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CN-122010779-A - Chiral binaphthol-cyano stilbene compound and preparation method and application thereof

CN122010779ACN 122010779 ACN122010779 ACN 122010779ACN-122010779-A

Abstract

The present invention discloses a chiral naphthol cyano stilbene compound and its preparation method and application, which relates to the technical field of chiral aggregation induced luminescent liquid crystal materials. The present invention synthesizes a novel chiral naphthol cyano stilbene compound and discovers its use as a chiral aggregation induced luminescent liquid crystal material. The material combines chiral structure, aggregation induced luminescent properties, and liquid crystal orderliness organically, and can not only efficiently emit light while forming a liquid crystal phase, but also achieve circularly polarized luminescence, providing new ideas for the design of multifunctional luminescent materials.

Inventors

  • FENG HUIYI
  • ZHANG MIN
  • YIN CHENCHEN
  • FENG CHAO
  • GUO CHUNYAN
  • LI HAIYAN

Assignees

  • 蚌埠学院

Dates

Publication Date
20260512
Application Date
20251229

Claims (10)

  1. 1. A chiral binaphthol-cyano stilbene compound, R-BIN-DCyn for short, has the following structural formula: ; wherein n=4 to 16.
  2. 2. The process for preparing chiral binaphthol-cyanobiphenyl compounds according to claim 1, characterized in that it comprises the following steps: (1) 4-hydroxyphenylacetonitrile and terephthalaldehyde undergo Knoevenagel condensation reaction to obtain an intermediate 1; ; (2) Carrying out Suzuki coupling reaction on R-6,6 '-dihalogen-1, 1' -bi-2-naphthol and 4-ether phenylboronic acid to obtain an intermediate 2; ; (3) The intermediate 2 and 1-halogenated dodecane undergo substitution reaction to obtain an intermediate 3; ; (4) The intermediate 3 and 1, 4-dihalobutane undergo substitution reaction to obtain an intermediate 4; ; (5) The intermediate 1 and the intermediate 4 undergo substitution reaction to obtain R-BIN-DCyn; ; wherein n=4 to 16, and R is one of F, cl and Br.
  3. 3. The method for producing chiral binaphthol-cyano stilbene compound according to claim 2, wherein the molar ratio of 4-hydroxyphenylacetonitrile to terephthalaldehyde is (2-4): 1; preferably, the Knoevenagel condensation reaction is carried out under the action of a base; preferably, the base is selected from at least one of sodium hydroxide, pyridine, piperidine and potassium tert-butoxide; preferably, the reaction temperature of the Knoevenagel condensation reaction is 50-85 ℃.
  4. 4. The method for preparing chiral binaphthol-cyano stilbene compound according to claim 2, wherein the molar ratio of R-6,6 '-dihalogenated-1, 1' -bi-2-naphthol to 4-ether phenylboronic acid is 1 (2.5-4.5); preferably, the Suzuki coupling reaction is performed under the action of a base and a palladium catalyst; Preferably, the alkali is at least one selected from potassium acetate, potassium carbonate, sodium acetate, sodium carbonate and magnesium carbonate; Preferably, the reaction temperature of the Suzuki coupling reaction is 100-150 ℃.
  5. 5. The method for producing chiral binaphthol-cyano stilbene compounds according to claim 2, wherein the molar ratio of the intermediate 2 to 1-halododecane is 1.2-1.8.
  6. 6. The method for producing chiral binaphthol-cyanobiphenyl compounds according to claim 2, wherein the molar ratio of the intermediate 3 to 1, 4-dihalobutane is (1.5-3): 1.
  7. 7. The method for producing chiral binaphthol-cyano stilbene compound according to claim 2, wherein the molar ratio of the intermediate 1 to the intermediate 4 is 1 (3-5).
  8. 8. The method for preparing chiral binaphthol-cyano stilbene compound according to claim 2, wherein the substitution reaction is carried out in the presence of an acid binding agent selected from at least one of potassium carbonate, sodium sulfate, potassium iodide, potassium bromide, sodium iodide, sodium carbonate, sodium acetate, pyridine and triethylamine; Preferably, the reaction temperature of the substitution reaction is 70-95 ℃.
  9. 9. The use of a chiral binaphthol-cyanostilbene compound according to claim 1 as a chiral aggregation-induced emission liquid crystal material.
  10. 10. Use of the chiral aggregation-induced emission liquid crystal material according to claim 9 in organic electroluminescent diodes and chiral fluorescence sensors.

Description

Chiral binaphthol-cyano stilbene compound and preparation method and application thereof Technical Field The invention relates to the technical field of chiral aggregation-induced emission liquid crystal materials, in particular to a chiral binaphthol-cyano stilbene compound and a preparation method and application thereof. Background Liquid Crystals (LCs) are a special self-assembled medium and are widely used in field effect crystals, optical sensing materials, organic Light Emitting Diodes (OLEDs), organic photovoltaic cells, etc. due to the unique pi-pi stacking structure and the rapid transport of charge carriers along the columnar axis in mesogens. Among them, the high-fluorescence liquid crystal effectively combines inherent luminescence characteristics and molecular self-assembly characteristics, making it advantageous in terms of simplified design of devices, low power consumption, high brightness, and high contrast. However, most fluorescent liquid crystal molecules are susceptible to aggregation-induced quenching (ACQ) in an aggregated state, inhibiting fluorescence emission. In addition, intermolecular pi-pi stacking hinders the formation of liquid crystal phases, resulting in the generation of a coating or linear medium of mesophases. In 2001, the group Tang Benzhong first observes aggregation-induced emission (AIE) phenomenon in 1-methyl-1, 2,3,4, 5-penta-phenylsilole Molecules (MPPS), and the research result effectively solves the ACQ problem of the traditional fluorescent material and widens the application of the molecules in the fields of liquid crystal, circular polarization luminescence and the like. Based on this, various AIE molecules are successively constructed as highly efficient fluorescent liquid crystal materials, such as a cyanobiphenyl derivative, which is favored by virtue of its light stability, mechanochromatism, and AIE properties. However, the design and synthesis of the liquid crystal molecules with light-emitting characteristics still face great challenges. Firstly, after functional luminescent groups are introduced into the liquid crystal molecular structure, the original liquid crystal property of the compound is difficult to maintain, and secondly, most of the compounds obtained by connecting the luminescent groups with the liquid crystal molecules can emit strong light only in dilute solution, so that the original AIE characteristics are not maintained. Considering that cyano-stilbene is a high fluorescence liquid crystal element, chiral R-1,1' -bi-2-naphthol (R-BINOL) units are introduced into the structure of the cyano-stilbene, so that not only can the phi F value in the aggregation state or solid state of chiral luminescent liquid crystal molecules be effectively improved, but also the intrinsic Circular Polarized Luminescence (CPL) performance of the molecules can be improved through a highly ordered spiral aggregation state structure. Two naphthalenes in the R-BINOL molecule are limited to rotate around the symmetry axis of C 2 to generate a stable chiral structure and higher chiral induction, so that the R-BINOL and the derivatives thereof gradually become ideal chiral sources for constructing CPL materials. Related researches show that the fluorescence quantum yield (phi F) and the luminescence asymmetry factor (g lum) are key parameters for measuring the practical application value of the CPL material. The chiral optical properties of CPL materials are also closely related to the aggregation state structure, and the ordered helical aggregation state structure of molecules helps to improve the g lum value. However, chiral luminescent molecules have difficulty forming highly ordered helical structures in the dispersed state, resulting in weak or even no chiral optical response of the CPL signal. In other words, CPL materials cannot have both a large g lum value and a high Φ F in good solutions. According to literature reports, the g lum values of chiral liquid crystal CPL materials are generally higher than those of other CPL materials. If the advantages of AIE performance and liquid crystal characteristics inherent in the cyano stilbene aggregation state can be combined, the chiral liquid crystal material with strong fluorescence, large g lum value and high phi F is expected to be prepared. Disclosure of Invention The technical problem to be solved by the invention is to provide the chiral binaphthol-cyano stilbene compound and the preparation method thereof, wherein the compound has AIE characteristics, liquid crystallinity and circular polarization luminescence characteristics, can efficiently emit light after forming a liquid crystal phase aggregate, and overcomes the aggregation-induced quenching phenomenon of the traditional luminescent material in an aggregation state, thereby providing a new thought for designing and synthesizing a novel chiral aggregation-induced luminescent liquid crystal material. The technical problems to be solved by the invention