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CN-121974869-A - Electron donor-acceptor type benzothiadiazole liquid luminescent material, preparation method thereof and piezochromic application

CN121974869ACN 121974869 ACN121974869 ACN 121974869ACN-121974869-A

Abstract

The invention discloses an electron donor-acceptor type benzothiadiazole liquid luminescent material, a preparation method and a piezochromic application thereof, wherein the liquid luminescent material is a single component compound with the following structural formula, wherein an N, N-diphenyl naphthalene-1-amine group is used as an electron donor, the benzothiadiazole group is used as an electron acceptor, the electron donor-acceptor endows the benzothiadiazole group with a narrower excited state-ground state energy gap, the Stokes displacement is greatly expanded, the self-absorption problem is avoided, meanwhile, a tetraethylene glycol chain space isolates the benzothiadiazole unit, pi-pi accumulation among conjugated molecules is blocked, and aggregation-induced quenching and photo-bleaching problems of condensed phase fluorescent groups are inhibited. The luminescent material is oily, emits light in bright red, is extremely sensitive to hydrostatic pressure, has the characteristics of reversible piezochromic property, printing, integration and the like due to the liquid property, and has the advantages of simple preparation method, mild reaction condition and great application potential.

Inventors

  • LIU JING
  • XUE YIFAN
  • Zeng Jiayue

Assignees

  • 陕西师范大学

Dates

Publication Date
20260505
Application Date
20260209

Claims (9)

  1. 1. An electron donor-acceptor type benzothiadiazole liquid luminescent material, characterized in that the molecular structure of the liquid luminescent material is as follows: 。
  2. 2. a method for preparing the electron donor-acceptor type benzothiadiazole liquid luminescent material according to claim 1, characterized by comprising the steps of: Step 1, under the protection of N 2 , adding a compound of the formula I into a reaction solvent, and carrying out Suzuki coupling reaction with 4- (N- (naphthalene-1-yl) -N-anilino) phenylboronic acid under the alkaline condition provided by potassium carbonate and the catalysis of triphenylphosphine palladium to generate a compound of the formula II; The structural formula of the compound of the formula I is as follows: the structural formula of the 4- (N- (naphthalene-1-yl) -N-anilino) phenylboronic acid is as follows: the structural formula of the compound of the formula II is as follows: Step 2, adding a compound of a formula II and a compound of a formula III into an organic solvent, and sequentially adding a dehydrating agent and triethylamine under the catalysis of 1-hydroxybenzotriazole to react to generate an electron donor-acceptor type benzothiadiazole liquid luminescent material; the structural formula of the compound of the formula III is as follows: The dehydrating agent is dicyclohexylcarbodiimide or 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride.
  3. 3. The method for preparing the electron donor-acceptor type benzothiadiazole liquid luminescent material according to claim 2, wherein in the step 1, the molar ratio of the compound of the formula I to 4- (N- (naphthalene-1-yl) -N-anilino) phenylboric acid, potassium carbonate and triphenylphosphine palladium is 1:1-2:5-10:0.05-0.1.
  4. 4. The preparation method of the electron donor-acceptor type benzothiadiazole liquid luminescent material according to claim 2 is characterized in that in step 1, the Suzuki coupling reaction is carried out at the reflux temperature of a reaction solvent for 18-24 hours, and the reaction solvent is a mixed solvent of 1, 4-dioxane and water or a mixed solvent of tetrahydrofuran and water.
  5. 5. The method for preparing an electron donor-acceptor type benzothiadiazole liquid luminescent material according to claim 4, wherein the volume ratio of 1, 4-dioxane or tetrahydrofuran to water in the mixed solvent is 1:0.1-0.2.
  6. 6. The method for preparing an electron donor-acceptor type benzothiadiazole liquid luminescent material according to claim 2, wherein in the step 2, the molar ratio of the compound of formula II to the compound of formula III, the dehydrating agent, triethylamine and 1-hydroxybenzotriazole is 1:1.5-2.5:1-2:2-3:0.5-1.
  7. 7. The method for preparing an electron donor-acceptor type benzothiadiazole liquid luminescent material according to claim 2, wherein in the step 2, the reaction is performed in an ice bath for 0.5 to 1 hour and then at 20 to 40 ℃ for 16 to 24 hours.
  8. 8. The method for preparing an electron donor-acceptor type benzothiadiazole liquid luminescent material according to claim 2, wherein in step 2, the organic solvent is any one of dichloromethane and tetrahydrofuran.
  9. 9. Use of an electron donor-acceptor type benzothiadiazole liquid luminescent material according to claim 1 as piezochromic material.

Description

Electron donor-acceptor type benzothiadiazole liquid luminescent material, preparation method thereof and piezochromic application Technical Field The invention belongs to the technical field of liquid luminescent materials, and particularly relates to a benzothiadiazole liquid luminescent material with an intramolecular charge transfer characteristic and application of the liquid luminescent material as a novel pressure-sensitive material. Background Under external mechanical stress, luminescent materials tend to exhibit significant changes in luminescent properties. Pressure is one of them, which is widely found in nature and industrial applications. The change of pressure can break the original energy balance state of the material, trigger a series of remarkable physical and chemical transformation, such as the reduction of the atomic distance and the reconstruction of the lattice structure in the material in the compression process, and further change the luminescent property of the material. Piezochromic materials are of great interest by virtue of their unique advantages. Such materials can undergo significant color changes under external pressure or mechanical abrasion stimulation, and based on this property, piezochromic materials have been widely used in pressure sensitive sensing and optical recording systems. However, the traditional pressure-sensitive fluorescent material also has a plurality of challenges, and the performance improvement and the application expansion of the traditional pressure-sensitive fluorescent material are restricted. The traditional pressure-sensitive fluorescent material mostly exists in a crystal or powder form, most of the solid materials have the problems of self-absorption, aggregation-induced quenching, photodegradation and the like, and in addition, the solid materials generally have a rigid structure, are difficult to process and form, have poor pressure-sensitive reversibility and cannot adapt to the diversified requirements of the emerging fields such as flexible electronics, wearable equipment and the like on the processing performance of the materials. We therefore direct their eyes towards liquid luminescent materials, which are expected to replace traditional solid luminescent materials. The solvent-free organic liquid (SOLs) is paid attention to as a novel functional oily compound, and the oily dye molecules move relatively freely, so that key problems of aggregation quenching, photodegradation and the like which limit the application of the oily dye molecules can be avoided, meanwhile, the solvent-free characteristic also endows the oily luminescent molecules with good light stability, and important potential is shown in the fields of photoelectric materials and devices. Meanwhile, the liquid material has excellent processing adaptability, can realize the preparation of flexible and foldable devices through simple coating, printing or blending, and has wide application prospect in the fields of sensing, display, illumination and the like. At present, few reports on liquid pressure-sensitive materials with high luminous efficiency, strong processability and excellent performance are provided, and therefore, development of novel pressure-sensitive liquid luminous materials is needed. Disclosure of Invention Aiming at the problems of easy quenching of luminescence, photodegradation, irreversible pressure response and the like of the existing crystalline or powdery piezochromic material, the invention provides an electron donor-acceptor type benzothiadiazole liquid luminescent material and a preparation method thereof. The molecular structure of the electron donor-acceptor type benzothiadiazole liquid luminescent material provided by the invention is shown as follows: the preparation method of the electron donor-acceptor type benzothiadiazole liquid luminescent material comprises the following steps: Under the protection of N 2, adding the compound of the formula I into an organic solvent, and carrying out Suzuki coupling reaction with 4- (N- (naphthalene-1-yl) -N-anilino) phenylboronic acid under the alkaline condition provided by potassium carbonate and the catalysis of triphenylphosphine palladium to generate the compound of the formula II. The structural formula of the compound of the formula I is as follows: the structural formula of the 4- (N- (naphthalene-1-yl) -N-anilino) phenylboronic acid is as follows: the structural formula of the compound of the formula II is as follows: And 2, adding the compound of the formula II and the compound of the formula III into an organic solvent, and sequentially adding a dehydrating agent and triethylamine under the catalysis of 1-hydroxybenzotriazole to react to generate the electron donor-acceptor type benzothiadiazole fluorescent compound. The structural formula of the compound of the formula III is as follows: The dehydrating agent is dicyclohexylcarbodiimide or 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydro