CN117003753A - Carbonyl arylamine pi stacking fluorescent dye and preparation method thereof - Google Patents

Carbonyl arylamine pi stacking fluorescent dye and preparation method thereof Download PDF

Info

Publication number
CN117003753A
CN117003753A CN202310809764.4A CN202310809764A CN117003753A CN 117003753 A CN117003753 A CN 117003753A CN 202310809764 A CN202310809764 A CN 202310809764A CN 117003753 A CN117003753 A CN 117003753A
Authority
CN
China
Prior art keywords
bis
tert
phenyl
acid
butyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202310809764.4A
Other languages
Chinese (zh)
Inventor
陈文铖
开聪聪
李尚儒
伍昱岚
郑帆
戚琳娜
霍延平
籍少敏
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangdong University of Technology
Original Assignee
Guangdong University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Guangdong University of Technology filed Critical Guangdong University of Technology
Priority to CN202310809764.4A priority Critical patent/CN117003753A/en
Publication of CN117003753A publication Critical patent/CN117003753A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/06—Peri-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/10—Triplet emission

Abstract

The patent application discloses preparation of carbonyl arylamine pi stacking fluorescent dye. The structure takes triphenylamine or N- (2-bromophenyl) carbazole as an electron donor, carbonyl nitrogen is introduced between methyl and triphenylamine as an acceptor, a series of organic luminescent molecules with space donor acceptor pi stacking are prepared, and the carbonyl arylamine pi stacking fluorescent dye has good luminous intensity and extremely high fluorescence quantum yield by inhibiting non-radiative transition, and has obvious economic value in the application fields of luminescent materials, luminescent devices or intelligent materials and the like as a novel luminescent molecule with excellent performance.

Description

Carbonyl arylamine pi stacking fluorescent dye and preparation method thereof
Technical Field
The application relates to the field of organic compounds, in particular to a carbonyl arylamine pi stacking fluorescent dye and a preparation method thereof.
Background
An organic electroluminescent device (OLED: organic Light Emission Diodes) is a device with a sandwich-like structure, comprising positive and negative electrode layers and an organic functional material layer sandwiched between the electrode layers. Because the OLED device has the advantages of high brightness, quick response, wide viewing angle, simple process, flexibility and the like, the OLED device has a great deal of attention in the novel display technical field and the novel illumination technical field. At present, the technology is widely applied to display panels of products such as novel illumination lamps, smart phones and tablet computers, and further expands the application field of large-size display products such as televisions, and is a novel display technology with rapid development and high technical requirements. In order to prepare the OLED light-emitting device with lower driving voltage, better light-emitting efficiency and longer service life of the device, the performance of the OLED device is continuously improved, the structure and the manufacturing process of the OLED device are required to be optimized, and the organic light-emitting molecular material in the OLED device is required to be continuously and deeply researched to prepare the functional material with higher performance.
However, the existing organic luminescent molecules have certain disadvantages, such as low luminescent intensity, low fluorescence quantum yield, and serious efficiency roll-off caused by molecular aggregation due to the existence of non-radiative transition, and the designed molecules have unique molecular structure and smaller deltaE ST The vibrator strength solves some technical problems of the existing fluorescent dye.
Content of the patent application
To overcome one of the problems in the prior art, the primary object of the present application is to provide a carbonyl arylamine pi-stack fluorescent dye. The carbonyl arylamine pi stacking fluorescent dye has good luminous intensity and extremely high fluorescence quantum yield by inhibiting non-radiative transition.
Another object of the present application is to provide a method for preparing the above carbonyl arylamine pi-stack fluorescent dye.
The above purpose of the present patent application is achieved by the following technical solutions:
a carbonyl arylamine pi-stack fluorescent dye, wherein the main ring structure in the structural general formula of the carbonyl arylamine pi-stack fluorescent dye is as follows:
wherein R represents hydrogen, methyl, phenoxathiazide, phenothiazine, 1,3,6, 8-tetramethyl-9H-carbazole, N-methylcarbazole or 5-phenyl-5, 10-dihydrophenazine
Preferably, the carbonyl arylamine pi stacking fluorescent dye in the present application is selected from one of the following specific compounds:
the application also provides a preparation method of M1 and M2 in the carbonyl arylamine pi stacking fluorescent dye.
Compared with the prior art, the beneficial effect of this patent application is:
the fluorescent dye of the patent application is connected with a donor and an acceptor unit through rigid linking fluorene, and carbonyl nitrogen is introduced between the donor and a large steric hindrance group to serve as an acceptor, so that a series of organic small molecules with emission wavelengths from green to yellow are prepared, and in addition, the carbonyl arylamine pi-stacking fluorescent dye can inhibit non-radiative transition to realize high efficiency.
Therefore, the invention has good application prospect in the fields of full-color display and solid-state illumination as a luminescent material or an intelligent material.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a compound M1 prepared in example 1 of the present patent application;
FIG. 2 is a mass spectrum of compound M1 prepared in example 1 of the present patent application;
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of the compound M2 prepared in example 2 of the present patent application;
FIG. 4 is a mass spectrum of compound M2 prepared in example 2 of the present patent application;
FIG. 5 shows that the compound M1 prepared in example 1 of the present patent application is at 1.0X10 -5 Ultraviolet absorption spectrum and fluorescence emission spectrum in toluene solution of M;
FIG. 6 shows that the compound M2 prepared in example 2 of the present patent application is at 1.0X10 -5 Ultraviolet absorption spectrum and fluorescence emission spectrum in toluene solution of M.
Detailed Description
Embodiments of the present application will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustration of the present application and should not be construed as limiting the scope of the present application. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
It should be noted that:
in this patent application, all the embodiments mentioned herein and the preferred methods of implementation can be combined with each other to form new solutions, if not specifically stated.
In the present patent application, a percentage (%) or part refers to a weight percentage or part by weight with respect to the composition, unless otherwise specified.
In this patent application, the components concerned or their preferred components can be combined with one another to form new solutions, unless otherwise specified.
In this patent application, unless otherwise indicated, the numerical ranges "a-b" represent shorthand representations of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "1-5" means that all real numbers between "1-5" have been listed throughout, and "1-5" is only a shorthand representation of a combination of these values.
The "range" disclosed in this patent application may be in the form of a lower limit and an upper limit, respectively, of one or more lower limits and one or more upper limits.
In this application, unless otherwise indicated, the various reactions or steps may be performed sequentially or sequentially. Preferably, the reaction processes herein are performed sequentially.
Unless otherwise defined, the technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition, any method or material similar or equivalent to those described may be used in the present application.
The present application provides a carbonyl aromatic amine pi-stacking fluorescent dye. The main ring structure in the structural general formula of the carbonyl arylamine pi-stacking fluorescent dye is as follows:
wherein R represents hydrogen, methyl, phenoxathiazide, phenothiazine, 1,3,6, 8-tetramethyl-9H-carbazole, N-methylcarbazole or 5-phenyl-5, 10-dihydrophenazine
In some preferred embodiments, the carbonyl-arylamine pi-stack fluorescent dye of the present application is selected from one of the following specific compounds:
in some more preferred embodiments, the carbonyl-arylamine pi-stack fluorescent dye is selected from one of the following specific compounds:
the fluorescent dye of the patent application is connected with a donor and an acceptor unit through rigid linking fluorene, carbonyl nitrogen is introduced between the donor and a large steric hindrance group to serve as an acceptor, so that a series of organic small molecules with emission wavelengths from green to yellow are prepared, in addition, the carbonyl arylamine pi-stacking fluorescent dye can inhibit non-radiative transition to realize high efficiency, and the specific:
the molecules have a small delta EST as shown in the above graph, and the small delta EST can lead to higher luminous intensity and higher luminous efficiency of lower-energy luminescence, and the small oscillator intensity can inhibit non-radiative transition while inhibiting structural relaxation, so that the series of molecules can well inhibit the non-radiative transition to realize higher efficiency. The strong electronic coupling between the donor and acceptor units is also sufficient to allow efficient direct absorption of the CT state.
Rigid exciplex emitters have very high luminescence quantum yields, exceeding 90%, when added to solid matrices, compared to more flexible or less coupled conventional exciplex. And has a similar ΔEST and a faster RISC rate than the conventional pi-linked TADF molecules. Therefore, the invention has good application prospect in the fields of full-color display and solid-state illumination as a luminescent material or an intelligent material.
The application also provides a preparation method of the carbonyl arylamine pi-stacking fluorescent dye M1. The method comprises the following steps:
s11, dissolving 2-bromo-3-methylbenzoic acid in an organic solvent, adding iodobenzene diacetic acid, iodine and palladium acetate, and reacting for 16-24 hours at 90-110 ℃ under the catalysis of palladium acetate to obtain a corresponding iodized product;
s12, dissolving the iodized product obtained in the step S1 in an organic solvent, sequentially adding inorganic alkali and methyl iodide, and obtaining a corresponding esterified product at 60-90 ℃ for 3-6 hours in a hydrolysis reaction time;
s13, dissolving the esterified product, pinacol phenylborate, tetraphenylphosphine palladium and inorganic alkali prepared in the step S2 in a solvent, and reacting for 6-8 hours at 40-60 ℃ under the action of the tetraphenylphosphine palladium to prepare a corresponding biphenyl pinacol borate product;
s14, dissolving the biphenyl boric acid pinacol ester product prepared in the step S3 in methyl sulfonic acid, and carrying out ring closure reaction for 6-10 h at the temperature of 60-90 ℃ to prepare a corresponding fluorenone derivative;
s15, reacting the corresponding fluorenone derivative prepared in the step S4 with 2-bromotriphenylamine in an inert gas atmosphere at the temperature of minus 78 ℃ for 1h through n-butyllithium reaction, and transferring to room temperature overnight; intermediate a is prepared;
S16, oxidizing 2, 5-dibromo-m-xylene and potassium permanganate to obtain 2, 5-dibromo-isophthalic acid;
s17, carrying out acylation reaction on the 2, 5-dibromoisophthalic acid prepared in the S1, oxalyl chloride and methanol to generate 2, 5-dibromoisophthalic acid dimethyl ester;
s18, reacting dimethyl 2, 5-dibromoisophthalate with di-tert-butylaniline under the action of copper catalyst by using o-dichlorobenzene as a solvent to obtain dimethyl 2- (bis (4- (tert-butyl) phenyl) amino) -5-bromoisophthalic acid;
s19, performing hydrolysis reaction on the 2- (bis (4- (tert-butyl) phenyl) amino) -5-bromoisophthalic acid dimethyl ester prepared in the S3 under the condition of an alkaline aqueous solution by using ethanol as a solvent to generate 2- (bis (4- (tert-butyl) phenyl) amino) -5-bromoisophthalic acid;
s20, reacting the 2- (bis (4- (tert-butyl) phenyl) amino) -5-bromoisophthalic acid prepared in the S4 with oxalyl chloride, and reacting in the presence of a catalyst tin tetrachloride to generate 2- (bis (4- (tert-butyl) phenyl) -bromobenzoazabicyclo hexane ring;
s21, adding the 2- (bis (4- (tert-butyl) phenyl) -bromobenzoazabicyclo hexane ring, pinacol biborate and potassium acetate prepared in the step S9 into a solvent 1, 4-dioxane in [1, 1' -bis (diphenylphosphino) ferrocene ] palladium dichloride, and reacting for 20-24 hours at 90-110 ℃ under the action of inert gas to prepare a 2- (bis (4- (tert-butyl) phenyl) -bromobenzoazabicyclo hexane cycloborate pinacol ester product;
S22, adding the intermediate a, the tetraphenylphosphine palladium and the potassium carbonate prepared in the step S5 into a solvent in the 2- (bis (4- (tert-butyl) phenyl) -bromobenzoazabicyclo-hexane cyclic-boric acid pinacolate product prepared in the step S10, and reacting for 20-24 hours at 90-120 ℃ under the action of inert gas to prepare a target product M1:
in the preparation method described in the present application, in the step S12, the molar ratio of the iodo product, inorganic base, and methyl iodide is: 1 (1.5-2.5), 1.5-2, and/or;
in the step S13, the mole ratio of the esterification product, the pinacol phenylborate, the tetraphenylphosphine palladium and the inorganic base is 1: (0.9-1.1): (0.04-0.06): (1.5-2.5), and/or;
the molar ratio of the intermediate a, 2-bromotriphenylamine to n-butyllithium in the step S15 is as follows: 1:1.2:1.32, and/or;
in the step S20, the molar ratio of the 2- (bis (4- (tert-butyl) phenyl) -bromobenzoazabicyclo hexane, pinacol biborate, potassium acetate and [1, 1' -bis (diphenylphosphino) ferrocene ] palladium dichloride is 1 (1-1.2): 2.5-3.5): 0.04-0.06.
The application also provides a preparation method of the carbonyl arylamine pi stacking fluorescent dye M2, which comprises the following steps:
S11, dissolving 2-bromo-3-methylbenzoic acid in an organic solvent, adding iodobenzene diacetic acid, iodine and palladium acetate, and reacting for 16-24 hours at 90-110 ℃ under the catalysis of palladium acetate to obtain a corresponding iodized product;
s12, dissolving the iodized product obtained in the step S1 in an organic solvent, sequentially adding inorganic alkali and methyl iodide, and obtaining a corresponding esterified product at 60-90 ℃ for 3-6 hours in a hydrolysis reaction time;
s13, dissolving the esterified product, pinacol phenylborate, tetraphenylphosphine palladium and inorganic alkali prepared in the step S2 in a solvent, and reacting for 6-8 hours at 40-60 ℃ under the action of the tetraphenylphosphine palladium to prepare a corresponding biphenyl pinacol borate product;
s14, dissolving the biphenyl boric acid pinacol ester product prepared in the step S3 in methyl sulfonic acid, and carrying out ring closure reaction for 6-10 h at the temperature of 60-90 ℃ to prepare a corresponding fluorenone derivative;
s25, oxidizing 2, 5-dibromo-m-xylene and potassium permanganate to obtain 2, 5-dibromo-isophthalic acid;
s26, carrying out acylation reaction on the 2, 5-dibromoisophthalic acid prepared in the S1, oxalyl chloride and methanol to generate 2, 5-dibromoisophthalic acid dimethyl ester;
s27, reacting dimethyl 2, 5-dibromoisophthalate with di-tert-butylaniline under the action of copper catalyst by using o-dichlorobenzene as a solvent to obtain dimethyl 2- (bis (4- (tert-butyl) phenyl) amino) -5-bromoisophthalic acid;
S28, reacting the dimethyl 2- (bis (4- (tert-butyl) phenyl) amino) -5-bromoisophthalic acid prepared in the step S3 with ethanol serving as a solvent under the condition of an alkaline aqueous solution to generate 2- (bis (4- (tert-butyl) phenyl) amino) -5-bromoisophthalic acid;
s29, reacting the 2- (bis (4- (tert-butyl) phenyl) amino) -5-bromoisophthalic acid prepared in the S4 with oxalyl chloride, and performing cyclization reaction in the presence of a catalyst tin tetrachloride to generate 2- (bis (4- (tert-butyl) phenyl) -bromobenzoazabicyclo hexane ring;
s30, adding the 2- (bis (4- (tert-butyl) phenyl) -bromobenzoazabicyclo hexane ring, pinacol biborate and potassium acetate prepared in the step S10 into a solvent 1, 4-dioxane in [1, 1' -bis (diphenylphosphino) ferrocene ] palladium dichloride, and reacting for 20-24 hours at 90-110 ℃ under the action of inert gas to prepare a 2- (bis (4- (tert-butyl) phenyl) -bromobenzoazabicyclo hexane cycloborate pinacol ester product;
s31, reacting the corresponding fluorenone derivative prepared in the step S4 with N- (2-bromophenyl) carbazole in an inert gas atmosphere at the temperature of minus 78 ℃ for 1h through N-butyllithium reaction, and transferring to room temperature overnight; intermediate b is prepared;
s32, adding the intermediate b, the tetraphenylphosphine palladium and the potassium carbonate prepared in the step S5 into a solvent to react for 20-24 hours at 90-120 ℃ under the action of inert gas to prepare a target product, wherein the pinacol ester product is the 2- (bis (4- (tert-butyl) phenyl) -bromobenzoazabicyclo-hexane cyclic borate prepared in the step S10:
In some preferred embodiments, in the step 30, the molar ratio of 2- (bis (4- (tert-butyl) phenyl) -bromobenzoazabicyclo hexane, pinacolato biborate, potassium acetate, [1, 1' -bis (diphenylphosphino) ferrocene ] palladium dichloride is 1 (1-1.2): (2.5-3.5): (0.04-0.06).
In some preferred embodiments, in the step S31, the molar ratio of the intermediate b, N- (2-bromophenyl) carbazole to N-butyllithium is: 1:1.2:1.32.
in some preferred embodiments, in the step S11, the organic solvent is one of toluene, dimethyl sulfoxide, N-dimethylformamide, and/or; in the step S12, the organic solvent is acetone.
In some preferred embodiments, the inorganic base described in steps S12, S13 in the synthetic methods described herein is potassium carbonate, and/or; the solvent in the step S13 is a mixture of any one of toluene, tetrahydrofuran and N, N-dimethylformamide and water.
The method for preparing the carbonyl arylamine pi-stack fluorescent dye compounds of formulas M1 and M2 will be described in detail below.
Example 1
The embodiment describes the preparation method of carbonyl arylamine pi stacking fluorescent dye M1 in detail, and the structural formula of the molecule M1 is shown as M1:
The preparation method of the compound comprises the following steps:
preparation of S11.2-bromo-6-iodo-3-methylbenzoic acid:
in a 250mL flask, 2-bromo-3-methylbenzoic acid (5 g,23.4 mmol), palladium acetate (0.26 g,1.17 mmol), iodobenzene diacetic acid (7.35 g,23.4 mmol) and iodine (5.95 g,23.4 mmol) were dissolved in an N, N-dimethylformamide solution (60 mL). After stirring at 100℃for 24h, the reaction mixture was cooled to room temperature, diluted with 50ml of ethyl acetate, and then 200ml of aqueous hydrochloric acid (0.5N) was added to wash out N, N-dimethylformamide, and the crude product was extracted 3 times with ethyl acetate. The organic phase was collected, washed with saturated brine, and dried over anhydrous sodium sulfate. After removal of the organic solvent by rotary evaporation under vacuum at 0-700 mbar for 30min, the residue was purified by column chromatography on silica gel to give 6.71g (yield: 85%) of iodinated product 2-bromo-6-iodo-3-methylbenzoic acid as a white solid.
S12, preparing methyl 2-bromo-6-iodo-3-methylbenzoate;
2-bromo-6-iodo-3-methylbenzoic acid (6.71 g,18.8 mmol) was dissolved in acetone (50.0 mL), followed by addition of potassium carbonate (5.2 g,37.6 mmol) and methyl iodide (4 g,28.2 mmol). The reaction mixture was reacted under reflux for 3 hours and then quenched with water. The crude product was extracted 3 times with ethyl acetate, the organic phase was collected, and the organic phase was washed with brine, dried over anhydrous sodium sulfate, concentrated in vacuo at 0 to 700mbar for 30min by rotary evaporator, and after removal of the organic solvent, 6.64g (yield: 95%) of methyl 2-bromo-6-iodo-3-methylbenzoate was obtained. This material was used in the next reaction without further purification.
Preparation of S13.3-bromo-4-methyl- [1,1' -biphenyl ] -2-carboxylic acid methyl ester;
to a double-necked flask equipped with a reflux condenser were added methyl 2-bromo-6-iodo-3-methylbenzoate (6.64 g,17.9 mmol), phenylboronic acid (2.2 g,17.9 mmol), tetrakis triphenylphosphine palladium (1.04 g,0.9 mmol) and potassium carbonate (4.5 g,35.8 mmol), followed by N, N-dimethylformamide (50 mL) and water (8 mL), and the mixture was obtained and then the system was evacuated and nitrogen was purged. The resulting mixture was stirred at 55℃for 7 hours, cooled to room temperature, poured into saturated brine, and extracted 3 times with ethyl acetate. The organic layer was collected, and the collected organic layer was washed with saturated brine and then dried over anhydrous sodium sulfate. The residue was purified by column chromatography on silica gel after removal of the organic solvent by rotary evaporation under vacuum for 30min at 0-700 mbar to give 4.3g of methyl 3-bromo-4-methyl- [1,1' -biphenyl ] -2-carboxylate as an oily product. (yield: 75%)
S14.1-bromo-2-methyl-9H-fluorenone preparation;
3-bromo-4-methyl- [1,1' -biphenyl ] -2-carboxylic acid methyl ester (4.3 g,13.4 mmol) was dissolved in methanesulfonic acid (10 ml). The reaction was stirred at 65 ℃ for 6 hours, then quenched with water and extracted 3 more times with ethyl acetate. The organic layer was collected, washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under vacuum at 0 to 700mbar for 30min by rotary evaporator to remove the organic solvent to give 3.6g (yield: 92%) of 1-bromo-2-methyl-9H-fluorenone as a yellow solid.
Preparation of S15.2, 5-dibromoisophthalic acid
2, 5-Dibromometaxylene (3.96 g,15 mmol), potassium permanganate (9.48 g,60 mmol) were added sequentially to a 100ml two-neck round bottom flask, followed by 30ml t-butanol and 20ml deionized water, and 1g/ml NaOH solution, and stirred at 75℃for 12h. Filtration, elution with deionized water followed by acidification, filtration and drying of the filter cake gave 3.89g of compound 1 as a white solid ((yield 80%).
In some preferred embodiments of the present application, the molar ratio of 2, 5-dibromometaxylene to potassium permanganate in step S16 is (1-2): (1-6); more preferably, the molar ratio of 2, 5-dibromometaxylene to potassium permanganate in step S16 is 1:3.
In some preferred embodiments of the present patent application, the solvent used in the oxidation of 2, 5-dibromometaxylene by the strong oxidizing agent potassium permanganate in step S16 is t-butanol;
in some preferred embodiments of the present application, the temperature of the reaction in step S16 is 70 to 95 ℃ and the reaction time is 10 to 20 hours; more preferably, the reaction temperature is 79 ℃ and the reaction time is 12 hours;
in some preferred embodiments of the present application, the post-treatment described in step S16 is acidification, filtration, washing, drying. The reacted solution is acidified by strong acid, then filtered, washed three times by water after filtration, and the filter cake is dried to obtain the product 2, 5-dibromoisophthalic acid.
S16.2, preparation of 5-dibromo-isophthalic acid dimethyl ester:
compound 1 (1.77 g,4.5 mmol) was added to a 100mL two-necked flask with dichloromethane (45 mL), oxalyl chloride (3.8 g,30 mmol) was added dropwise at low temperature, DMF (0.5 g.6.8 mmol) was reacted at 30℃for 2 hours with stirring, and concentrated under reduced pressure to give 1.6g (yield 82%) of an off-white solid.
In some preferred embodiments of the present application, the molar ratio of 2, 5-dibromoisophthalic acid, oxalyl chloride and methanol described in step S17 is (1-2): (3-12): (4-10); more preferably, the ratio of 2, 5-dibromoisophthalic acid, oxalyl chloride and methanol in step S142 is 1:3:6.
in some preferred embodiments of the present application, the solvent used in step S17 is methylene chloride. In some preferred embodiments of the present application, the reaction temperature in step S17 is 10 to 40 ℃ and the reaction time is 2 to 6 hours; more preferably, the reaction temperature in step S17 is 25℃and the reaction time is 3 hours.
In some preferred embodiments of the present application, the post-treatment in step S17 is concentration, separation. After the reaction is completed, the organic phase is concentrated under reduced pressure to obtain crude product of dimethyl 2, 5-dibromoisophthalate.
Preparation of dimethyl 2- (bis (4- (tert-butyl) phenyl) amino) -5-bromoisophthalic acid:
Dimethyl 2, 5-dibromoisophthalate (4.00 g,11.4 mmol), di-t-butylaniline (3.20 g,11.4 mmol), potassium carbonate (2.36 g,11.7 mmol), copper powder (0.10 g,1.5 mmol), cuprous iodide (0.15 g,0.79 mmol) were successively added to a 150ml two-necked flask, the flask was evacuated under vacuum and replaced three times with dry argon, then orthodichlorobenzene (36 ml) was added, after stirring and reacting at 120℃for 30 hours, cooling and filtering, and the filtrate was distilled under reduced pressure to obtain a yellow solid, which was obtained by column chromatography using silica gel powder as a stationary phase and petroleum ether/ethyl acetate as an eluent. (yield 45%).
In some preferred embodiments of the present application, in step S18, the molar ratio of dimethyl 2, 5-dibromoisophthalate, di-t-butylaniline, potassium carbonate is (1-2): (1.5-4): (2-6), more preferably, the molar ratio of dimethyl 2, 5-dibromoisophthalate, di-t-butylaniline and potassium carbonate is 1:1.5:3.
in some preferred embodiments of the present application, the reaction solvent in step S18 is o-dichlorobenzene.
In some preferred embodiments of the present application, the conditions of the reaction are heated under reflux under inert gas. The inert gas in step S18 is nitrogen, argon or helium. More preferably, the inert gas in step S18 is argon. In some preferred embodiments of the present application, the temperature of the reaction in step S18 is 120 to 200℃and the reaction time is 12 to 50 hours. More preferably, the reaction temperature in step S18 is 130℃and the reaction time is 28 hours.
In some preferred embodiments of the present application, the reaction in step S18 is catalyzed by a metal, more preferably copper.
In some preferred embodiments of the present application, the treatment in step S18 is filtration, drying, concentration, separation. Filtering the reaction liquid after the reaction is finished, and concentrating under reduced pressure to obtain a crude product after the filtration is finished; finally, separating the 2- (bis (4- (tert-butyl) phenyl) amino) -5-bromoisophthalic acid dimethyl ester by using petroleum ether and methylene dichloride as eluent through silica gel column chromatography.
Preparation of S18.2- (bis (4- (tert-butyl) phenyl) amino) -5-bromoisophthalic acid:
dimethyl 2- (bis (4- (tert-butyl) phenyl) amino) -5-bromoisophthalic acid (4.60 g,8.33 mmol), sodium hydroxide (1.2 g,30 mmol), deionized water 30ml, ethanol 30ml were added sequentially to a 150ml two-necked flask, the flask was evacuated under vacuum and replaced three times under dry argon, and after stirring at 80 ℃ for 18 hours, cooled, acidified, filtered, and dried under vacuum to give a yellow solid, 3.06g of a yellow solid was obtained. (yield 70%).
In some preferred embodiments of the present application, the molar ratio of dimethyl 2- (bis (4- (tert-butyl) phenyl) amino) -5-bromoisophthalic acid to ethanol in step S19 is (1-1.5): (3-8). More preferably, the molar ratio of dimethyl 2- (bis (4- (tert-butyl) phenyl) amino) -5-bromoisophthalic acid to ethanol in step S19 is 1:2.5. in some preferred embodiments of the present application, the hydrolysis reaction temperature described in step S19 is 65 to 90 ℃ and the reaction time is 5 to 10 hours.
In some preferred embodiments of the present application, the hydrolysis reaction solvent in step S19 is water.
In some preferred embodiments of the present application, the catalyst employed in the hydrolysis reaction in step S19 is a strong base, which is sodium hydroxide or potassium hydroxide.
In some preferred embodiments of the present application, the reaction conditions described in step S19 are heated under reflux under inert gas. In some preferred embodiments of the present application, the inert gas in step S19 is nitrogen, argon or helium. In some more preferred embodiments of the present application, the inert gas in step S19 is argon.
In some preferred embodiments of the present application, the treatment in step S19 is cooling, concentrating, acidifying, filtering, drying. Cooling the reacted solution to room temperature, and concentrating under reduced pressure; then dissolved with water, acidified with acid, and filtered again, leaving a solid dried in a vacuum oven to give 2- (bis (4- (tert-butyl) phenyl) amino) -5-bromoisophthalic acid.
Preparation of S19.2- (bis (4- (tert-butyl) phenyl) -bromobenzazepine ring:
2- (bis (4- (tert-butyl) phenyl) amino) -5-bromoisophthalic acid (2.60 g,4.96 mmol) and oxalyl chloride (3.77 g,29.8 mmol) were added sequentially to a 150ml two-necked flask. The flask was evacuated under vacuum and replaced three times under dry argon, the reaction was stirred at 25℃for 1h, then tin tetrachloride (2.65 g,10.20 mmol) was added dropwise and the reaction was continued at 40℃for 12 h. After the reaction was completed, the mixture was cooled and added to a 1mol/L strong alkali solution, extraction was performed with methylene chloride, and distillation was performed under reduced pressure to obtain a yellowish green solid. 1.45g of a yellowish green powder was obtained by column chromatography using silica gel powder as a stationary phase and petroleum ether/methylene chloride as an eluent. (yield 58%).
In some preferred embodiments of the present application, the molar ratio of 2- (bis (4- (tert-butyl) phenyl) amino) -5-bromoisophthalic acid, oxalyl chloride and tin tetrachloride in step S20 is (1 to 1.5): (3-8): (0.3-0.6). In some more preferred embodiments of the present application, the molar ratio of 2- (bis (4- (tert-butyl) phenyl) amino) -5-bromoisophthalic acid, oxalyl chloride and tin tetrachloride in step S20 is 1:3:0.4.
in some preferred embodiments of the present application, the solvent employed in the reaction in step S20 is methylene chloride.
In some preferred embodiments of the present application, the conditions for the cyclization reaction in step S20 are heated under reflux under inert gas.
In some preferred embodiments of the present application, the inert gas in step S20 is nitrogen, argon or helium. In some more preferred embodiments of the present application, the inert gas in step S20 is argon. In some preferred embodiments of the present application, the hydrolysis reaction temperature described in step S20 is 25 to 40 ℃ and the reaction time is 5 to 10 hours. In some more preferred embodiments of the present application, the temperature of the reaction is 25 ℃; the reaction time was 10 hours.
In some preferred embodiments of the present application, the treatment in step S20 is cooling, extraction, drying, concentration, separation. Cooling the reacted solution to room temperature, extracting the obtained mixed solution with dichloromethane for three times, and combining organic phases obtained by the three extractions; drying with anhydrous sodium sulfate, and concentrating the organic phase under reduced pressure to obtain a crude product; finally, separating the 2- (bis (4- (tert-butyl) phenyl) -bromobenzoazabicyclo hexane by using dichloromethane and petroleum ether as eluent through silica gel column chromatography.
S20.2 preparation of pinacol ester of bis (4- (tert-butyl) phenyl) -bromobenzoazabicyclo hexane cyclic borate:
2- (bis (4- (tert-butyl) phenyl) -bromobenzoazabicyclo hexane (5 g,18.5 mol) was dissolved in 150 ml of 1, 4-dioxane, pinacol biboronate (31 g,20 mol), potassium acetate (5.4, 55.5 mol) and [1,1' -bis (diphenylphosphine) ferrocene ] palladium dichloride (0.75 g,0.925 mol) were added in this order, the temperature was raised to 100℃under the protection of argon, heating was stopped after stirring for 24 hours, the reaction solution was filtered, 100ml of ethyl acetate was washed cake, the filtrate was concentrated to dryness, and the residue was separated by column chromatography to give 6.34g of 2- (bis (4- (tert-butyl) phenyl) -bromobenzoazabicyclo-hexane) pinacol borate as a yellow solid (yield 90%).
Preparation of S21.1-bromo-2-methyl-10-phenyl-10H-spiro [ acridine-9, 9' -fluorene ]:
in a two-necked flask, 2-bromotriphenylamine (4.4 g,13.5 mmol) was dissolved in 50mL of dehydrated tetrahydrofuran under nitrogen. The mixture was cooled to-78 ℃ and held for 10 minutes. 2.4M n-butyllithium (6.2 ml,14.8 mmol) was then added dropwise over 10 minutes and the mixture was stirred for a further 1h at-78 ℃. After that, 1-bromo-2-methyl-9H-fluorenone (4.6 g,16.9 mmol) was added, and after a further reaction of 15min at-78 ℃, the mixture was slowly warmed to room temperature and stirred overnight. Then 10mL of distilled water was added to quench the reaction. The mixture was concentrated under reduced pressure to remove tetrahydrofuran, then extracted 3 times with dichloromethane, and the dichloromethane was removed under reduced pressure. The residue was dissolved in 30mL of acetic acid, followed by the addition of 3mL of hydrochloric acid. The mixture was stirred at 110℃for 4 hours. After cooling to room temperature, the mixture was poured into 100mL of ice water and filtered to give a crude product. The crude product was purified by silica gel column chromatography to give 1-bromo-2-methyl-10-phenyl-10H-spiro [ acridine-9, 9' -fluorene ] (i.e., intermediate a) as a solid product (yield: 85%).
Preparation of S22.3, 11-di-tert-butyl-7- (2 '-methyl-10-phenyl-10H-spiroacridine-9, 9' -fluorenyl) quinolino [3,2,1-de ] acridine-5, 9-dione:
1-bromo-2-methyl-10-phenyl-10H-spiro [ acridine-9, 9' -fluorene ] (3.6 g,12.4 mmol), 2- (bis (4- (t-butyl) phenyl) -bromobenzoazabicyclo-hexane-cyclohexane-boric acid (4.72 g,13.7 mmol), tetrakis triphenylphosphine palladium (0.7 g,0.62 mmol) and potassium carbonate (8.1 g,24.8 mmol) were added under nitrogen atmosphere, N-dimethylformamide (40 mL) and water (8 mL) were further added, the system was evacuated and filled with nitrogen, then heated under reflux in an oil bath at 110℃for 24 hours, after the reaction was completed, cooled to room temperature, and filtered to obtain 3, 11-di-tert-butyl-7- (2 ' -methyl-10-phenyl-10H-spiroacridine-9, 9' -fluorenyl) quinoline-3, 2, 1-de-acridine-5, 9-dione (M1) (yield: 60%).
Example 2
In another preparation method of carbonyl arylamine pi stacking fluorescent dye in the embodiment, the structural formula is shown as M2:
the preparation method of the compound comprises the following steps:
preparation of S11.2-bromo-6-iodo-3-methylbenzoic acid:
in a 250mL flask, 2-bromo-3-methylbenzoic acid (5 g,23.4 mmol), palladium acetate (0.26 g,1.17 mmol), iodobenzene diacetic acid (7.35 g,23.4 mmol) and iodine (5.95 g,23.4 mmol) were dissolved in N, N-dimethylformamide (60 mL). After stirring at 100℃for 24h, the reaction mixture was cooled to room temperature, diluted with 50ml of ethyl acetate, and then 200ml of aqueous hydrochloric acid (0.5N) was added to wash out N, N-dimethylformamide, and the crude product was extracted 3 times with ethyl acetate. The organic phase was collected, washed with saturated brine, and dried over anhydrous sodium sulfate. After removal of the organic solvent by rotary evaporation under vacuum at 0-700 mbar for 30min, the residue was purified by column chromatography on silica gel to give 6.71g of iodinated product 2-bromo-6-iodo-3-methylbenzoic acid as a white solid. (yield: 85%)
S12, preparing methyl 2-bromo-6-iodo-3-methylbenzoate;
2-bromo-6-iodo-3-methylbenzoic acid (6.71 g,18.8 mmol) was dissolved in acetone (50.0 mL), followed by addition of potassium carbonate (5.2 g,37.6 mmol) and methyl iodide (4 g,28.2 mmol). The reaction mixture was reacted under reflux for 3 hours and then quenched with water. The crude product was extracted 3 times with ethyl acetate, the organic phase was collected, and the organic phase was washed with brine, dried over anhydrous sodium sulfate, concentrated under vacuum at 0 to 700mbar for 30min by rotary evaporator, and after removal of the organic solvent, 6.64g of methyl 2-bromo-6-iodo-3-methylbenzoate was obtained. This material was used in the next reaction without further purification.
(yield: 95%)
Preparation of S13.3-bromo-4-methyl- [1,1' -biphenyl ] -2-carboxylic acid methyl ester;
to a double-necked flask equipped with a reflux condenser were added methyl 2-bromo-6-iodo-3-methylbenzoate (6.64 g,17.9 mmol), pinacol phenylborate (2.2 g,17.9 mmol), palladium tetraphenylphosphine (1.04 g,0.9 mmol) and potassium carbonate (4.5 g,35.8 mmol), followed by N, N-dimethylformamide (50 mL) and water (8 mL), and the mixture was obtained and then evacuated and nitrogen-filled. The resulting mixture was stirred at 55℃for 7 hours, cooled to room temperature, poured into saturated brine, and extracted 3 times with ethyl acetate. The organic layer was collected, and the collected organic layer was washed with saturated brine and then dried over anhydrous sodium sulfate. The residue was purified by column chromatography on silica gel after removal of the organic solvent by rotary evaporation under vacuum for 30min at 0-700 mbar to give 4.3g of methyl 3-bromo-4-methyl- [1,1' -biphenyl ] -2-carboxylate as an oily product. (yield: 75%)
S14.1-bromo-2-methyl-9H-fluorenone preparation;
/>
3-bromo-4-methyl- [1,1' -biphenyl ] -2-carboxylic acid methyl ester (4.3 g,13.4 mmol) was dissolved in methanesulfonic acid (10 ml). The reaction was stirred at 65 ℃ for 6 hours, then quenched with water and extracted 3 more times with ethyl acetate. The organic layer was collected, washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under vacuum at 0 to 700mbar for 30min by rotary evaporator to remove the organic solvent to give 3.6g (yield: 92%) of 1-bromo-2-methyl-9H-fluorenone as a yellow solid.
Preparation of S15.2, 5-dibromoisophthalic acid
2, 5-Dibromometaxylene (3.96 g,15 mmol), potassium permanganate (9.48 g,60 mmol) were added sequentially to a 100ml two-neck round bottom flask, followed by 30ml t-butanol and 20ml deionized water, and 1g/ml NaOH solution, and stirred at 75℃for 12h. Filtration, elution with deionized water followed by acidification, filtration and drying of the filter cake gave 3.89g of a white solid (80% yield).
In some preferred embodiments of the present application, the molar ratio of 2, 5-dibromometaxylene to potassium permanganate in step S16 is (1-2): (1-6); more preferably, the molar ratio of 2, 5-dibromometaxylene to potassium permanganate in step S1 is 1:3.
In some preferred embodiments of the present patent application, the solvent used in the oxidation of 2, 5-dibromometaxylene by the strong oxidizing agent potassium permanganate in step S16 is t-butanol;
in some preferred embodiments of the present application, the temperature of the reaction in step S16 is 70 to 95 ℃ and the reaction time is 10 to 20 hours; more preferably, the reaction temperature is 79 ℃ and the reaction time is 12 hours;
in some preferred embodiments of the present application, the post-treatment described in step S16 is acidification, filtration, washing, drying. The reacted solution is acidified by strong acid, then filtered, washed three times by water after filtration, and the filter cake is dried to obtain the product 2, 5-dibromoisophthalic acid.
S16.2, preparation of 5-dibromo-isophthalic acid dimethyl ester:
compound 1 (1.77 g,4.5 mmol) was added to a 100mL two-necked flask with dichloromethane (45 mL), oxalyl chloride (3.8 g,30 mmol) was added dropwise at low temperature, DMF (0.5 g.6.8 mmol) was reacted at 30℃for 2 hours with stirring, and concentrated under reduced pressure to give 1.6g (yield 82%) of an off-white solid.
In some preferred embodiments of the present application, the molar ratio of 2, 5-dibromoisophthalic acid, oxalyl chloride and methanol described in step S17 is (1-2): (3-12): (4-10), more preferably, the ratio of 2, 5-dibromoisophthalic acid, oxalyl chloride and methanol in step S6 is 1:3:6.
In some preferred embodiments of the present application, the solvent used in step S17 is methylene chloride. In some preferred embodiments of the present application, the reaction temperature in step S17 is 10 to 40 ℃ and the reaction time is 2 to 6 hours; more preferably, the reaction temperature in step S6 is 25℃and the reaction time is 3 hours.
In some preferred embodiments of the present application, the post-treatment in step S17 is concentration, separation. After the reaction is completed, the organic phase is concentrated under reduced pressure to obtain crude product of dimethyl 2, 5-dibromoisophthalate.
Preparation of dimethyl 2- (bis (4- (tert-butyl) phenyl) amino) -5-bromoisophthalic acid:
dimethyl 2, 5-dibromoisophthalate (4.00 g,11.4 mmol), di-t-butylaniline (3.20 g,11.4 mmol), potassium carbonate (2.36 g,11.7 mmol), copper powder (0.10 g,1.5 mmol), cuprous iodide (0.15 g,0.79 mmol) were successively added to a 150ml two-necked flask, the flask was evacuated under vacuum and replaced three times with dry argon, then orthodichlorobenzene (36 ml) was added, after stirring and reacting at 120℃for 30 hours, cooling and filtering, and the filtrate was distilled under reduced pressure to obtain a yellow solid, which was obtained by column chromatography using silica gel powder as a stationary phase and petroleum ether/ethyl acetate as an eluent. (yield 45%).
In some preferred embodiments of the present application, in step S18, the molar ratio of dimethyl 2, 5-dibromoisophthalate, di-t-butylaniline, potassium carbonate is (1-2): (1.5-4): (2-6), more preferably, the molar ratio of dimethyl 2, 5-dibromoisophthalate, di-t-butylaniline and potassium carbonate is 1:1.5:3.
in some preferred embodiments of the present application, the reaction solvent in step S18 is o-dichlorobenzene.
In some preferred embodiments of the present application, the conditions of the reaction are heated under reflux under inert gas. The inert gas in step S18 is nitrogen, argon or helium. More preferably, the inert gas in step S18 is argon. In some preferred embodiments of the present application, the temperature of the reaction in step S18 is 120 to 200℃and the reaction time is 12 to 50 hours. More preferably, the reaction temperature in step S18 is 130℃and the reaction time is 28 hours.
In some preferred embodiments of the present application, the reaction in step S18 is catalyzed by a metal, more preferably copper.
In some preferred embodiments of the present application, the treatment in step S18 is filtration, drying, concentration, separation. Filtering the reaction liquid after the reaction is finished, and concentrating under reduced pressure to obtain a crude product after the filtration is finished; finally, separating the 2- (bis (4- (tert-butyl) phenyl) amino) -5-bromoisophthalic acid dimethyl ester by using petroleum ether and methylene dichloride as eluent through silica gel column chromatography.
Preparation of S18.2- (bis (4- (tert-butyl) phenyl) amino) -5-bromoisophthalic acid:
dimethyl 2- (bis (4- (tert-butyl) phenyl) amino) -5-bromoisophthalic acid (4.60 g,8.33 mmol), sodium hydroxide (1.2 g,30 mmol), deionized water 30ml, ethanol 30ml were added sequentially to a 150ml two-necked flask, the flask was evacuated under vacuum and replaced three times under dry argon, and after stirring at 80 ℃ for 18 hours, cooled, acidified, filtered, and dried under vacuum to give a yellow solid, 3.06g of a yellow solid was obtained. (yield 70%).
In some preferred embodiments of the present application, the molar ratio of dimethyl 2- (bis (4- (tert-butyl) phenyl) amino) -5-bromoisophthalic acid to ethanol in step S19 is (1-1.5): (3-8). More preferably, the molar ratio of dimethyl 2- (bis (4- (tert-butyl) phenyl) amino) -5-bromoisophthalic acid to ethanol in step S19 is 1:2.5. in some preferred embodiments of the present application, the hydrolysis reaction temperature described in step S19 is 65 to 90 ℃ and the reaction time is 5 to 10 hours.
In some preferred embodiments of the present application, the hydrolysis reaction solvent in step S19 is water.
In some preferred embodiments of the present application, the catalyst employed in the hydrolysis reaction in step S19 is a strong base, which is sodium hydroxide or potassium hydroxide.
In some preferred embodiments of the present application, the reaction conditions described in step S19 are heated under reflux under inert gas. In some preferred embodiments of the present application, the inert gas in step S19 is nitrogen, argon or helium. In some more preferred embodiments of the present application, the inert gas in step S19 is argon.
In some preferred embodiments of the present application, the treatment in step S19 is cooling, concentrating, acidifying, filtering, drying. Cooling the reacted solution to room temperature, and concentrating under reduced pressure; then dissolved with water, acidified with acid, and filtered again, leaving a solid dried in a vacuum oven to give 2- (bis (4- (tert-butyl) phenyl) amino) -5-bromoisophthalic acid.
Preparation of S19.2- (bis (4- (tert-butyl) phenyl) -bromobenzazepine ring:
2- (bis (4- (tert-butyl) phenyl) amino) -5-bromoisophthalic acid (2.60 g,4.96 mmol) and oxalyl chloride (3.77 g,29.8 mmol) were added sequentially to a 150ml two-necked flask. The flask was evacuated under vacuum and replaced three times under dry argon, the reaction was stirred at 25℃for 1h, then tin tetrachloride (2.65 g,10.20 mmol) was added dropwise and the reaction was continued at 40℃for 12 h. After the reaction was completed, the mixture was cooled and added to a 1mol/L strong alkali solution, extraction was performed with methylene chloride, and distillation was performed under reduced pressure to obtain a yellowish green solid. 1.45g of a yellowish green powder was obtained by column chromatography using silica gel powder as a stationary phase and petroleum ether/methylene chloride as an eluent. (yield 58%).
In some preferred embodiments of the present application, the molar ratio of 2- (bis (4- (tert-butyl) phenyl) amino) -5-bromoisophthalic acid, oxalyl chloride and tin tetrachloride in step S20 is (1 to 1.5): (3-8): (0.3-0.6). In some more preferred embodiments of the present application, the molar ratio of 2- (bis (4- (tert-butyl) phenyl) amino) -5-bromoisophthalic acid, oxalyl chloride and tin tetrachloride in step S20 is 1:3:0.4.
in some preferred embodiments of the present application, the solvent employed in the reaction in step S20 is methylene chloride.
In some preferred embodiments of the present application, the conditions for the cyclization reaction in step S20 are heated under reflux under inert gas.
In some preferred embodiments of the present application, the inert gas in step S20 is nitrogen, argon or helium. In some more preferred embodiments of the present application, the inert gas in step S20 is argon. In some preferred embodiments of the present application, the hydrolysis reaction temperature described in step S20 is 25 to 40 ℃ and the reaction time is 5 to 10 hours. In some more preferred embodiments of the present application, the temperature of the reaction is 25 ℃; the reaction time was 10 hours.
In some preferred embodiments of the present application, the treatment in step S20 is cooling, extraction, drying, concentration, separation. Cooling the reacted solution to room temperature, extracting the obtained mixed solution with dichloromethane for three times, and combining organic phases obtained by the three extractions; drying with anhydrous sodium sulfate, and concentrating the organic phase under reduced pressure to obtain a crude product; finally, separating the 2- (bis (4- (tert-butyl) phenyl) -bromobenzoazabicyclo hexane by using dichloromethane and petroleum ether as eluent through silica gel column chromatography.
S20.2- (bis (4- (tert-butyl) phenyl) -bromobenzoazabicyclo-hexane cyclic boronic acid pinacol ester preparation;
2- (bis (4- (tert-butyl) phenyl) -bromobenzoazabicyclo hexane (5 g,18.5 mol) was dissolved in 150 ml of 1, 4-dioxane, pinacol biboronate (31 g,20 mol), potassium acetate (5.4, 55.5 mol) and [1,1' -bis (diphenylphosphine) ferrocene ] palladium dichloride (0.75 g,0.925 mol) were added in this order, the temperature was raised to 100℃under the protection of argon, heating was stopped after stirring for 24 hours, the reaction solution was filtered, 100ml of ethyl acetate was washed cake, the filtrate was concentrated and evaporated to dryness, and the residue was separated by column chromatography to give 6.34g of 2- (bis (4- (tert-butyl) phenyl) -bromobenzoazabicyclo cyclohexane pinacolate) (yield 90%).
S21.1-bromo-2-methyl spirofluorene [ fluorene-9, 8' -indole [3,2, 1-des ] acridine ] preparation;
n- (2-bromophenyl) carbazole (4.4 g,13.5 mmol) was dissolved in 50mL of dehydrated tetrahydrofuran in a two-necked flask under nitrogen atmosphere. The mixture was cooled to-78 ℃ and held for 10 minutes. 2.4M n-butyllithium (6.2 ml,14.8 mmol) was then added dropwise over 10 minutes and the mixture was stirred for a further 1h at-78 ℃. After that, 1-bromo-2-methyl-9H-fluorenone (4.6 g,16.9 mmol) was added, and after a further reaction of 15min at-78 ℃, the mixture was slowly warmed to room temperature and stirred overnight. Then 10mL of distilled water was added to quench the reaction. The mixture was concentrated under reduced pressure to remove tetrahydrofuran, then extracted 3 times with dichloromethane, and the dichloromethane was removed under reduced pressure. The residue was dissolved in 30mL of acetic acid, followed by the addition of 3mL of hydrochloric acid. The mixture was stirred at 110℃for 4 hours. After cooling to room temperature, the mixture was poured into 100mL of ice water and filtered to give a crude product. The crude product was purified by silica gel column chromatography to give 1-bromo-2-methylspirofluorene [ fluorene-9, 8' -indole [3,2, 1-des ] acridine ] (i.e. intermediate b) as a solid product (yield: 85%).
Preparation of (S) -3, 11-di-tert-butyl-7- (2-methyl spirofluorene-9, 8' -indol [3,2,1-de ] acridin ] -1-yl) quinolino [3,2, 1-des ] acridin-5, 9-dione;
1-bromo-2-methylspirofluorene [ fluorene-9, 8 '-indole [3,2, 1-des ] acridine ] (3.6 g,12.4 mmol), 2- (bis (4- (t-butyl) phenyl) -bromophenylazabicyclo-hexane cyclic boric acid (4.72 g,13.7 mmol), tetrakis triphenylphosphine palladium (0.7 g,0.62 mmol) and potassium carbonate (8.1 g,24.8 mmol) were added to a two-necked flask under nitrogen atmosphere, N-dimethylformamide (40 mL) and water (8 mL) were further added, and the system was evacuated to a nitrogen atmosphere, then heated and refluxed in an oil bath at 110℃for 24 hours, after the completion of the reaction, cooled to room temperature, and filtered to obtain yellow solid (S) -3, 11-di-t-butyl-7- (2-methylspirofluorene-9, 8' -indole [3,2,1-de ] acridine ] -1-yl) quino [3,2,1-de ] acridine-5, 9-dione (M2) (yield: 60%).
Characterization and performance testing
The carbonyl arylamine pi stacked fluorescent dyes M1 and M2 obtained in examples 1 and 2 were characterized and tested for performance.
The test method is as follows:
compound structure detection: using a Bruker 400MHz superconducting nuclear magnetic resonance apparatus, wherein the solvent used in MI is deuterated chloroform, and the solvent used in M2 is deuterated chloroform;
mass spectrometry detection: m1 prepared in example 1 and M2 prepared in example 2 are dissolved in dichloromethane to prepare a solution with the concentration of 1mg/mL, and a Siemens-Fei Q exact ultra-high resolution quadrupole combined electrostatic field track trap liquid chromatograph is adopted to carry out mass spectrometry.
Ultraviolet absorption spectrum detection: using a Shimadzu ultraviolet-visible spectrophotometer UV-2700, the scan range is
260～750nm；
And (3) emission spectrum detection: using a steady state/transient fluorescence spectrometer (FLS 980), excitation wavelength was 320nm,
the test temperature was 300K under nitrogen protection.
The test results were as follows:
the molecular hydrogen spectrum of the carbonyl aromatic amine pi-stack fluorescent dye prepared in example 1 for preparing the compound M1 is shown in figure 1.
Example 2 preparation of carbonyl arylamine pi stacked fluorescent dye the molecular hydrogen spectrum of the preparation compound M2 is shown in figure 5.
The M1 and M2 prepared in the example are dissolved in toluene (Tol) solution to prepare 1X 10 by using an Shimadzu ultraviolet-visible spectrophotometer UV-2700 -3 The mol/L mother liquor is diluted to 1X 10 -5 mol/L was tested.
FIG. 3 shows that M1 prepared in example 1 is at 1X 10 -5 An ultraviolet visible absorption spectrum diagram, an ultraviolet visible absorption spectrum diagram and a fluorescence emission spectrum diagram in mol/L toluene. As can be seen from FIG. 3, the M1 has a main absorption peak position of 300nm and a main emission peak position of 580nm.
FIG. 4 shows that M2 prepared in example 2 is at 1X 10 -5 Ultraviolet visible absorption spectrum and fluorescence emission spectrum in mol/L toluene. As is clear from FIG. 4, the M2 has a main absorption peak position of 310nm and a main emission peak position of 474nm.
The fluorescent dyes of the present patent application have very high luminescence quantum yields of over 90% when added to a solid matrix, compared to more flexible or less coupled traditional exciplex. And has a similar ΔEST and a faster RISC rate than the conventional pi-linked TADF molecules. Therefore, the invention has good application prospect in the fields of full-color display and solid-state illumination as a luminescent material or an intelligent material.
In the application, besides M1 and M2 compounds, other multiple carbonyl arylamine pi stacked fluorescent dyes are similar to the structures of the M1 and M2 compounds, and belong to a series of organic small molecules with green to yellow emission wavelength, which are prepared by connecting a donor and an acceptor unit through rigid linking fluorene and introducing carbonyl nitrogen between the donor and a large steric hindrance group as an acceptor, and in addition, the carbonyl arylamine pi stacked fluorescent dye can inhibit non-radiative transition so as to realize high efficiency. The strong electronic coupling between the donor and acceptor units is also sufficient to allow efficient direct absorption of the CT state.
The application selects a fluorophore aromatic ring imide with wide application as a matrix, connects different stabilizing groups and groups with strong electron donating ability, replaces oxygen atoms on the aromatic ring imide with sulfur atoms, and synthesizes the carbonyl aromatic amine pi stacking fluorescent dye. The carbonyl arylamine pi stacking fluorescent dye prepared by the application is a thiocarbonyl compound, the thiocarbonyl compound has stronger spin-orbit coupling effect (SOC) than the carbonyl compound between a singlet state and a triplet state, the probability of intersystem crossing (ISC) is higher, the triplet excited state with longer service life can be generated, and the light absorption coefficient is also improved. The ultraviolet-visible light absorption of the carbonyl arylamine pi stacked fluorescent dye has a larger degree of red shift in a solvent with larger polarity such as DMF, can efficiently realize triplet-triplet annihilation up-conversion (TTA-UC) from red light to blue light, and the energy emitted by up-conversion can be transferred to a photoinitiator to initiate polymerization reaction, thus having important application value in the field of photopolymerization.
In the description of the present specification, reference to the terms "one embodiment," "some embodiments," "illustrative embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present patent application. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
While several embodiments of the present patent application have been shown and described, it will be understood by those of ordinary skill in the art that: many changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the application, the scope of which is defined by the claims and their equivalents.

Claims (10)

1. The carbonyl arylamine pi stacking fluorescent dye is characterized in that the main ring structure in the structural general formula of the carbonyl arylamine pi stacking fluorescent dye is as follows:
Wherein R represents hydrogen, methyl, phenoxathiazide, phenothiazine, 1,3,6, 8-tetramethyl-9H-carbazole, N-methyl carbazole or 5-phenyl-5, 10-dihydro-phenazine.
2. The carbonyl arylamine pi stacked fluorescent dye according to claim 1, wherein the carbonyl arylamine pi stacked fluorescent dye is selected from one of the following specific compounds:
3. the carbonyl arylamine pi stacked fluorescent dye according to claim 2, wherein the carbonyl arylamine pi stacked fluorescent dye is selected from one of the following specific compounds:
4. the method for preparing the carbonyl aromatic amine pi-stacking fluorescent dye according to claim 2, which is characterized by comprising the following steps:
s11, dissolving 2-bromo-3-methylbenzoic acid in an organic solvent, adding iodobenzene diacetic acid, iodine and palladium acetate, and reacting for 16-24 hours at 90-110 ℃ under the catalysis of palladium acetate to obtain a corresponding iodized product;
s12, dissolving the iodized product obtained in the step S11 in an organic solvent, sequentially adding inorganic alkali and methyl iodide, and obtaining a corresponding esterified product at 60-90 ℃ for 3-6 hours in a hydrolysis reaction time;
s13, dissolving the esterified product, pinacol phenylborate, tetraphenylphosphine palladium and inorganic alkali prepared in the step S12 in a solvent, and reacting for 6-8 hours at 40-60 ℃ under the action of the tetraphenylphosphine palladium to prepare a corresponding biphenyl pinacol borate product;
S14, dissolving the biphenyl boric acid pinacol ester product prepared in the step S13 in methyl sulfonic acid, and carrying out ring closure reaction for 6-10 h at the temperature of 60-90 ℃ to prepare a corresponding fluorenone derivative;
s15, reacting the corresponding fluorenone derivative prepared in the step S14 with 2-bromotriphenylamine in an inert gas atmosphere at the temperature of minus 78 ℃ for 1h through n-butyllithium reaction, and transferring to room temperature overnight; intermediate a is prepared;
s16, oxidizing 2, 5-dibromo-m-xylene and potassium permanganate to obtain 2, 5-dibromo-isophthalic acid;
s17, carrying out acylation reaction on the 2, 5-dibromoisophthalic acid prepared in the S16, oxalyl chloride and methanol to generate 2, 5-dibromoisophthalic acid dimethyl ester;
s18, reacting dimethyl 2, 5-dibromoisophthalate with di-tert-butylaniline under the action of copper catalyst by using o-dichlorobenzene as a solvent to obtain dimethyl 2- (bis (4- (tert-butyl) phenyl) amino) -5-bromoisophthalic acid;
s19, reacting the dimethyl 2- (bis (4- (tert-butyl) phenyl) amino) -5-bromoisophthalic acid prepared in the S18 with ethanol serving as a solvent under the condition of an alkaline aqueous solution to generate 2- (bis (4- (tert-butyl) phenyl) amino) -5-bromoisophthalic acid;
s20, reacting the 2- (bis (4- (tert-butyl) phenyl) amino) -5-bromoisophthalic acid prepared in the step S19 with oxalyl chloride, and reacting in the presence of a catalyst tin tetrachloride to generate 2- (bis (4- (tert-butyl) phenyl) -bromobenzoazabicyclo hexane ring;
S21, adding the 2- (bis (4- (tert-butyl) phenyl) -bromobenzoazabicyclo hexane ring, pinacol biborate and potassium acetate prepared in the step S20 into a solvent 1, 4-dioxane in [1, 1' -bis (diphenylphosphino) ferrocene ] palladium dichloride, and reacting for 20-24 hours at 90-110 ℃ under the action of inert gas to prepare a 2- (bis (4- (tert-butyl) phenyl) -bromobenzoazabicyclo hexane cycloborate pinacol ester product;
s22, adding the intermediate a, the tetraphenylphosphine palladium and the potassium carbonate prepared in the step S15 into a solvent in the 2- (bis (4- (tert-butyl) phenyl) -bromobenzoazabicyclo-hexane cyclic-boric acid pinacolate product prepared in the step S21, and reacting for 20-24 hours at 90-120 ℃ under the action of inert gas to prepare a target product M1:
5. the method for preparing a carbonyl aromatic amine pi stacked fluorescent dye according to claim 4, wherein the molar ratio of 2-bromo-3-methylbenzoic acid, iodobenzene diacetic acid, iodine and palladium acetate in the step S11 is 1: (1-1.2): (1-1.2): (0.04 to 0.06), and/or;
in the step S12, the molar ratio of the iodinated product, the inorganic base, and the methyl iodide is: 1 (1.5-2.5), 1.5-2, and/or;
in the step S13, the mole ratio of the esterification product, the pinacol phenylborate, the tetraphenylphosphine palladium and the inorganic base is 1: (0.9-1.1): (0.04-0.06): (1.5-2.5), and/or;
The molar ratio of the intermediate a, 2-bromotriphenylamine to n-butyllithium in the step S15 is as follows: 1:1.2:1.32 And/or;
in the step S20, the molar ratio of the 2- (bis (4- (tert-butyl) phenyl) -bromobenzoazabicyclo hexane, pinacol biborate, potassium acetate and [1, 1' -bis (diphenylphosphino) ferrocene ] palladium dichloride is 1 (1-1.2): 2.5-3.5): 0.04-0.06.
6. The method for preparing the carbonyl aromatic amine pi-stacking fluorescent dye according to claim 2, which is characterized by comprising the following steps:
s11, dissolving 2-bromo-3-methylbenzoic acid in an organic solvent, adding iodobenzene diacetic acid, iodine and palladium acetate, and reacting for 16-24 hours at 90-110 ℃ under the catalysis of palladium acetate to obtain a corresponding iodized product;
s12, dissolving the iodized product obtained in the step S11 in an organic solvent, sequentially adding inorganic alkali and methyl iodide, and obtaining a corresponding esterified product at 60-90 ℃ for 3-6 hours in a hydrolysis reaction time;
s13, dissolving the esterified product, pinacol phenylborate, tetraphenylphosphine palladium and inorganic alkali prepared in the step S12 in a solvent, and reacting for 6-8 hours at 40-60 ℃ under the action of the tetraphenylphosphine palladium to prepare a corresponding biphenyl pinacol borate product;
S14, dissolving the biphenyl boric acid pinacol ester product prepared in the step S13 in methyl sulfonic acid, and carrying out ring closure reaction for 6-10 h at the temperature of 60-90 ℃ to prepare a corresponding fluorenone derivative;
s16, oxidizing 2, 5-dibromo-m-xylene and potassium permanganate to obtain 2, 5-dibromo-isophthalic acid;
s17, carrying out acylation reaction on the 2, 5-dibromoisophthalic acid prepared in the S16, oxalyl chloride and methanol to generate 2, 5-dibromoisophthalic acid dimethyl ester;
s18, reacting dimethyl 2, 5-dibromoisophthalate with di-tert-butylaniline under the action of copper catalyst by using o-dichlorobenzene as a solvent to obtain dimethyl 2- (bis (4- (tert-butyl) phenyl) amino) -5-bromoisophthalic acid;
s19, reacting the dimethyl 2- (bis (4- (tert-butyl) phenyl) amino) -5-bromoisophthalic acid prepared in the S18 with ethanol serving as a solvent under the condition of an alkaline aqueous solution to generate 2- (bis (4- (tert-butyl) phenyl) amino) -5-bromoisophthalic acid;
s20, reacting the 2- (bis (4- (tert-butyl) phenyl) amino) -5-bromoisophthalic acid prepared in the step S19 with oxalyl chloride, and reacting in the presence of a catalyst tin tetrachloride to generate 2- (bis (4- (tert-butyl) phenyl) -bromobenzoazabicyclo hexane ring;
s21, adding the 2- (bis (4- (tert-butyl) phenyl) -bromobenzoazabicyclo hexane ring, pinacol biborate and potassium acetate prepared in the step S20 into a solvent 1, 4-dioxane in [1, 1' -bis (diphenylphosphino) ferrocene ] palladium dichloride, and reacting for 20-24 hours at 90-110 ℃ under the action of inert gas to prepare a 2- (bis (4- (tert-butyl) phenyl) -bromobenzoazabicyclo hexane cycloborate pinacol ester product;
S23, reacting the corresponding fluorenone derivative prepared in the step S14 with N- (2-bromophenyl) carbazole in an inert gas atmosphere at the temperature of minus 78 ℃ for 1h through N-butyllithium reaction, and transferring to room temperature overnight; intermediate b is prepared;
s24, adding the intermediate b, the tetraphenylphosphine palladium and the potassium carbonate prepared in the step S23 into a solvent in the 2- (bis (4- (tert-butyl) phenyl) -bromobenzoazabicyclo-hexane cyclic-boric acid pinacolate product prepared in the step S21, and reacting for 20-24 hours at 90-120 ℃ under the action of inert gas to prepare a target product M2:
7. the method for preparing a carbonyl aromatic amine pi-stacking fluorescent dye according to claim 6, wherein in the step 30, the molar ratio of 2- (bis (4- (tert-butyl) phenyl) -bromobenzoazabicyclo hexane ring, pinacol biborate, potassium acetate and [1, 1' -bis (diphenylphosphino) ferrocene ] palladium dichloride is 1 (1-1.2): (2.5-3.5): (0.04-0.06).
8. The method for preparing a carbonyl aromatic amine pi stacked fluorescent dye according to claim 6, wherein in the step S31, a molar ratio of the intermediate b, N- (2-bromophenyl) carbazole to N-butyllithium is: 1:1.2:1.32.
9. the method for preparing the carbonyl-arylamine pi-stacking fluorescent dye according to claim 4 or 6, wherein the method comprises the following steps: in the step S11, the organic solvent is one of toluene, dimethyl sulfoxide, N-dimethylformamide, and/or; in the step S12, the organic solvent is acetone.
10. The method for preparing the carbonyl-arylamine pi-stacking fluorescent dye according to claim 4 or 6, wherein the method comprises the following steps: the inorganic base in the steps S12 and S13 is potassium carbonate and/or; the solvent in the step S13 is a mixture of any one of toluene, tetrahydrofuran and N, N-dimethylformamide and water.
CN202310809764.4A 2023-07-03 2023-07-03 Carbonyl arylamine pi stacking fluorescent dye and preparation method thereof Pending CN117003753A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310809764.4A CN117003753A (en) 2023-07-03 2023-07-03 Carbonyl arylamine pi stacking fluorescent dye and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310809764.4A CN117003753A (en) 2023-07-03 2023-07-03 Carbonyl arylamine pi stacking fluorescent dye and preparation method thereof

Publications (1)

Publication Number Publication Date
CN117003753A true CN117003753A (en) 2023-11-07

Family

ID=88564574

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310809764.4A Pending CN117003753A (en) 2023-07-03 2023-07-03 Carbonyl arylamine pi stacking fluorescent dye and preparation method thereof

Country Status (1)

Country Link
CN (1) CN117003753A (en)

Similar Documents

Publication Publication Date Title
TWI640513B (en) Phenanthroimidazole compound and organic light emitting diode including the same
CN102229623B (en) Spirofluorene xanthene phosphine oxide electro-phosphorescent main materials and synthesis and application methods thereof
CN109928936B (en) Organic electroluminescent compounds and use thereof
CN112625042B (en) Organic electroluminescent material and application thereof
CN114853769B (en) Carbazole derivative, organic electroluminescent element, display device and lighting device
CN114105955A (en) Fluorospirotriphenylamine derivative compound and preparation method and application thereof
CN109575046A (en) A kind of four aryl of dithienothiophene replace and double luxuriant and rich with fragrance condensed compounds and preparation
CN110183302B (en) Condensed terphenyl compound and preparation method and application thereof
CN114891000B (en) Indole derivative, organic electroluminescent element, display device and lighting device
CN114805381B (en) Organic material containing heterocyclic structure and application thereof
CN117003753A (en) Carbonyl arylamine pi stacking fluorescent dye and preparation method thereof
CN111423450B (en) Compound, display panel and display device
CN112961175B (en) Polycyclic aromatic organic compound, synthesis process thereof, light-emitting material and organic electroluminescent device
CN111362953A (en) Compound taking ethylenic bond-containing seven-membered ring structure as core and application thereof
CN114573593B (en) Dicarbazole compound, intermediate, organic electroluminescent device and display device
CN115010710B (en) Quinazoline derivative, organic electroluminescent element, display device and lighting device
CN115925661B (en) Light-emitting auxiliary material, preparation method and application thereof in organic electroluminescent device
CN114315695B (en) Thermal activity delayed fluorescence molecular material based on indole condensed ring unit and application thereof
CN110790795B (en) Organic phosphorus luminescent material, preparation method and application thereof
CN110467545B (en) Anthracene derivative and preparation method and application thereof
CN112062765B (en) Organic photoelectric luminescent compound and preparation method thereof
CN114716376A (en) Derivative compound based on sulfone electron acceptor and preparation method and application thereof
CN116987119A (en) Phosphine oxide boron nitrogen compound, and preparation method and application thereof
CN116082236A (en) TADF luminescent material suitable for full solution process treatment technology and preparation method thereof
CN116987120A (en) Phosphine-containing multi-resonance aryl boron compound and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination