氰基二苯乙烯桥联苯并菲二联体刺激响应盘状液晶: 合成、性质与应用

doi:10.6023/cjoc202302025

摘要/Abstract

通过经典的Knoevenagel和Suzuki偶联反应合成并表征了具有D-A结构的氰基二苯乙烯苯并菲类盘状液晶化合物PBTPA, 并通过核磁共振氢谱(¹H NMR)、碳谱(¹³C NMR)和高分辨质谱(HRMS)对其进行表征. PBTPA在溶液与薄膜态都有良好的荧光发射, 表现出明显的聚集诱导发光增强效应, 最大荧光强度比初始值提高了4.2倍, 有效地克服了聚集诱导盘状分子猝灭的弊端. PBTPA在不同溶剂中表现出由蓝到橙明显的溶致变色, 最大荧光量子产率高达74%, 密度泛函理论计算发现PBTPA分子内存在明显的电荷转移. PBTPA具有研磨刺激响应, 研磨前后荧光由黄色变为橙色, X射线衍射(XRD)和扫描电子显微镜(SEM)证明该过程归因于晶型的转变. 这一性质可以设计数据复写纸, 并通过研磨和二氯甲烷蒸气熏蒸的方式实现数据重写纸的重复使用. PBTPA还有良好的液晶性, 偏光显微镜(POM)织构呈现明显的扇形焦锥织构. 随温度的变化表现出矩形柱状相, 相变过程伴随着荧光的变化, 这归因于粘度和聚集形式的变化. 此外, PBTPA还有良好的电致发光性能, 其制备的黄光有机发光二极管(OLED)管色纯度高达99%, 光效可达16 lm/W. 因此在液晶半导体、数据加工、OLED等领域具有良好的应用潜力.

关键词: 苯并菲, 氰基二苯乙烯, 盘状液晶, 有机发光二极管(OLED), 聚集诱导效应, 刺激响应发光

A dibranched cyanostilbene triphenylene dimer liquid crystal compound PBTPA with D-A structure was synthesized by the classical Knoevenagel and Suzuki coupling reaction, and characterized by nuclear magnetic resonance hydrogen spectrum (¹H NMR) and carbon spectrum (¹³C NMR), and high resolution mass spectrometry (HRMS). PBTPA has excellent fluorescence emission in both solution and film states, showing obvious aggregation-induced emission enhancement effect, and the maximum fluorescence intensity is 4.2 times higher than the initial value. This effectively overcomes the drawbacks of aggregation-induced quenching of discotic molecules. PBTPA exhibits noticeable solvatochromic behavior from blue to orange in solvents with different polarities. The fluorescence emission wavelength is red-shifted by 110 nm, and the maximum absolute fluorescence quantum yield is as high as 74%. Density functional theory calculations show that there is outstanding charge transfer in PBTPA molecules. PBTPA has an obvious reversible grinding stimulation response. The fluorescence changes from yellow to orange before and after grinding. X-ray diffraction (XRD) and scanning electron microscope (SEM) prove that the process is accompanied by a crystal transformation. Based on this property, data rewriting paper can be designed easily with grinding and dichloromethane fuming, which can be used repeatedly by grinding and dichloromethane vapor fumigation. Additionally, PBTPA also has great liquid crystal properties, and polarizing optical microscopy (POM) texture appears apparently fan-shaped focal cone texture. With the change of temperature, it shows rectangular columnar phase to crystal phase, accompanied by fluorescence conversion, which is attributed to the change of viscosity and aggregation form. In addition, PBTPA is also a good electroluminescent material, and the color purity of yellow organic light-emitting diode prepared by PBTPA is as high as 99% at the turn-on voltage of 3.2 V. The highest luminous efficiency can reach 16 lm/W, so it has preeminent application potential in liquid crystal semiconductor, data processing, organic light emitting diode and other fields.

Key words: triphenylene, cyanostilbene, discotic liquid crystals, organic light-emitting diode (OLED), aggregation-induced emission (AIE), multi-stimuli responsive

引用此文

曾崇洋, 胡平, 汪必琴, 方文彦, 赵可清. 氰基二苯乙烯桥联苯并菲二联体刺激响应盘状液晶: 合成、性质与应用[J]. 有机化学, 2023, 43(9): 3287-3296.

Chongyang Zeng, Ping Hu, Biqin Wang, Wenyan Fang, Keqing Zhao. Cyanostilbene Bridged Triphenylene Dyad Stimuli-Responsive Discotic Liquid Crystal: Synthesis, Properties and Applications[J]. Chinese Journal of Organic Chemistry, 2023, 43(9): 3287-3296.

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图/表 9

图式1. PBTPA的合成及收率

Scheme 1. Synthesis and yield of PBTPA

图1. PBTPA在溶液及薄膜的吸收光谱(a),发射光谱(b)和电子云分布(c)

Figure 1. Absorption spectra (a) and emission spectra (b) in solution and film, electron cloud distribution (c) of PBTPA

Compd.	Solvent	λ^a/nm	ε^b/(×10⁴ L•cm^–1•mol^–1)	λ_e^c/nm	QY^d/%	Δν^e/cm^–1	Δf^h
PBTPA	CHX	376	19.62	460	73.85	4857	0.0095
	CCl₄	374	21.27	468	45.17	5730	0.0029
	TOL	376	9.41	474	33.25	5499	0.0171
	DOX	372	24.98	487	29.12	6348	0.0246
	EA	368	21.31	523	12.74	7907	0.1996
	EtOH	378	22.16	550	11.18	8273	0.2901
	DMF	384	24.12	570	—	8497	0.2751

表1. PBTPA的线性光物理参数

Table 1. Photophysical property parameters of PBTPA

图2. PBTPA在不同溶剂中的荧光发射光谱(a)与Lippert-Mataga曲线(b)

Figure 2. Emission spectra (a) and Lippert-Mataga curves (b) of PBTPA in different solvents Excitation wavelength 365 nm

图3. PBTPA在不同含水量THF/H2O中的吸收光谱(a)、发射光谱(b)、I/I0曲线(c)与荧光照片(d)

Figure 3. Absorption spectra (a), emission spectra (b) (excitation wavelength 365 nm), I/I0 curve (c) and fluorescence photo (d) of PBTPA in THF/H2O with different water contents Excitation wavelength 365 nm

图4. 研磨前后PBTPA的发射光谱(a)、波长-周期循环(b)、XRD (c)与复写数据示意图(d)

Figure 4. Eemission spectra (a), wavelength-period cycle (b), XRD (c) of PBTPA before and after grinding and data rewriting (d) Excitation wavelength 365 nm

Compd.	Process	Phase transition^b/℃ [∆H/(kJ•mol^–1)]
PBTPA	2nd heating	Cr 128 (11.56) Col_rec158 (4.55) I
PBTPA	1st cooling	I 144 (11.78) Col_rec 119 (15.91) Cr

表2. PBTPA的相转变温度和焓变a

Table 2. Thermodynamic property of PBTPA

图5. (a) PBTPA在135 ℃下的XRD(插入图片为该温度下的荧光照片与堆积模式, 右侧为该温度下的POM图); (b) PBTPA在45 ℃下的XRD(插入图片为该温度下的荧光照片,右侧为该温度下的POM图)

Figure 5. (a) XRD of PBTPA at 135 ℃ (the inserted are the fluorescence photo and stacking mode at this temperature, the right side is the POM); (b) the XRD of PBTPA at 45 ℃ (the inserted picture is the fluorescence photo at this temperature, the right side is the POM)

图6. PBTPA的电致发光光谱(a)、J-V特性曲线(b)、光电效率曲线(c)、光效曲线(d)与OLED结构及CIE1931色坐标图(e)

Figure 6. EL spectra (a), J-V characteristics (b), external EL quantum efficiency against J (c), power conversion efficiency against J (d) and CIE1931 chromaticity diagram (e) of PBTPA LED

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