Search

CN-121990983-A - Preparation method of supramolecular assembly fluorescent dye and pyrenyl pyridine derivative used in preparation method

CN121990983ACN 121990983 ACN121990983 ACN 121990983ACN-121990983-A

Abstract

The invention belongs to the field of fluorescent materials, and relates to a novel pyrenyl pyridine derivative supermolecule assembly fluorescent material. In particular to a preparation method and a characterization method of pyrenyl pyridine derivatives and supermolecule assembly fluorescent materials. The invention provides a pyrenyl pyridine derivative and a preparation method thereof. The invention also provides a preparation method of the supramolecular assembly fluorescent dye, which utilizes the pyrenyl pyridine derivative, cucurbituril is used as a main body unit, and the pyrenyl pyridine derivative is used as a guest unit, and the supramolecular assembly fluorescent dye is obtained through interaction of the main body and the guest.

Inventors

  • XU HAN
  • XU CHEN
  • LIN XIAOHAN
  • QIAN CHAO
  • ZHOU SHAODONG
  • RUAN JIANCHENG
  • LU BIN

Assignees

  • 浙江大学
  • 浙江大学衢州研究院

Dates

Publication Date
20260508
Application Date
20251204

Claims (10)

  1. 1. A pyrenyl pyridine derivative is characterized by having the structural formula: 。
  2. 2. The preparation method of the pyrenyl pyridine derivative is characterized by comprising the following steps of: Adding 1-bromo-6- (4-pyridyl) pyrene and 1- (3-bromopropyl) -4- (4-bromophenyl) pyridin-1-ium into N, N-dimethylformamide for heating reaction, wherein the reaction temperature is 60-120 ℃, and the reaction time is 24-120 hours; the feeding molar ratio of the 1-bromo-6- (4-pyridyl) pyrene to the 1- (3-bromopropyl) -4- (4-bromophenyl) pyridin-1-ium is 1:1-2; and then filtering to obtain the pyrenyl pyridine derivative.
  3. 3. The method for preparing pyrenyl pyridine derivative according to claim 2, wherein the method for preparing 1-bromo-6- (4-pyridyl) pyrene comprises the steps of: Adding 1, 6-dibromopyrene, pyridine-4-boric acid and a palladium catalyst into tetrahydrofuran, then adding an alkaline solution, and heating for reaction under an inert gas atmosphere, wherein the reaction temperature is 60-100 ℃, the reaction time is 24-120 h, the molar ratio of 1, 6-dibromopyrene to pyridine-4-boric acid=1:2-5.2, and the molar ratio of 1, 6-dibromopyrene to palladium catalyst=1:0.1-0.5; Tetrahydrofuran, wherein the volume ratio of alkaline solution=2-4:1, and the alkaline solution is aqueous solution with the concentration of alkali or alkaline salt of 1-3 mol/L; the reaction product is cooled and filtered, and the filtrate is separated by column chromatography, and the methylene dichloride/methanol is used as an eluent to obtain the 1-bromo-6- (4-pyridyl) pyrene.
  4. 4. A method for producing a pyrenyl pyridine derivative according to claim 3, wherein: the palladium catalyst is tetrakis (triphenylphosphine) palladium or a mixture of tris (dibenzylideneacetone) dipalladium and triphenylphosphine in a molar ratio of 1:4.
  5. 5. The method for producing a pyrenyl pyridine derivative as claimed in claim 4, wherein: The alkali of the alkaline solution is NaOH and KOH, and the alkaline salt of the alkaline solution is K 2 CO 3 .
  6. 6. The method for producing a pyrenyl pyridine derivative as claimed in claim 5, wherein: The eluent is mixed liquid of dichloromethane and methanol with the volume ratio of 200-500:1.
  7. 7. A method for preparing a supramolecular assembly fluorescent dye, characterized in that pyrenyl pyridine derivatives as claimed in claim 1 are used, The cucurbituril is used as a main body unit, the pyrenyl pyridine derivative is used as a guest unit, and the supermolecule assembly fluorescent dye is obtained through interaction of the main body and the guest.
  8. 8. The method for preparing a supramolecular assembly fluorescent dye as claimed in claim 7, wherein: Cucurbituril is cucurbituril [7] uril, pyrenyl pyridine derivative, wherein the molar ratio of cucurbituril [7] uril=1:0.1-2, and the obtained supramolecular assembly fluorescent dye is named as Py/CB [7] assembly fluorescent dye; The cucurbituril is cucurbituril [8] uril, pyrenyl pyridine derivative, wherein the molar ratio of cucurbituril [8] uril=1:0.1-1, and the obtained supermolecule assembly fluorescent dye is named as Py/CB [8] assembly fluorescent dye.
  9. 9. The method for preparing a supramolecular assembly fluorescent dye as claimed in claim 8, wherein: And dissolving the pyrenyl pyridine derivative and cucurbituril in deionized water to form a system, and performing ultrasonic treatment for 4-6 minutes to obtain the supramolecular assembly fluorescent dye.
  10. 10. The method for preparing a supramolecular assembly fluorescent dye as claimed in claim 9, wherein: In the system, the concentration of the pyrenyl pyridine derivative is 1× -4 ~1×10 -5 M.

Description

Preparation method of supramolecular assembly fluorescent dye and pyrenyl pyridine derivative used in preparation method Technical Field The invention belongs to the field of fluorescent materials, and relates to a novel pyrenyl pyridine derivative supermolecule assembly fluorescent material. In particular to a preparation method and a characterization method of pyrenyl pyridine derivatives and supermolecule assembly fluorescent materials. Background Fluorescence is a phenomenon of luminescence generated in the process of energy absorption by molecules, electron transition to a singlet excited state, and radiation transition back to a ground state. Along with the change of the time demand, the development direction of the fluorescent material is continuously adjusted. The application of the fluorescent powder is expanded to a plurality of fields such as plant cultivation, military illumination, health detection, biosensing and the like, and has wide application prospect. In recent years, organic conjugated systems which have been attracting attention have been widely used in the fields of organic photovoltaics, fluorescence sensing, bioimaging, and the like. Patent CN120441492a provides a molecular system with blue fluorescence using phenanthroimidazole as a donor unit and condensed ring aromatic conjugated group as an acceptor unit, which has great potential in application of organic light emitting diode. Novel organic conjugated system applications focus on novel functional molecule design synthesis. Pyrene is a member of the polycyclic aromatic hydrocarbon family, has the functions of electron donating and electron withdrawing, and has good optical properties. Pyrene has the advantages of 1) it has good thermal stability, 2) it has high luminous efficiency. On the other hand, the pyrene unit conjugated system has a large range, the electron delocalization is obvious, and pi-pi transition easily occurs when the pyrene unit conjugated system is excited by light. Based on the above advantages, pyrene is a fluorescent unit commonly used to construct large conjugated systems. Patent CN120097867a provides a mechanically discolored pyrenyl derivative material which has important application in fingerprint extraction, but the raw materials are not readily available, the cost is relatively high, and the material does not have water solubility. Patent CN119954685A provides a water-soluble mono-benzene ring fluorescent dye, which has simple structure but is difficult to modify. Therefore, the preparation of the novel high-performance organic photoelectric material containing pyrene condensed ring structural units and the exploration of the luminous mechanism thereof have important significance. Disclosure of Invention The invention aims to provide a preparation method of a supramolecular assembly fluorescent dye and a pyrenyl pyridine derivative used by the same. In order to solve the above problems, the present invention provides a pyrenyl pyridine derivative, which has the structural formula: 。 the invention also provides a preparation method of the pyrenyl pyridine derivative, which comprises the following steps: Adding 1-bromo-6- (4-pyridyl) pyrene and 1- (3-bromopropyl) -4- (4-bromophenyl) pyridin-1-ium into N, N-dimethylformamide for heating reaction at 60-120 ℃ for 24-120 h (preferably 60-90 ℃ and 48+/-2 h); the feeding molar ratio of 1-bromo-6- (4-pyridyl) pyrene to 1- (3-bromopropyl) -4- (4-bromophenyl) pyridin-1-ium is 1:1-2 (preferably 1:1.1-1.3, more preferably 1:1.15-1.2); and then filtering to obtain the pyrenyl pyridine derivative. In general, 1mmol of 1-bromo-6- (4-pyridyl) pyrene is used together with (10.+ -. 2) mL of N N-dimethylformamide. The reaction chemical formula is as follows: As an improvement of the preparation method of the pyrenyl pyridine derivative, the preparation method of the 1-bromo-6- (4-pyridyl) pyrene comprises the following steps: Adding 1, 6-dibromopyrene, pyridine-4-boric acid and a palladium catalyst into tetrahydrofuran, adding an alkaline solution, and heating and reacting in an inert gas atmosphere (comprising N 2), wherein the reaction temperature is 60-100 ℃, the reaction time is 24-120 h (preferably 60-80 ℃ and 60+/-2 h), the molar ratio of 1, 6-dibromopyrene to pyridine-4-boric acid=1:2-5.2, and the molar ratio of 1, 6-dibromopyrene to palladium catalyst=1:0.1-0.5; Tetrahydrofuran, wherein the volume ratio of alkaline solution=2-4:1, and the alkaline solution is aqueous solution with the concentration of alkali or alkaline salt of 1-3 mol/L; Cooling the reaction product (to normal temperature), filtering, separating filtrate by column chromatography, and eluting with dichloromethane/methanol to obtain 1-bromo-6- (4-pyridyl) pyrene. In general, 1, 6-dibromopyrene was used in an amount of (120.+ -. 20) mL of tetrahydrofuran per 7mmol of 1, 6-dibromopyrene. The chemical formula of the reaction is as follows: 。 Further improvement of the preparation method of pyrenyl py