A carbonyl ring-closed arylamine fluorescent compound with narrow spectrum band emission and a preparation method and application thereof

Abstract

The patent application discloses a narrow-band emission carbonyl closed-loop arylamine fluorescent compound and a preparation method and application thereof. The multiple resonance compound in the patent application utilizes a carbonyl nitrogen ring resonance ring as a bridge, introduces two opposite-acting groups of electron-donating and electron-withdrawing groups on the benzene ring at the para position of the carbonyl nitrogen resonance ring by means of the resonance structure of the carbonyl nitrogen ring on the ring, and it is found that the synthesized compound still maintains the research and further improves the device performance, and at the same time, a narrow light spectrum with very narrow half peak width and high color purity of sky blue emission can be generated. Therefore, the arylamine carbonyl nitrogen ring resonance derivative has remarkable economic value in the application aspects of light-emitting devices, light-emitting materials, display materials, intelligent materials, energy materials and the like.

Description

Technical Field

[0001] This patent application relates to the field of organic light-emitting materials technology, and more specifically, to a narrow-band emission carbonyl-closed-ring aromatic amine fluorescent compound, its preparation method, and its application. Background Technology

[0002] Organic light-emitting diodes (OLEDs) have enormous application potential in full-color displays, smartphones, flat-screen TVs, flexible light-emitting devices, and solid-state light-emitting devices due to their advantages such as light weight, flexibility, wide operating temperature range, high brightness and contrast, wide viewing angle, and short response time. Among these, OLED devices are of decisive significance for display technologies such as full-color displays, solid-state light-emitting devices, and high-resolution displays.

[0003] To date, numerous materials based on small-molecule organic electroluminescent devices have been reported. Traditional donor-π-acceptor molecular structures can form distorted conformations upon excitation, leading to efficient charge transfer and donor-acceptor separation, thereby achieving a smaller ΔE. ST .

[0004] However, these traditional molecules suffer from significant structural sluggishness, leading to drawbacks such as broadened emission half-width, insufficient color purity, and low quantum yield. Commercial organic light-emitting diode (OLED) technology demands high device efficiency, excellent color purity, high resolution display, and long device lifetime. Therefore, discovering and fabricating a small-molecule organic electroluminescent device material with high color purity and narrow half-width is a technical problem that needs to be solved by those skilled in the art.

[0005] Patent application content

[0006] To overcome one of the problems existing in the prior art, the primary objective of this patent application is to provide a narrow-band emission carbonyl-closed-ring aromatic amine fluorescent compound. This narrow-band emission carbonyl-closed-ring aromatic amine fluorescent compound possesses high color purity and narrow half-maximum width, and exhibits space charge transfer characteristics, effectively promoting multi-channel charge transfer, thereby achieving the advantage of high quantum yield.

[0007] Another objective of this patent application is to provide a method for preparing the above-mentioned carbonyl-closed-ring aromatic amine fluorescent compounds based on narrow-band emission.

[0008] Another objective of this patent application is to provide the application of the aforementioned narrow-band emission carbonyl closed-ring aromatic amine fluorescent compounds in the preparation of luminescent materials, organic electroluminescent devices, full-color displays, and lighting.

[0009] The above-mentioned objective of this patent application is achieved through the following technical solution:

[0010] A narrow-band emission carbonyl-closed-ring aromatic amine fluorescent compound, simultaneously incorporating both a donor and an acceptor, has the following molecular structure:

[0011]

[0012] In the formula, R1 and R2 can be the same or different, and R1 and R2 are selected from one of the following structural formulas a to f.

[0013]

[0014] D is selected from one of the following structural formulas 1 to 20:

[0015]

[0016]

[0017] This patent application also provides a method for preparing the above-mentioned narrow-band emission carbonyl-closed-ring aromatic amine fluorescent compound, comprising the following steps:

[0018] S11. 2-Bromo-3-fluorobenzonitrile is reacted with carbazole under alkaline conditions to produce 4-bromo-3-(9H-carbazole-9-yl)benzylnitrile;

[0019] S12. 2-Bromo-3-fluorobenzonitrile is reacted with 3,6-di-tert-butylcarbazole under alkaline conditions to generate 4-bromo-3-(3,6-di-tert-butyl-9H-carbazole-9-yl)benzylnitrile;

[0020] S13. 4-Bromo-2-fluorobenzonitrile is reacted with carbazole under alkaline conditions to produce 4-bromo-2-(9H-carbazole-9-yl)benzylnitrile;

[0021] S20. 2-Bromophthalic acid is prepared by oxidation reaction of 2,6-xylenebromobenzene and potassium permanganate;

[0022] S21. The 2-bromoisophthalic acid obtained in S20 is reacted with thionyl chloride and methanol to produce dimethyl 2-bromoisophthalate.

[0023] S22. The 2-bromoisophthalate dimethyl ester obtained in S21 is reacted with di-tert-butylaniline under the action of a catalyst and with o-dichlorobenzene as a solvent to obtain 2-(bis(4-(tert-butyl)phenyl)amino)isophthalate dimethyl ester;

[0024] S23. The 2-(bis(4-(tert-butyl)phenyl)amino)isophthalate dimethyl ester obtained in S22 is reacted with ethanol as solvent under alkaline aqueous solution conditions to generate 2-(bis(4-(tert-butyl)phenyl)amino)isophthalic acid;

[0025] S24. The 2-(bis(4-(tert-butyl)phenyl)amino)isophthalic acid obtained in S23 is reacted with oxalyl chloride in the presence of tin tetrachloride catalyst to produce 3,11-di-tert-butylquinoline[3,2,1-de]acridin-5,9-dione.

[0026] S25. The 3,11-di-tert-butylquinoline[3,2,1-de]acrid-5,9-dione obtained in step S24 is reacted with N-bromosuccinimide to generate the product 2-(bis(4-(tert-butyl)phenyl)-bromophenylazine-biscyclohexane ring;

[0027] S26. The 2-(bis(4-(tert-butyl)phenyl)-bromophenylazine-biscyclohexane ring) obtained in step S25 is reacted with bis(pinacolyl)diboron under palladium catalyst to generate 3,11-ditert-butyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)quinolino[3,2,1-de]acridin-5,9-dione;

[0028] S27. The 3,11-di-tert-butyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaboran-2-yl)quinolino[3,2,1-de]acridin-5,9-dione obtained in S26 is reacted with the 4-bromo-3-(9H-carbazol-9-yl)benzylnitrile obtained in S11 to obtain the target product 3-(9H-carbazol-9-yl)-4-(3,11-di-tert-butyl-5,9-dioxo-5,9-dihydroquinolino[3,2,1-de]acridin-7-yl)benzylnitrile, the structure of which is shown below:

[0029]

[0030] S28. The 3,11-di-tert-butyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaboran-2-yl)quinolino[3,2,1-de]acridin-5,9-dione obtained in S26 is reacted with the 4-bromo-3-(3,6-di-tert-butyl-9H-carbazole-9-yl)benzylnitrile obtained in S12 to obtain the target product 4-(3,11-di-tert-butyl-5,9-dioxo-5,9-dihydroquinolino[3,2,1-de]acridin-7-yl)-3-(3,6-di-tert-butyl-9H-carbazole-9-yl)benzylnitrile, the structural formula of which is shown below:

[0031]

[0032] S29. The 3,11-di-tert-butyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)quinolino[3,2,1-de]acridin-5,9-dione obtained in step S26 is reacted with the 4-bromo-2-(9H-carbazole-9-yl)benzylnitrile obtained in S13 under the action of the catalyst tetra-triphenylphosphine palladium to obtain the target product 2-(9H-carbazole-9-yl)-4-(3,11-di-tert-butyl-5,9-dioxo-5,9-dihydroquinolino[3,2,1-de]acridin-7-yl)benzylnitrile, the structural formula of which is shown below:

[0033]

[0034] Compared with the prior art, the beneficial effects of this patent application are:

[0035] The narrow-band emission carbonyl-closed cyclic aromatic amine fluorescent compound in this patent application introduces both a donor and an acceptor. Utilizing the carbonyl nitrogen ring resonance ring as a bridge, it achieves multiple short-range charge transfer resonance effects based on the electron-withdrawing effect of the carbonyl nitrogen ring on the acceptor nucleus and the electron-donating effect of the nitrogen atom. The donor (e.g., carbazole, tert-butylcarbazole, (R or S)1,1'-bi-2-naphthol p-cyanophenyl, etc.) provides electron-donating power, while the acceptor (cyano, triazine, diazine, etc.) provides electron-withdrawing power. Simultaneously, the highly distorted spatial structure generated by the donor and the MR carbonyl nitrogen acceptor nucleus promotes charge transfer, suppresses nonradiative transitions, and improves quantum yield, resulting in a narrow spectrum with a very narrow half-width and high color purity fluorescence emission.

[0036] Meanwhile, the narrow-band emission carbonyl-closed-ring aromatic amine fluorescent compound in this patent application exhibits ultra-high efficiency green light emission in organic solvents. This narrow-band emission carbonyl-closed-ring aromatic amine fluorescent compound relies on the carbonyl nitrogen ring as its resonance structure, which can efficiently enhance π-electron delocalization, resulting in a more balanced carrier injection and transport, thus improving device performance. Therefore, it has significant economic value in applications such as light-emitting devices, light-emitting materials, display materials, and smart materials. Attached Figure Description

[0037] Figure 1 The CNO-RTP-o-Br-Cz obtained in step S27 1 HMNR diagram.

[0038] Figure 2 The CNO-RTP-o-Br-2tBuCz obtained in step S28 1 HMNR diagram.

[0039] Figure 3 The CNO-RTP-o-CN-Br obtained in step S29 1 HMNR diagram.

[0040] Figure 4 The mass spectrum of CNO-RTP-o-Br-Cz obtained in step S27 is shown.

[0041] Figure 5 The mass spectrum of CNO-RTP-o-Br-2tBuCz obtained in step S28 is shown.

[0042] Figure 6 The mass spectrum of CNO-RTP-o-CN-Cz obtained in step S29 is shown.

[0043] Figure 7 The UV-Vis absorption spectra of compounds CNO-RTP-o-Br-Cz, CNO-RTP-o-Br-2tBuCz, and CNO-RTP-o-CN-Br in toluene solution are shown.

[0044] Figure 8 The fluorescence emission spectra of compounds CNO-RTP-o-Br-Cz, CNO-RTP-o-Br-2tBuCz, and CNO-RTP-o-CN-Br in toluene solution are shown.

[0045] Figure 9 The diagram shows the intermolecular interactions and scatter plot of the compound CNO-RTP-o-Br-Cz.

[0046] Figure 10 The diagram shows the intermolecular interactions and scatter plot of the compound CNO-RTP-o-Br-2tBuCz. Detailed Implementation

[0047] The embodiments of this patent application will be described in detail below with reference to examples. However, those skilled in the art will understand that the following examples are for illustrative purposes only and should not be construed as limiting the scope of this patent application. Where specific conditions are not specified in the examples, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products.

[0048] It should be noted that:

[0049] Unless otherwise specified, all embodiments and preferred embodiments mentioned herein can be combined to form new technical solutions.

[0050] In this patent application, unless otherwise specified, percentage (%) or parts refer to weight percentage or parts relative to the composition.

[0051] Unless otherwise specified, the components or preferred components involved in this patent application may be combined with each other to form new technical solutions.

[0052] In this patent application, unless otherwise stated, the numerical range "a~b" represents an abbreviation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "1~5" means that all real numbers between "1~5" have been listed herein, and "1~5" is simply an abbreviation of these numerical combinations.

[0053] The “scope” disclosed in this patent application may be in the form of a lower limit and an upper limit, and may be one or more lower limits and one or more upper limits, respectively.

[0054] In this patent application, unless otherwise stated, the various reactions or operation steps may be performed sequentially or in a particular order. Preferably, the reaction methods described herein are performed sequentially.

[0055] Unless otherwise stated, the technical and scientific terms used herein have the same meanings as those familiar to a person skilled in the art. Furthermore, any methods or materials similar to or equivalent to those described herein may also be used in this patent application.

[0056] This patent application provides a narrow-band emission carbonyl-closed-ring aromatic amine fluorescent compound that simultaneously incorporates a donor and an acceptor. The narrow-band emission carbonyl-closed-ring aromatic amine fluorescent compound has the following molecular structure: In the formula, R1 and R2 can be the same or different, and R1 and R2 are selected from one of the following structural formulas a to f.

[0057] D is selected from one of the following structural formulas 1 to 20:

[0058]

[0059]

[0060] Specifically, the narrow-band emission carbonyl-closed ring aromatic amine fluorescent compound of this patent application has one of the following molecular structures:

[0061]

[0062]

[0063]

[0064] Specifically, the narrow-band emission carbonyl-closed ring aromatic amine fluorescent compound of this patent application has one of the following molecular structures:

[0065]

[0066] The narrow-band emission carbonyl-closed aromatic amine fluorescent compound in this patent application introduces both a donor and an acceptor. Utilizing the carbonyl nitrogen ring resonance ring as a bridge, it achieves multiple short-range charge transfer resonance effects based on the electron-withdrawing effect of the carbonyl nitrogen ring in the acceptor nucleus and the electron-donating effect of the nitrogen atom. The donor (e.g., carbazole, tert-butylcarbazole, (R or S)1,1'-bi-2-naphthol p-cyanophenyl, etc.) provides electron-donating power, while the acceptor (cyano, triazine, diazine, etc.) provides electron-withdrawing power. Simultaneously, the highly distorted spatial structure generated by the donor and the MR carbonyl nitrogen acceptor nucleus promotes charge transfer, suppresses nonradiative transitions, and increases reverse intersystem crossing (RISC), further enhancing quantum yield. This results in a narrow spectrum with a very narrow half-width and high color purity fluorescence emission.

[0067] Meanwhile, the narrow-band emission carbonyl-closed-ring aromatic amine fluorescent compound in this patent application exhibits ultra-high efficiency green light emission in organic solvents. This narrow-band emission carbonyl-closed-ring aromatic amine fluorescent compound relies on the carbonyl nitrogen ring as its resonance structure, which can efficiently enhance π-electron delocalization, resulting in a more balanced carrier injection and transport, thus improving device performance. Therefore, it has significant economic value in applications such as light-emitting devices, light-emitting materials, display materials, and smart materials.

[0068] This patent application also provides a method for preparing the above-mentioned narrow-band emission carbonyl-closed-ring aromatic amine fluorescent compounds. The method includes the following steps:

[0069] S11. 2-Bromo-3-fluorobenzonitrile is reacted with carbazole under alkaline conditions to produce 4-bromo-3-(9H-carbazole-9-yl)benzylnitrile;

[0070] S12. 2-Bromo-3-fluorobenzonitrile is reacted with 3,6-di-tert-butylcarbazole under alkaline conditions to generate 4-bromo-3-(3,6-di-tert-butyl-9H-carbazole-9-yl)benzylnitrile;

[0071] S13. 4-Bromo-2-fluorobenzonitrile is reacted with carbazole under alkaline conditions to produce 4-bromo-2-(9H-carbazole-9-yl)benzylnitrile;

[0072] S20. 2-Bromophthalic acid is prepared by oxidation reaction of 2,6-xylenebromobenzene and potassium permanganate;

[0073] S21. The 2-bromoisophthalic acid obtained in S20 is reacted with thionyl chloride and methanol to produce dimethyl 2-bromoisophthalate.

[0074] S22. The 2-bromoisophthalate dimethyl ester obtained in S21 is reacted with di-tert-butylaniline under the action of a catalyst and with o-dichlorobenzene as a solvent to obtain 2-(bis(4-(tert-butyl)phenyl)amino)isophthalate dimethyl ester;

[0075] S23. The 2-(bis(4-(tert-butyl)phenyl)amino)isophthalate dimethyl ester obtained in S22 is reacted with ethanol as solvent under alkaline aqueous solution conditions to generate 2-(bis(4-(tert-butyl)phenyl)amino)isophthalic acid;

[0076] S24. The 2-(bis(4-(tert-butyl)phenyl)amino)isophthalic acid obtained in S23 is reacted with oxalyl chloride in the presence of tin tetrachloride catalyst to produce 3,11-di-tert-butylquinoline[3,2,1-de]acridin-5,9-dione.

[0077] S25. The 3,11-di-tert-butylquinoline[3,2,1-de]acrid-5,9-dione obtained in step S24 is reacted with N-bromosuccinimide to generate the product 2-(bis(4-(tert-butyl)phenyl)-bromophenylazine-biscyclohexane ring;

[0078] S26. The 2-(bis(4-(tert-butyl)phenyl)-bromophenylazine-biscyclohexane ring) obtained in step S25 is reacted with bis(pinacolyl)diboron under palladium catalyst to generate 3,11-ditert-butyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)quinolino[3,2,1-de]acridin-5,9-dione;

[0079] S27. The 3,11-di-tert-butyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaboran-2-yl)quinolino[3,2,1-de]acridin-5,9-dione obtained in S26 is reacted with the 4-bromo-3-(9H-carbazol-9-yl)benzylnitrile obtained in S11 to obtain the target product 3-(9H-carbazol-9-yl)-4-(3,11-di-tert-butyl-5,9-dioxo-5,9-dihydroquinolino[3,2,1-de]acridin-7-yl)benzylnitrile, the structure of which is shown below:

[0080]

[0081] S28. The 3,11-di-tert-butyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaboran-2-yl)quinolino[3,2,1-de]acridin-5,9-dione obtained in S26 is reacted with the 4-bromo-3-(3,6-di-tert-butyl-9H-carbazole-9-yl)benzylnitrile obtained in S12 to obtain the target product 4-(3,11-di-tert-butyl-5,9-dioxo-5,9-dihydroquinolino[3,2,1-de]acridin-7-yl)-3-(3,6-di-tert-butyl-9H-carbazole-9-yl)benzylnitrile, the structural formula of which is shown below:

[0082]

[0083] S29. The 3,11-di-tert-butyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)quinolino[3,2,1-de]acridin-5,9-dione obtained in step S26 is reacted with the 4-bromo-2-(9H-carbazole-9-yl)benzylnitrile obtained in S13 under the action of the catalyst tetra-triphenylphosphine palladium to obtain the target product 2-(9H-carbazole-9-yl)-4-(3,11-di-tert-butyl-5,9-dioxo-5,9-dihydroquinolino[3,2,1-de]acridin-7-yl)benzylnitrile, the structural formula of which is shown below:

[0084]

[0085] In the method for preparing narrow-band emission carbonyl-closed cyclic aromatic amine fluorescent compounds in this patent application, in steps S27, S28, and S29, the molar ratio of 3,11-di-tert-butyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)quinolino[3,2,1-de]acridin-5,9-dione to 4-bromo-3-(9H-carbazole-9-yl)benzylnitrile generated in step S11, or 4-bromo-3-(3,6-di-tert-butyl-9H-carbazole-9-yl)benzylnitrile generated in step S12, or 4-bromo-2-(9H-carbazole-9-yl)benzylnitrile generated in step S13, to tetraphenylphosphine palladium is (1–1.5):(1–2):(0.01–0.20), the reaction temperature is 65–100 °C, and the reaction time is 10–18 hours.

[0086] This patent application also provides the application of the above-mentioned carbonyl-based closed-ring aromatic amine fluorescent compounds in the preparation of luminescent materials, organic electroluminescent devices, full-color displays, and lighting.

[0087] In some preferred embodiments of this patent application, the molar ratio of potassium permanganate and 2,6-dimethylbromobenzene in step S20 is (1-2):(1-8); the reaction temperature is 70-95°C, and the reaction time is 10-20 hours.

[0088] In a more preferred embodiment of this patent application, step S20 specifically involves the following steps:

[0089] Preparation of 2-bromoisophthalic acid (compound 1)

[0090] 3.66 g (20 mmol) of 2,6-xylenebromobenzene and 11.06 g (60 mmol) of potassium permanganate were added sequentially to a 100 mL two-necked round-bottom flask. Then, 30 mL of tert-butanol, 20 mL of deionized water, and a 1 mol / L NaOH solution were added. The mixture was stirred at 75 °C for 10 h. The mixture was filtered, eluted with deionized water, acidified, filtered again, and the filter cake was dried to obtain 3.92 g of a white solid (70% yield).

[0091] The chemical reaction equation is as follows:

[0092]

[0093] In some preferred embodiments of this patent application, the molar ratio of 2-bromoisophthalic acid, thionyl chloride and methanol in step S21 is (1-2):(3-10):(30-60).

[0094] More preferably, the ratio of 2-bromoisophthalic acid, oxaloyl chloride and methanol in step S21 is 1:3:6.

[0095] In some preferred embodiments of this patent application, the solvent used in step S21 is dichloromethane.

[0096] In some preferred embodiments of this patent application, the reaction temperature in step S21 is 10–40°C and the reaction time is 2–8 hours; more preferably, the reaction temperature in step S21 is 25°C and the reaction time is 3 hours.

[0097] In some preferred embodiments of this patent application, the post-processing in step S21 involves concentration and separation. After the reaction is complete, the organic phase is concentrated under reduced pressure to obtain the crude product 2-bromoisophthalic acid.

[0098] In a more preferred embodiment of this patent application, step S21 specifically involves the following steps:

[0099] Preparation of dimethyl 2-bromoisophthalate (compound 2):

[0100] Compound 1 (1.2 g, 4.5 mmol) and dichloromethane (45 mL) were added to a 100 mL two-necked flask. Oxaloyl chloride (3.8 g, 30 mmol) and DMF (0.5 g, 6.8 mmol) were added dropwise at low temperature. The mixture was stirred at 30 °C for 2 hours and concentrated under reduced pressure to give 1.3 g of yellowish-white solid (yield 82%).

[0101] The reaction equation is as follows:

[0102]

[0103] In some preferred embodiments of this patent application, the molar ratio of dimethyl 2-bromoisophthalate, di-tert-butylaniline, and potassium carbonate in step S22 is (1-2):(1.5-4):(2-8); more preferably, the molar ratio of dimethyl 2-bromoisophthalate, di-tert-butylaniline, and potassium carbonate is 1:1.8:3.

[0104] In some preferred embodiments of this patent application, the reaction solvent in step S22 is o-dichlorobenzene.

[0105] In some preferred embodiments of this patent application, the reaction in step S22 is carried out under reflux under the protection of an inert gas. The inert gas in step S22 is nitrogen, argon, or helium. More preferably, the inert gas in step S3 is argon.

[0106] In some preferred embodiments of this patent application, the reaction temperature in step S22 is 120–200°C, and the reaction time is 12–50 hours. More preferably, the reaction temperature in step S22 is 130°C, and the reaction time is 28 hours.

[0107] In some preferred embodiments of this patent application, the reaction in step S22 uses a metal as a catalyst, more preferably copper.

[0108] In some preferred embodiments of this patent application, the treatment in step S22 is filtration, drying, concentration, and separation. After the reaction is complete, the reaction solution is filtered, and after filtration, it is concentrated under reduced pressure to obtain a crude product; finally, 2-(bis(4-(tert-butyl)phenyl)amino)isophthalate is separated by silica gel column chromatography using petroleum ether and dichloromethane as eluents.

[0109] In a more preferred embodiment of this patent application, the specific steps of step S22 are as follows:

[0110] Preparation of dimethyl 2-(bis(4-(tert-butyl)phenyl)amino)isophthalate (compound 3):

[0111] Dimethyl 2-bromoisophthalate (2.71 g, 10 mmol), di-tert-butylaniline (5.06 g, 18 mmol), copper powder (0.10 g, 1.5 mmol), and cuprous iodide (0.15 g, 0.79 mmol) were sequentially added to a 150 mL two-necked flask. The flask was evacuated under vacuum and purged three times with dry argon. Then, o-dichlorobenzene (36 mL) was added. The mixture was stirred at 120 °C for 30 hours, cooled, filtered, and the filtrate was distilled under reduced pressure to obtain a yellow solid. Using silica gel powder as the stationary phase and petroleum ether / ethyl acetate as the eluent, 2.10 g of the yellow solid was obtained by column chromatography (yield 45%).

[0112] The reaction equation is as follows:

[0113]

[0114] In some preferred embodiments of this patent application, the molar ratio of 2-(bis(4-(tert-butyl)phenyl)amino)isophthalate to ethanol in step S23 is (1-1.5):(3-8); more preferably, the molar ratio of 2-(bis(4-(tert-butyl)phenyl)amino)isophthalate to ethanol in step S23 is 1:3. In some preferred embodiments of this patent application, the reaction temperature in step S23 is 65-90°C, and the reaction time is 5-10 hours.

[0115] In some preferred embodiments of this patent application, the reaction solvent in step S23 is water.

[0116] In some preferred embodiments of this patent application, the catalyst used in step S23 is a strong base, specifically sodium hydroxide or potassium hydroxide.

[0117] In some preferred embodiments of this patent application, the reaction conditions in step S23 are heating under reflux in the presence of an inert gas.

[0118] In some preferred embodiments of this patent application, the inert gas in step S23 is nitrogen, argon, or helium. In some more preferred embodiments of this patent application, the inert gas in step S23 is argon.

[0119] In some preferred embodiments of this patent application, the process described in step S23 is cooling, concentration, acidification, filtration, and drying. The reacted solution is cooled to room temperature and then concentrated under reduced pressure; it is then dissolved in water, acidified, filtered, and the remaining solid is dried in a vacuum drying oven to obtain 2-(bis(4-(tert-butyl)phenyl)amino)-5-bromoisophthalic acid.

[0120] In a more preferred embodiment of this patent application, step S23 involves the following steps:

[0121] Preparation of 2-(bis(4-(tert-butyl)phenyl)amino)-5-bromoisophthalic acid (compound 4):

[0122] Dimethyl 2-(bis(4-(tert-butyl)phenyl)amino)-5-bromoisophthalate (3.30 g, 7 mmol), sodium hydroxide (1.2 g, 30 mmol), deionized water (30 ml), and ethanol (30 ml) were sequentially added to a 150 ml two-necked flask. The flask was evacuated under vacuum and purged three times with dry argon. The mixture was stirred at 80 °C for 18 hours, cooled, acidified, filtered, and dried under vacuum to obtain a yellow solid. 2.98 g of the yellow solid was obtained (yield 70%).

[0123] The reaction equation is as follows:

[0124]

[0125] In some preferred embodiments of this patent application, the molar ratio of 2-(bis(4-(tert-butyl)phenyl)amino)isophthalic acid, oxaloyl chloride, and tin tetrachloride in step S24 is (1–1.5):(3–8):(0.3–0.6). In some more preferred embodiments of this patent application, the molar ratio of 2-(bis(4-(tert-butyl)phenyl)amino)isophthalic acid, oxaloyl chloride, and tin tetrachloride in step S24 is 1:3:0.4.

[0126] In some preferred embodiments of this patent application, the solvent used in step S24 is dichloromethane.

[0127] In some preferred embodiments of this patent application, the cyclization reaction in step S24 is performed under reflux with an inert gas atmosphere.

[0128] In some preferred embodiments of this patent application, the inert gas in step S24 is nitrogen, argon, or helium. In some more preferred embodiments of this patent application, the inert gas in step S24 is argon. In some preferred embodiments of this patent application, the hydrolysis reaction temperature in step S24 is 25–40°C, and the reaction time is 5–10 hours. In some more preferred embodiments of this patent application, the reaction temperature is 25°C, and the reaction time is 10 hours.

[0129] In some preferred embodiments of this patent application, step S24 involves cooling, extraction, drying, concentration, and separation. After cooling the reaction solution to room temperature, the resulting mixture is extracted three times with dichloromethane, and the organic phases obtained from the three extractions are combined. Then, the mixture is dried with anhydrous sodium sulfate, and the organic phase is concentrated under reduced pressure to obtain a crude product. Finally, 3,11-di-tert-butylquinoline[3,2,1-de]acridin-5,9-dione is separated by silica gel column chromatography using dichloromethane and petroleum ether as eluents.

[0130] In a more preferred embodiment of this patent application, the specific operation steps of step S24 are as follows: Preparation of 3,11-di-tert-butylquinoline[3,2,1-de]acrid-5,9-dione (compound 5):

[0131] 2-(bis(4-(tert-butyl)phenyl)amino)-isophthalic acid (2.80 g, 6.29 mmol) and oxaloyl chloride (3.77 g, 29.8 mmol) were sequentially added to a 150 mL two-necked flask. The flask was evacuated under vacuum and purged three times with dry argon. The reaction was stirred at 25 °C for 1 h, and then tin tetrachloride (2.65 g, 10.20 mmol) was added dropwise. The reaction was carried out at 40 °C for 12 h. After the reaction was complete, the mixture was cooled and added to a 1 mol / L strong alkali solution. The mixture was extracted with dichloromethane and distilled under reduced pressure to obtain a yellow-green solid. Using silica gel powder as the stationary phase and petroleum ether / dichloromethane as the eluent, 1.45 g of a yellow-green powder was obtained by column chromatography (yield 58%).

[0132] The reaction equation is as follows:

[0133]

[0134] In some preferred embodiments of this patent application, the molar ratio of 3,11-di-tert-butylquinoline[3,2,1-de]acridin-5,9-dione to N-bromosuccinimide in step S25 is (1-2:(2-4); more preferably, the molar ratio of 3,11-di-tert-butylquinoline[3,2,1-de]acridin-5,9-dione to N-bromosuccinimide in step S25 is 1.5:2.

[0135] In some preferred embodiments of this patent application, the reaction temperature in step S25 is 60–120°C; the reaction time is 12–24 hours.

[0136] In a more preferred embodiment of this patent application, the preparation of the 2-(bis(4-(tert-butyl)phenyl)-bromophenylazine dicyclohexane ring in step S25 is as follows, and the reaction equation is:

[0137]

[0138] In some preferred embodiments of this patent application, the molar ratio of 2-(bis(4-(tert-butyl)phenyl)-bromobenzylbiscyclohexane ring, bis(pinacolyl)diboron in step S26 is (1-2):(2-6), the reaction temperature is 60-100°C, and the reaction time is 6-18 hours.

[0139] The preparation of 3,11-di-tert-butyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaboran-2-yl)quinolino[3,2,1-de]acridin-5,9-dione in step S26 is as follows:

[0140]

[0141] In some preferred embodiments of this patent application, the reaction solvent in step S27 is anhydrous toluene.

[0142] In some preferred embodiments of this patent application, the reaction in step S27 is catalyzed by a strong base; the strong base is potassium carbonate or sodium carbonate.

[0143] In some preferred embodiments of this patent application, the reaction conditions in step S27 are heating under reflux under the protection of an inert gas. In some preferred embodiments of this patent application, the inert gas in step S27 is nitrogen, argon, or helium. More preferably, the inert gas in step S27 is argon. In some preferred embodiments of this patent application, the reaction temperature is 90–100°C; the reaction time is 12–24 hours; more preferably, the reaction temperature is 95°C; and the reaction time is 12 hours.

[0144] In some preferred embodiments of this patent application, the treatment in step S27 is cooling, extraction, drying, concentration, and separation. After cooling the reaction solution to room temperature, the resulting mixture is extracted three times with dichloromethane, and the organic phases obtained from the three extractions are combined; then dried with anhydrous sodium sulfate, and the organic phase is concentrated under reduced pressure to obtain the crude product; finally, the target product 3-(9H-carbazole-9-yl)-4-(3,11-di-tert-butyl-5,9-dioxo-5,9-dihydroquinolino[3,2,1-de]acridin-7-yl)benzyl nitrile (i.e., CNO-RTP-o-Br-Cz) is separated by silica gel column chromatography using dichloromethane and petroleum ether as eluent.

[0145] In a more preferred embodiment of this patent application, the specific steps of step S27 are as follows:

[0146] Preparation of 3-(9H-carbazol-9-yl)-4-(3,11-di-tert-butyl-5,9-dioxo-5,9-dihydroquinolino[3,2,1-de]acridin-7-yl)benzyl nitrile (CNO-RTP-o-Br-Cz):

[0147] 3,11-Di-tert-butyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaboran-2-yl)quinolino[3,2,1-de]acridin-5,9-dione (1.0 g, 1.8 mmol), 4-bromo-3-(9H-carbazol-9-yl)benzyl nitrile (0.75 g, 2.2 mmol), abbreviated as o-Br-Cz, and tetraphenylphosphine palladium (0.11 g, 0.095 mmol) generated in step S11 were sequentially added to a 100 mL two-necked flask. The flask was evacuated under vacuum and purged three times with dry nitrogen. Then, 25 mL of toluene, 5 mL of anhydrous ethanol, and 5 mL of saturated K₂CO₃ solution were added. The reaction mixture was heated to reflux at 95 °C with stirring for 16 hours. Extraction was performed using water and dichloromethane. Reduced pressure distillation yielded a yellow solid. Using silica gel powder as the stationary phase and petroleum ether / ethyl acetate as the eluent, column chromatography was used to obtain 0.67 g of a pale yellow powder (68% yield).

[0148] The reaction equation is as follows:

[0149]

[0150] The NMR spectrum of compound CNO-RTP-o-Br-Cz is as follows: Figure 1 As shown. From Figure 1 It can be seen that the peak energy corresponds one-to-one with the resonance plane of the carbonyl nitrogen ring and the hydrogen atoms on the aromatic ring, and the number is reasonable. This indicates that the 3-(9H-carbazole-9-yl)-4-(3,11-di-tert-butyl-5,9-dioxo-5,9-dihydroquinolino[3,2,1-de]acridin-7-yl)benzyl nitrile compound has a simple structure and high purity.

[0151] Figure 4 The mass spectra of the molecule CNO-RTP-o-Br-Cz are shown.

[0152] In some preferred embodiments of this patent application, the molar ratio of 3,11-di-tert-butyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)quinolino[3,2,1-de]acridin-5,9-dione, o-Br-Cz, and tetratriphenylphosphine palladium in step S27 is (1-2):(2-4):(0.05-0.10); in a more preferred embodiment, the molar ratio of 3,11-di-tert-butyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)quinolino[3,2,1-de]acridin-5,9-dione, o-Br-Cz, and tetratriphenylphosphine palladium in step S27 is 1.5:2:0.07.

[0153] In some preferred embodiments of this patent application, the reaction solvent in step S27 is anhydrous toluene.

[0154] In some preferred embodiments of this patent application, the reaction in step S27 is catalyzed by a strong base; the strong base is potassium carbonate or sodium carbonate.

[0155] In some preferred embodiments of this patent application, the reaction conditions in step S27 are heating under reflux under the protection of an inert gas. In some preferred embodiments of this patent application, the inert gas in step S27 is nitrogen, argon, or helium; more preferably, the inert gas in step S27 is nitrogen. In some preferred embodiments of this patent application, the reaction temperature is 90–100°C; the reaction time is 12–24 hours; in some more preferred embodiments of this patent application, the reaction temperature is 95°C; the reaction time is 12 hours.

[0156] In some preferred embodiments of this patent application, the treatment in step S27 is cooling, extraction, drying, concentration, and separation. After cooling the reaction solution to room temperature, the resulting mixture is extracted three times with dichloromethane, and the organic phases obtained from the three extractions are combined; then dried with anhydrous sodium sulfate, and the organic phase is concentrated under reduced pressure to obtain the crude product; finally, the target product 3-(9H-carbazole-9-yl)-4-(3,11-di-tert-butyl-5,9-dioxo-5,9-dihydroquinolino[3,2,1-de]acridin-7-yl)benzyl nitrile (i.e., CNO-RTP-o-Br-Cz) is separated by silica gel column chromatography using dichloromethane and petroleum ether as eluent.

[0157] In a more preferred embodiment of this patent application, the specific steps of step S28 are as follows:

[0158] Preparation of 4-(3,11-di-tert-butyl-5,9-dioxo-5,9-dihydroquinolino[3,2,1-de]acridin-7-yl)-3-(3,6-di-tert-butyl-9H-carbazole-9-yl)benzyl nitrile (i.e., CNO-RTP-o-Br-2tBuCz)

[0159] 3,11-Di-tert-butyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaboran-2-yl)quinolino[3,2,1-de]acridin-5,9-dione (1.0 g, 1.8 mmol), o-Br-2tBuCz (0.98 g, 2.20 mmol), and tetraphenylphosphine palladium (0.11 g, 0.095 mmol) were sequentially added to a 100 mL two-necked flask. The flask was evacuated under vacuum and purged three times with dry nitrogen. Then, 25 mL of toluene, 5 mL of anhydrous ethanol, and 5 mL of saturated K₂CO₃ solution were added. The mixture was heated to reflux at 95 °C with stirring for 16 hours. Extraction was performed with water and dichloromethane. The solid was distilled under reduced pressure to obtain a yellow solid. Using silica gel as the stationary phase and petroleum ether / ethyl acetate as the eluent, 0.60 g of a pale yellow powder (50% yield) was obtained by column chromatography.

[0160] The reaction equation is as follows:

[0161]

[0162] The NMR spectrum of compound CNO-RTP-o-Br-2tBuCz is as follows: Figure 2 As shown, the peak energies correspond one-to-one with the resonance plane of the carbonyl nitrogen ring and the hydrogen atoms on the aromatic ring, and the number is reasonable. This indicates that the 4-(3,11-di-tert-butyl-5,9-dioxo-5,9-dihydroquinolino[3,2,1-de]acridin-7-yl)-3-(3,6-di-tert-butyl-9H-carbazole-9-yl)benzylnitrile compound has a simple structure and high purity. Figure 5 The mass spectra of the molecule CNO-RTP-o-Br-2tBuCz are shown.

[0163] In some preferred embodiments of this patent application, the solvent used in step S28 is anhydrous toluene.

[0164] In some preferred embodiments of this patent application, the reaction in step S28 is catalyzed by a strong base; the strong base is potassium carbonate or sodium carbonate.

[0165] In some preferred embodiments of this patent application, the reaction conditions in step S28 are heating under reflux under the protection of an inert gas; in some preferred embodiments of this patent application, the inert gas in step S28 is nitrogen, argon, or helium; in some more preferred embodiments of this patent application, the inert gas in step S28 is nitrogen. In some preferred embodiments of this patent application, the reaction temperature is 90–100°C; the reaction time is 12–24 hours; in some more preferred embodiments of this patent application, the reaction temperature is 95°C; the reaction time is 12 hours.

[0166] In some preferred embodiments of this patent application, the treatment in step S28 is cooling, extraction, drying, concentration, and separation. After cooling the reaction solution to room temperature, the resulting mixture is extracted three times with dichloromethane, and the organic phases obtained from the three extractions are combined; then dried with anhydrous sodium sulfate, and the organic phase is concentrated under reduced pressure to obtain the crude product; finally, the target product 4-(3,11-di-tert-butyl-5,9-dioxo-5,9-dihydroquinolino[3,2,1-de]acridin-7-yl)-3-(3,6-di-tert-butyl-9H-carbazole-9-yl)benzyl nitrile (i.e., CNO-RTP-o-Br-2tBuCz) is separated by silica gel column chromatography using dichloromethane and petroleum ether as eluent.

[0167] In a more preferred embodiment of this patent application, the specific steps of step S29 are as follows:

[0168] Preparation of 2-(9H-carbazol-9-yl)-4-(3,11-di-tert-butyl-5,9-dioxo-5,9-dihydroquinolino[3,2,1-de]acridin-7-yl)benzyl nitrile (CNO-RTP-o-CN-Cz)

[0169] The following ingredients, prepared in step 5 of Example 1: 3,11-di-tert-butyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)quinolino[3,2,1-de]acridin-5,9-dione (1.0 g, 1.8 mmol), -o-CN-Cz (0.75 g, 2.2 mmol), and tetraphenylphosphine palladium (0.12 g, 0.10 mmol), were sequentially added to a 100 mL two-necked flask. The flask was evacuated under vacuum and purged three times with dry nitrogen. Then, 25 mL of toluene, 5 mL of anhydrous ethanol, and 5 mL of saturated K₂CO₃ solution were added. The mixture was heated to reflux at 95 °C with stirring for 16 hours. Extraction was performed using water and dichloromethane. The solid was distilled under reduced pressure to obtain a yellow solid. Using silica gel powder as the stationary phase and petroleum ether / ethyl acetate as the eluent, 0.67 g of a pale yellow powder (46% yield) was obtained by column chromatography.

[0170] The reaction equation is as follows:

[0171]

[0172] The NMR spectrum of compound CNO-RTP-o-CN-Cz is as follows: Figure 3 As shown. From Figure 3 It can be seen that the hydrogen atoms in the compound CNO-RTP-o-CN-Cz correspond one-to-one and the number is reasonable. This indicates that the compound has a simple structure and high purity.

[0173] Figure 6 The mass spectra of the molecule CNO-RTP-o-CN-Cz are shown.

[0174] In this patent application, apart from CNO-RTP-o-Br-Cz, CNO-RTP-o-Br-2tBuCz, and CNO-RTP-o-CN-Cz, the other multiple resonance compounds are structurally similar to the aforementioned three compounds. They all belong to the carbonyl nitrogen ring main ring structure. By utilizing the carbonyl nitrogen ring (as an electron acceptor) as a bridge and leveraging the resonance structure of the carbonyl nitrogen ring, the electron-withdrawing effect of the donor (such as carbazole, tert-butylcarbazole, etc.) on it can produce narrow spectra with very narrow half-width and high color purity fluorescence emission. Therefore, the preparation and characterization methods of the other five multiple resonance compounds are similar to those of the aforementioned three compounds, and will not be described in detail here.

[0175] Meanwhile, the preparation process of the compound described in this invention is simple, convenient, and can be prepared in large-scale batches. It is also economical and practical, which is conducive to industrial production and preparation, generates certain economic value, and facilitates its application and promotion.

[0176] Characterization and performance testing

[0177] Using compounds CNO-RTP-o-Br-Cz, CNO-RTP-o-Br-2tBuCz, and CNO-RTP-o-CN-Cz prepared in steps S27, S28, and S29 respectively as test objects, the photophysical properties of compounds CNO-RTP-o-Br-Cz, CNO-RTP-o-Br-2tBuCz, and CNO-RTP-o-CN-Cz were tested. The test results are as follows: Figure 7 , Figure 8 , Figure 9 and Figure 10 As shown.

[0178] Figure 7 and Figure 8 Normalized absorption and emission spectra of molecules CNO-RTP-o-Br-Cz, CNO-RTP-o-Br-2tBuCz, and CNO-RTP-o-CN-Cz in toluene solution, measured by a Shimadzu UV-2700 UV-Vis spectrophotometer and an Edinburgh FLS980 spectrophotometer.

[0179] like Figure 7 and Figure 8 As shown, CNO-RTP-o-Br-Cz has an absorption wavelength of 457 nm and an emission wavelength of 476 nm; CNO-RTP-o-Br-2tBuCz has an absorption wavelength of 453 nm and an emission wavelength of 471 nm.

[0180] The absorption of CNO-RTP-o-CN-Br is at 460 nm, and the emission is at 477 nm.

[0181] from Figure 7 and Figure 8 In addition, we can also calculate that the emission half-widths of CNO-RTP-o-Br-Cz, CNO-RTP-o-Br-2tBuCz and CNO-RTP-o-CN-Cz are 28 nm, 30 nm and 28 nm, respectively, which are much narrower than the half-widths of traditional thermally activated delayed fluorescence (TADF) molecules, which are greater than 80 nm.

[0182] Figure 9 and Figure 10 The diagrams show the intramolecular interactions of compounds CNO-RTP-o-Br-Cz and CNO-RTP-o-Br-2tBuCz, respectively. Figure 9 and Figure 10It can be seen that there is an interaction between the donor and acceptor in the molecules of compounds CNO-RTP-o-Br-Cz and CNO-RTP-o-Br-2tBuCz, resulting in intramolecular charge transfer. This effectively suppresses triplet annihilation, improves anti-intersystem crossing, and thus achieves high quantum yield, ultimately increasing the external quantum efficiency of the molecules. Quantum yield experiments show that CNO-RTP-o-Br-Cz has a quantum yield of 92%, CNO-RTP-o-Br-2tBuCz has a quantum yield of 85%, and CNO-RTP-o-CN-Br has a quantum yield of 90%.

[0183] Therefore, whether it is CNO-RTP-o-Br-Cz, CNO-RTP-o-Br-2tBuCz, or CNO-RTP-o-CN-Cz, they can all exhibit high-purity bright green light emission, making these narrow-band emitted carbonyl closed-ring aromatic amine fluorescent compounds have significant application and economic value in luminescent materials, smart materials, display materials, and light-emitting devices.

[0184] In this patent application, besides CNO-RTP-o-Br-Cz, CNO-RTP-o-Br-2tBuCz, and CNO-RTP-o-CN-Cz, several other carbonyl-closed-ring aromatic amine fluorescent compounds with multiple narrow-band emission are structurally similar to the aforementioned three compounds. They all belong to the carbonyl nitrogen ring-based structure and utilize the carbonyl nitrogen ring resonance ring (as an electron acceptor) as a bridge. Based on the electron-withdrawing effect of the carbonyl nitrogen ring in the acceptor nucleus and the electron-donating effect of the nitrogen atom, the opposing effects of these two factors create multiple short-range charge transfer resonance effects. The donor (e.g., carbazole, tert-butyl) Carbazole, (R or S)1,1'-bi-2-naphthol, p-cyanophenyl, etc., have electron-donating effects on it, and acceptors (cyano, triazine, diazine, etc.) have electron-withdrawing effects. At the same time, the highly distorted spatial structure generated by the donor and the MR carbonyl nitrogen acceptor nucleus promotes charge transfer, inhibits nonradiative transitions, and increases reverse intersystem crossing (RISC), which is more conducive to improving quantum yield. It can produce narrow spectra with very narrow half-width and high color purity fluorescence emission. Therefore, through the same characterization and testing methods, the other 5 multiple resonance compounds can also produce narrow spectra with very narrow half-width and high color purity fluorescence emission.

[0185] Testing revealed a quantum yield of 92% for CNO-RTP-o-Br-Cz, 85% for CNO-RTP-o-Br-2tBuCz, and 90% for CNO-RTP-o-CN-Br. Literature reports a quantum yield of only 75% for QAO. The carbonyl-closed-ring aromatic amine fluorescent compounds in this patent application, after modification, exhibit significantly improved quantum yields. The reported RISC for QAO in the literature is 4.6 × 10⁻⁶. 4 S -1The quantum yields of the three molecules synthesized in this application, CNO-RTP-o-Br-Cz, CNO-RTP-o-Br-2tBuCz, and CNO-RTP-o-CN-Br, are 2.4*10⁻⁶. 5 S -1 1.2*10 5 S -1 1.6*10 5 S -1 This is an order of magnitude higher than the QAO synthesized by previous researchers, demonstrating the superiority of the molecule synthesized in this patent application.

[0186] This patent application develops a narrow-band emission carbonyl-closed-ring aromatic amine fluorescent compound, which is an organic small molecule derivative with a carbonyl nitrogen ring resonance structure. This derivative, relying on the carbonyl nitrogen ring as its resonance structure, can efficiently improve π-electron delocalization, increase fluorescence quantum yield, and produce a narrower half-width at half-maximum (WHM) emission spectrum compared to traditional electroluminescent materials, exhibiting high-purity bright green light emission in solution. Furthermore, when using this narrow-band emission carbonyl-closed-ring aromatic amine fluorescent compound in the fabrication of OLED light-emitting devices, it can achieve a more balanced carrier injection and transport, improving device performance. Therefore, this narrow-band emission carbonyl-closed-ring aromatic amine fluorescent compound has significant application and economic value in light-emitting materials, smart materials, display materials, and light-emitting devices. In particular, some compounds provide new ideas for the synthesis of photoluminescent polymer resins for engineering applications.

[0187] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "illustrative embodiment," "example," "specific example," or "some examples," etc., indicate that a specific feature, structure, material, or characteristic described in connection with an embodiment or example is included in at least one embodiment or example of this patent application. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0188] Although several embodiments of this patent application have been shown and described, those skilled in the art will understand that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of this patent application, the scope of which is defined by the claims and their equivalents.

Claims

1. A narrow-band emission carbonyl-closed ring aromatic amine fluorescent compound, simultaneously incorporating a donor and an acceptor, characterized in that, The narrow-band emitted carbonyl-closed-ring aromatic amine fluorescent compound has one of the following molecular structures: 。 2. The method for preparing the narrow-band emission carbonyl-closed-ring aromatic amine fluorescent compound according to claim 1, characterized in that, Includes the following steps: S11. 4-Bromo-3-fluorobenzonitrile is reacted with carbazole under alkaline conditions to produce 4-bromo-3-(9H-carbazole-9-yl)benzylnitrile; S12. 4-Bromo-3-fluorobenzonitrile is reacted with 3,6-di-tert-butylcarbazole under alkaline conditions to generate 4-bromo-3-(3,6-di-tert-butyl-9H-carbazole-9-yl)benzylnitrile; S13. 4-Bromo-2-fluorobenzonitrile is reacted with carbazole under alkaline conditions to produce 4-bromo-2-(9H-carbazole-9-yl)benzylnitrile; S20. 2-Bromophthalic acid is prepared by oxidation reaction of 2,6-dimethylbromobenzene and potassium permanganate; S21. The 2-bromoisophthalic acid obtained in S20 is reacted with thionyl chloride and methanol to produce dimethyl 2-bromoisophthalate; S22. The 2-bromoisophthalate dimethyl ester obtained in S21 is reacted with di-tert-butylaniline in the presence of a catalyst and o-dichlorobenzene as a solvent to obtain 2-(bis(4-(tert-butyl)phenyl)amino)isophthalate dimethyl ester; S23. The 2-(bis(4-(tert-butyl)phenyl)amino)isophthalate dimethyl ester obtained in S22 is reacted with ethanol as solvent under alkaline aqueous solution conditions to generate 2-(bis(4-(tert-butyl)phenyl)amino)isophthalic acid; S24. The 2-(bis(4-(tert-butyl)phenyl)amino)isophthalic acid obtained in S23 is reacted with oxalyl chloride in the presence of tin tetrachloride catalyst to produce 3,11-di-tert-butylquinoline[3,2,1-de]acridin-5,9-dione; S25. The 3,11-di-tert-butylquinoline[3,2,1-de]acrid-5,9-dione obtained in step S24 is reacted with N-bromosuccinimide to generate the product 2-(bis(4-(tert-butyl)phenyl)-bromophenylazine-biscyclohexane ring; S26. The 2-(bis(4-(tert-butyl)phenyl)-bromophenylazine-biscyclohexane ring) obtained in step S25 is reacted with bis(pinacolyl)diboron under palladium catalyst to generate 3,11-ditert-butyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)quinolino[3,2,1-de]acridin-5,9-dione; S27. The 3,11-di-tert-butyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaboran-2-yl)quinolino[3,2,1-de]acridin-5,9-dione obtained in S26 was reacted with the 4-bromo-3-(9H-carbazol-9-yl)benzylnitrile obtained in S11 to obtain the target product 3-(9H-carbazol-9-yl)-4-(3,11-di-tert-butyl-5,9-dioxo-5,9-dihydroquinolino[3,2,1-de]acridin-7-yl)benzylnitrile, the structural formula of which is shown below: ； S28. The 3,11-di-tert-butyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaboran-2-yl)quinolino[3,2,1-de]acridin-5,9-dione obtained in S26 was reacted with the 4-bromo-3-(3,6-di-tert-butyl-9H-carbazole-9-yl)benzylnitrile obtained in S12 to obtain the target product 4-(3,11-di-tert-butyl-5,9-dioxo-5,9-dihydroquinolino[3,2,1-de]acridin-7-yl)-3-(3,6-di-tert-butyl-9H-carbazole-9-yl)benzylnitrile, the structural formula of which is shown below: ； S29. The 3,11-di-tert-butyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)quinolino[3,2,1-de]acridin-5,9-dione obtained in step S26 is reacted with the 4-bromo-2-(9H-carbazole-9-yl)benzylnitrile obtained in S13 under the action of the catalyst tetra-triphenylphosphine palladium to obtain the target product 2-(9H-carbazole-9-yl)-4-(3,11-di-tert-butyl-5,9-dioxo-5,9-dihydroquinolino[3,2,1-de]acridin-7-yl)benzylnitrile, the structural formula of which is shown below: 。 3. The method for preparing the narrow-band emission carbonyl-closed-ring aromatic amine fluorescent compound according to claim 2, characterized in that, In step S20, the molar ratio of potassium permanganate to 2,6-dimethylbromobenzene is (1~2):(1~8); the reaction temperature is 70~95℃, and the reaction time is 10~20 hours.

4. The method for preparing the narrow-band emission carbonyl-closed-ring aromatic amine fluorescent compound according to claim 2, characterized in that, In step S21, the molar ratio of 2-bromoisophthalic acid, thionyl chloride and methanol is (1~2):(3~10):(30~60), and the solvent used in step S21 is dichloromethane, the reaction temperature is 10~40℃, and the reaction time is 2~8 hours.

5. The method for preparing the narrow-band emission carbonyl-closed-ring aromatic amine fluorescent compound according to claim 2, characterized in that, In step S22, the molar ratio of dimethyl 2-bromoisophthalate, di-tert-butylaniline, and catalyst is (1~2):(1.5~4):(2~8), the reaction temperature is 100~130℃, the reaction time is 10~28 hours, and / or In step S23, the molar ratio of 2-(bis(4-(tert-butyl)phenyl)amino)isophthalate to ethanol is (1~1.5):(3~8), the reaction temperature is 65~90℃, the reaction time is 5~10 hours, and / or In step S24, the molar ratio of 2-(bis(4-(tert-butyl)phenyl)amino)isophthalic acid, oxaloyl chloride, and tin tetrachloride is (1~2):(2~3):(2~4), the reaction temperature is 25~40℃, and the reaction time is 3~8 hours.

6. The method for preparing the narrow-band emission carbonyl-closed-ring aromatic amine fluorescent compound according to claim 2, characterized in that, In step S25, the molar ratio of 3,11-di-tert-butylquinoline[3,2,1-de]acrid-5,9-dione to N-bromosuccinimide is (1~2):(2~4), the reaction temperature is 60~120℃, and the reaction time is 12~24 hours.

7. The method for preparing the narrow-band emission carbonyl-closed-ring aromatic amine fluorescent compound according to claim 2, characterized in that, In step S26, the molar ratio of 2-(bis(4-(tert-butyl)phenyl)-bromophenylazine dicyclohexane ring to bis(pinacol)diboron is (1~2):(2~6), the reaction temperature is 60~100℃, and the reaction time is 6~18 hours.

8. The method for preparing the narrow-band emission carbonyl-closed-ring aromatic amine fluorescent compound according to claim 2, characterized in that, In step S29, the molar ratio of 3,11-di-tert-butyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)quinolino[3,2,1-de]acridin-5,9-dione, 4-bromo-2-(9H-carbazol-9-yl)benzylnitrile generated in step S13, and tetra-triphenylphosphine palladium is (1~1.5):(1~2):(0.01~0.20), the reaction temperature is 65~100℃, and the reaction time is 10~18 hours.

9. The application of the narrow-band emission carbonyl-closed-ring aromatic amine fluorescent compound of claim 1 in the preparation of organic electroluminescent devices.

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