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CN-121991116-A - Polycyclic aromatic hydrocarbon cationic compound with high photo-thermal conversion efficiency, and synthetic method and application thereof

CN121991116ACN 121991116 ACN121991116 ACN 121991116ACN-121991116-A

Abstract

A polycyclic aromatic hydrocarbon cation compound with high photo-thermal conversion efficiency, a synthesis method and application thereof belong to the technical field of organic functional materials. The method realizes conjugate expansion through Scholl reaction, and introduces a large steric hindrance group for kinetic protection, so that the compound A is successfully obtained. The powder of the compound A shows excellent photo-thermal conversion performance under 1064nm near infrared light irradiation, has photo-thermal conversion efficiency of up to 90% under 1.4W cm ‑ power density, can be rapidly heated to more than 330 ℃, and shows excellent photo-thermal stability after multiple switching cycle performance without attenuation. The compound can be used as a photo-thermal agent for low-power non-contact precision welding of various metal materials, and has important application value in the fields of microelectronic manufacturing, precision instrument assembly and the like. The invention successfully solves the technical problem that the existing photo-thermal material is difficult to realize high photo-thermal conversion efficiency and high limit working temperature at the same time under the window of 1064 nm.

Inventors

  • SUN ZHE
  • TIAN XIAOQI
  • FU KAIYUE

Assignees

  • 天津大学

Dates

Publication Date
20260508
Application Date
20260130

Claims (8)

  1. 1. A polycyclic aromatic hydrocarbon cation compound A with high photo-thermal conversion efficiency is characterized by having the following structure: 。
  2. 2. a method for synthesizing a dibromoolefin condensed ring aromatic compound 4 prepared from a ketone precursor, wherein the synthetic route of the compound 4 is as follows: The synthesis steps comprise: (1) The method comprises the steps of carrying out trimerization reaction on a compound 1 and 1, 1' - (1, 2-ethynyl) bis [4- (1, 1-dimethylethyl) benzene ] under the catalysis of octacarbonyl cobalt, wherein the molar ratio is 1 (1-3) (1.2-2), the solvent is toluene, the reaction temperature is 90-120 ℃ and the reaction time is overnight, and purifying the reaction system after the reaction is completed by a reduced pressure distillation and silica gel column chromatography separation post-treatment mode to obtain a compound 2; (2) Carrying out Scholl reaction on the compound 2, DDQ and trifluoromethanesulfonic acid, wherein the molar ratio is 1 (5-7) (20-50), the solvent is methylene dichloride, the reaction temperature is 0 ℃, the reaction time is 20-30 min, and the reaction system after the reaction is finished is purified by extraction, drying, filtering, reduced pressure distillation and silica gel column chromatography separation post-treatment to obtain a product compound 3; (3) The compound 3 reacts with carbon tetrabromide and triphenylphosphine in a molar ratio of 1 (2-3) (4-6), the solvent is toluene, the reaction temperature is 110-130 ℃ and the reaction time is overnight, and the reaction system after the reaction is completed is purified by a reduced pressure distillation and silica gel column chromatography separation post-treatment mode to obtain the product compound 4.
  3. 3. A method for synthesizing a ketocondensed ring aromatic compound 8, characterized in that the synthetic route of the compound 8 is as follows: The synthesis steps comprise: (1) The compound 4 synthesized in the claim 2 is subjected to Suzuki reaction with the compound 5, tetra (triphenylphosphine) palladium and anhydrous potassium carbonate, the molar ratio is 1 (2-3) (0.1-0.3) (3-7), the solvent is a mixed solvent of toluene, 1, 4-dioxane and water, the reaction temperature is 90-120 ℃, the reaction time is overnight, and the reaction system after the reaction is subjected to extraction, drying, filtration, reduced pressure distillation and silica gel column chromatography separation post-treatment to obtain a product compound 6; (2) The method comprises the steps of (1) carrying out oxidation reaction on a compound 6 and potassium permanganate, wherein the molar ratio of (3-5), the potassium permanganate is added twice, the initial addition amount is 2-3 times of the molar number of the compound 6, the remaining potassium permanganate is added after 2-3 hours of reaction, the reaction is continued for 2-3 hours, the solvent is acetone, the reaction temperature is 20-40 ℃, the reaction system after the reaction is completed is subjected to reduced pressure distillation and filtration to obtain a crude product, the crude product is subjected to oxidation reaction with pyridine chlorochromate, the molar ratio of the compound 4 to the pyridine chlorochromate is 1 (1.5-3), the solvent is dichloromethane, the reaction temperature is 20-40 ℃, the reaction time is overnight, and the reaction system after the reaction is completed is purified by a reduced pressure distillation and silica gel column chromatographic separation post-treatment mode to obtain a product compound 7; (3) The compound 7, DDQ and trifluoromethanesulfonic acid are subjected to Scholl reaction, the molar ratio is 1 (3-7) (30-50), the solvent is methylene dichloride, the reaction temperature is 20-40 ℃, the reaction time is overnight, and the reaction system after the reaction is finished is purified by extraction, drying, filtration, reduced pressure distillation and silica gel column chromatography separation post-treatment to obtain a product compound 8.
  4. 4. A method for synthesizing a3, 5-di-tert-butylphenyl protected ketocondensed ring aromatic compound 10, characterized in that the compound 10 is synthesized according to the following route: The synthesis steps comprise: (1) The synthetic compound 8 is subjected to boron esterification reaction with bis (2-methoxyphenyl) iridium (III) dimer, 4 '-dimethyl-2, 2' -bipyridine and bis (pinacolato) diboron in the molar ratio of 1 (0.1-0.3) (0.2-0.6) (5-10), the solvent is tetrahydrofuran, the reaction temperature is 80-90 ℃, the reaction time is 4-5 days, the solvent is removed by reduced pressure distillation after the reaction is finished, the residue is added into dichloromethane and stirred at room temperature in air for overnight, and the reaction system after the reaction is purified by means of reduced pressure distillation and silica gel column chromatography separation post-treatment to obtain a product compound 9; (2) The compound 9, 3, 5-di-tert-butyl bromobenzene, tetra (triphenylphosphine) palladium and anhydrous potassium carbonate are subjected to Suzuki reaction, the molar ratio is 1 (3-7) (0.1-0.5) (5-30), the solvent is a mixed solvent of toluene, methanol and water, the reaction temperature is 100-120 ℃, the reaction time is overnight, and the reaction system after the completion of the reaction is purified by extraction, drying, filtration, reduced pressure distillation and silica gel column chromatography separation post-treatment to obtain the product compound 10.
  5. 5. The synthesis method of the polycyclic aromatic hydrocarbon single free radical compound 11 is characterized in that the synthesis route of the compound 11 is as follows: The synthesis method comprises the following steps: Dissolving triisopropylsilylaletylene in anhydrous tetrahydrofuran under the protection of argon, cooling to 0 ℃ in an ice bath, dropwise adding a hexane solution of n-butyllithium at the temperature, continuously stirring at the temperature for 1.5-3 hours after the dropwise adding is finished to obtain a reaction solution containing lithium salt, dissolving the compound 10 synthesized in the method of claim 4 in the anhydrous tetrahydrofuran to prepare a solution, dropwise adding the compound 10 into the reaction solution obtained in the last step at the temperature of 0 ℃, slowly heating the reaction system to room temperature, continuously stirring at the room temperature for 2-4 hours after the dropwise adding is finished, carrying out reduced pressure distillation on the reaction system to obtain a crude product, reacting the crude product with stannous chloride in a dichloromethane solvent at the temperature of 20-40 ℃ for 1-2 hours, carrying out reduced pressure distillation on the reaction system to remove the solvent, carrying out silica gel column chromatography on the obtained residue, and carrying out recrystallization and purification to obtain the compound 11, wherein the molar ratio of the compound 10, triisopropylsilyl and the n-butyllithium to stannous is 1 (10-30): 10-30.
  6. 6. A method for synthesizing the polycyclic aromatic hydrocarbon cationic compound a according to claim 1, wherein the synthetic route of the compound a is as follows: The synthesis method comprises the following steps: The compound 11 synthesized in the method of claim 5 and silver hexafluoroantimonate are subjected to oxidation reaction, the molar ratio is 1 (5-15), the solvent is methylene dichloride, the reaction temperature is 20-40 ℃, the reaction time is 3-6 hours, and the target product compound A is obtained by purifying a reaction system after the reaction is completed through reduced pressure distillation and recrystallization post-treatment.
  7. 7. Use of the Gao Guangre conversion efficiency polycyclic aromatic hydrocarbon cationic compound a according to claim 1, characterized in that the use is to use compound a powder as near infrared two-region photothermal agent, the photothermal conversion efficiency of the compound a under 1064 nm laser irradiation at a power density of 1.4W cm-2 is 90%, the maximum working temperature is 330 ℃, and the compound a has cyclic photothermal stability.
  8. 8. A non-contact welding method is characterized in that the photothermal agent is used, the photothermal agent is placed at a part to be welded, after welding flux is applied, the welding is realized by adopting 1064 nm laser irradiation, and the welding is suitable for precision welding of metal materials including zinc, iron and alloys thereof.

Description

Polycyclic aromatic hydrocarbon cationic compound with high photo-thermal conversion efficiency, and synthetic method and application thereof Technical Field The invention relates to the technical field of organic functional materials, in particular to a synthetic method of a polycyclic aromatic hydrocarbon cationic compound and application of the polycyclic aromatic hydrocarbon cationic compound as a near infrared two-region photo-thermal agent. Background Near infrared two-region (NIR-II, 1000-1700 nm) photothermal agents are receiving great attention due to their deeper light penetration depth and lower light scattering in the fields of biological tissue penetration, industrial processing, etc. However, it remains a challenge to develop solid organic photothermal agents that combine Gao Guangre conversion efficiency, high operating temperature and excellent stability at the NIR-II window, particularly at 1064nm, which is a broad industrial application. In the prior art, the performance of the near infrared two-region (NIR-II) organic photo-thermal material often cannot meet the severe requirements of industrial processing on the synergy of high efficiency and high temperature resistance under the mainstream laser wavelength of 1064 nm. For example, although some materials show higher photo-thermal conversion efficiency at 1064 nm, the working temperature is limited and cannot withstand high temperature environment exceeding 300 ℃, while other materials can reach high temperature above 400 ℃, the photo-thermal conversion efficiency at 1064 nm is remarkably low (only about 40%), and serious energy waste and low processing efficiency are caused. The unbalance in the performance severely restricts the comprehensive application of the material in the high-efficiency and high-precision laser processing field. Therefore, a new solid-state organic photo-thermal material is needed in the art, which can realize high photo-thermal conversion efficiency, high limit working temperature and excellent thermal cycling stability under the excitation of 1064 nm laser widely used in industry, so as to meet the severe requirements of high-end laser precision machining on efficiency, precision and reliability. Disclosure of Invention The invention aims to overcome the defects of the prior art and provides a novel polycyclic aromatic hydrocarbon cationic compound as well as a synthesis method and application thereof, so as to solve the problems of outstanding single performance and insufficient comprehensive performance. The compound can realize high light-heat conversion efficiency, high limit working temperature and excellent thermal cycle stability under the laser excitation of industrial main stream 1064 nm. In the invention, on the basis of reported molecules, seven-membered rings are introduced through trimerization reaction, the Scholl reaction realizes conjugated expansion, and a large steric hindrance group is introduced for kinetic protection, so that the compound A is successfully obtained. The solid powder of the molecule shows excellent performance under 1064 nm near infrared light irradiation, shows light-heat conversion efficiency of up to 90% under the power density of 1.4W cm -, can be quickly heated to more than 330 ℃ and is kept stable, the light-heat stability is excellent after the repeated switching cycle performance is not attenuated, and the non-contact welding method with low power and high precision is provided based on the solid powder. The technical scheme of the invention is as follows: a polycyclic aromatic hydrocarbon cation compound A with high photo-thermal conversion efficiency has the structure shown as follows: A synthetic method of a polycyclic aromatic hydrocarbon cationic compound A with high photo-thermal conversion efficiency uses a compound 1 as a starting material, and gradually constructs and modifies a molecular skeleton by sequentially carrying out cobalt-catalyzed trimerization reaction, scholl reaction, corey-Fuchs reaction, suzuki coupling reaction, stepwise oxidation of potassium permanganate and pyridinium chlorochromate, scholl reaction, iridium-catalyzed C-H boron esterification, suzuki coupling reaction and final single-electron reduction oxidation process, so as to finally obtain the target cationic compound A. The synthetic route of the compound is shown as follows: the invention firstly provides a synthesis method of dibromo-olefin condensed ring aromatic compound 4 prepared from ketone precursor, wherein the synthesis method of the compound 4 specifically comprises the following steps: Step one, the trimerization reaction of the compound 1 and 1, 1' - (1, 2-ethynyl) bis [4- (1, 1-dimethylethyl) benzene ] and octacarbonyl cobalt is carried out to obtain a compound 2, and the specific operation is as follows: The method comprises the steps of carrying out trimerization reaction on a compound 1 and 1, 1' - (1, 2-ethynyl) bis [4- (1, 1-dimethylethyl) benzene ] under the ca