac)), the red-light devices based on these two hosts were successfully fabricated. The maximum external quantum efficiencies (EQE) were 15.0% and 13.7% for 1,4-SBF-Nap and 1,8-Oct-Nap, respectively. The diversity of the PHC host materials can be expanded by the utilization of naphthalene.

Key words: organic light-emitting diode, host, 9,9'-spirobifluorene, naphthalene, octatomic ring

引用此文

郑琦, 文亚, 屈扬坤, 朱元皓, 冯敏强, 蒋佐权. 基于9,9'-螺二芴和萘的纯碳氢主体材料[J]. 有机化学, 2022, 42(2): 572-579.

Qi Zheng, Ya Wen, Yangkun Qu, Yuanhao Zhu, Mankeung Fung, Zuoquan Jiang. Pure Hydrocarbon Host Materials Based on 9,9'-Spirobifluorene/Naphthalene Hybrid[J]. Chinese Journal of Organic Chemistry, 2022, 42(2): 572-579.

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图/表 8

Scheme 1. Synthetic routes of 1,4-SBF-Nap and 1,8-Oct-Nap.

Figure 1. Theoretical calculations of the possible intermediate spatial structures of 1,8-Oct-Nap using DFT[24] (ground states) at the pbe0 [25] (em=gd3bj)[26]/def2svp[27] level

Figure 2. Theoretical HOMO/LUMO energy levels and distributions, singlet and triplet excitation energies, and electron-hole analysis of singlet and triplet excited states, for 1,4-SBF-Nap and 1,8-Oct-Nap using DFT (ground states) at the pbe0[25] (em=gd3bj)[26]/def2svp[27] level and TD-DFT (excited states) at the cam-b3lyp[30] (em=gd3bj)[26]/def2svp[27] level

Figure 3. Crystal structures and crystal packing modes of 1,4-SBF-Nap and 1,8-Oct-Nap

Figure 4. UV-vis absorption, fluorescence, and phosphorescent (77 K) spectra of 1,4-SBF-Nap and 1,8-Oct-Nap

Figure 5. Cyclic voltammetry in CH2Cl2/[Bu4NPF6] 0.1 mol/L (100 mV•s–1) of 1,4-SBF-Nap and 1,8-Oct-Nap

Figure 6. PhOLED device performance PhOLED device characteristics of 1,4-SBF-Nap (red), 1,8-Oct-Nap (blue) and mCP (black). (a) EQE versus luminance characteristics; (b) current density and luminance versus driving voltage (J-V-L) characteristics; (c) current efficiency and power efficiency versus luminance characteristics; (d) device structures of PhOLEDs based on 1,4-SBF-Nap, 1,8-Oct-Nap, and mCP, with functional materials including HAT-CN, TAPC, TCTA, Ir(MDQ)2(acac), B4PyMPM, Liq and Al

Host	V_on/V₁₀₀^a/V	CE_max^b/(cd•A^–1)	PE_max^b/(lm•W^–1)	EQE_max^b/%	λ_max^c/nm	CIE (x, y)^c
1,4-SBF-Nap	3.6/4.8	25.5/18.8/12.7	22.3/12.2/5.6	15.0/11.0/7.3	608	(0.61, 0.38)
1,8-Oct-Nap	3.0/4.2	21.9/14.4/9.7	22.9/10.8/5.1	13.7/9.0/6.1	608	(0.62, 0.38)
mCP	2.8/3.2	22.6/22.6/19.2	22.3/22.2/14.4	13.8/13.8/11.7	608	(0.61, 0.38)

Table 1. Summary of device performances

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