Cyanostilbene Bridged Triphenylene Dyad Stimuli-Responsive Discotic Liquid Crystal: Synthesis, Properties and Applications

doi:10.6023/cjoc202302025

Abstract

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

Cite this article

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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Fig. & Tab. 9

Scheme 1. Synthesis and yield of PBTPA

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

Table 1. Photophysical property parameters of PBTPA

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

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

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

Table 2. Thermodynamic property of PBTPA

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)

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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