Preparation and application of aza-fused ring derivative-based circularly polarized luminescent material

Abstract

The application discloses preparation and application of circularly polarized luminescent material based on nitrogenous fused ring derivative. The application adopts 15b-nitrogenous pentabenz[a,c,ef,h,j] heptacycloalkene with helical chirality as a chiral perturbation unit, connects carbonyl with electron-withdrawing property and 10H-phenoxazine or 9,9-dimethyl-9H-acridine and derivatives thereof with electron-donating property, and constructs circularly polarized luminescent molecules with twisted spatial structure. Due to the existence of the twisted spatial structure, the circularly polarized material can effectively inhibit strong long-range pi-pi interaction between molecules in an aggregated state, realizes effective anti-aggregation-induced quenching effect at high concentration, has good aggregation-induced emission and aggregation-induced delayed fluorescence enhancement, and has excellent circularly polarized luminescent properties. The circularly polarized luminescent material based on the nitrogenous fused ring derivative provided in the application can be used to prepare a circularly polarized electroluminescent device with high efficient solid-state luminescence, low efficiency roll-off, large luminescence asymmetry factor (glum) value and excellent performance. The nitrogenous fused ring derivative has remarkable economic value in the application of preparing luminescent material, luminescent device or intelligent material, and has good application prospect in the field of full-color display and solid-state lighting.

Description

Technical Field

[0001] This application relates to the field of organic light-emitting materials technology, and more specifically, to the preparation and application of a circularly polarized light-emitting material based on a nitrogen-containing fused ring derivative. Background Technology

[0002] Circularly polarized organic light-emitting diodes (CP-OLEDs) are a current research hotspot in the optoelectronic field. These devices do not require additional polarizers, quarter-wave plates, and anti-glare filters, which can significantly simplify the device structure and reduce the manufacturing cost. At the same time, they have the advantages of excellent luminous efficiency and bright colors, making them a core technology with great development potential in the next generation of display and lighting fields.

[0003] Circularly polarized light-emitting materials are a class of functional light-emitting materials with chiral structures. Under excitation light or electrical excitation, they can asymmetrically emit left- or right-handed circularly polarized light. In CP-OLED devices, they serve as the organic light-emitting layer, and their properties determine the device's luminescence brightness and spectral characteristics. An ideal circularly polarized light-emitting material should possess: 1) a high asymmetric emission factor (…). g lum ); 2) High photoluminescence quantum yield ( Φ PL ); 3) High thermal and chemical stability; 4) Good electrical conductivity and certain carrier transport capability; 5) High color purity; 6) Stable working life.

[0004] Meanwhile, some organic light-emitting molecules suffer from low solid-state light-emitting efficiency due to aggregation-induced quenching (ACQ) effect, resulting in device efficiency roll-off and reducing the performance of the corresponding devices to some extent. Patent application content

[0005] To overcome one of the problems existing in the prior art, the primary objective of this application is to provide a circularly polarized luminescent material based on aza-fused-ring derivatives. This material uses a spirochetal 15b-azapentabenzo[a,c,ef,h,j]heptacycloene as the chiral perturbation unit, connecting an electron-withdrawing carbonyl group and an electron-donating group 10H-phenoxazine or 9,9-dimethyl-9H-acridine and its derivatives, respectively, to construct a molecule with a distorted spatial structure. In the aggregated state, it can suppress strong intermolecular π-π interactions, while simultaneously possessing aggregation-induced emission and aggregation-induced delayed fluorescence properties.

[0006] Another objective of this application is to provide a method for preparing the above-mentioned circularly polarized luminescent material based on nitrogen-containing fused ring derivatives.

[0007] Another objective of this application is to provide applications of the aforementioned circularly polarized luminescent materials based on nitrogen-containing fused ring derivatives.

[0008] The above-mentioned objectives of this application are achieved through the following technical solutions: A circularly polarized luminescent material based on nitrogen-containing fused ring derivatives, which can be used in organic small molecule optoelectronic functional materials, has the following general structural formula as described in any of formulas I to III: ; Equation (I); Equation (II); Equation (III); R can be independently chosen as H, alkyl, alkoxy, aryl, aromatic heterocyclic, or halogen atom, provided that R contains at least one independent substituent of the following: ; Where R1~R 10 The atom can be independently and freely chosen to be H, alkyl, alkoxy, aryl, aromatic heterocyclic, or halogen.

[0009] This application utilizes 15 with axial helicity. b -azapentabenzo[ a,c,ef,h,j Heptacycloene, as a chiral perturbation unit, links an electron-withdrawing carbonyl group and an electron-donating 10-hydroxyl group. H -Phenoxazine or 9,9-dimethyl-9 H -Acridine and its derivatives can produce molecules that simultaneously possess aggregation-induced emission and aggregation-induced delayed fluorescence properties, enabling the fabrication of circularly polarized organic electroluminescent devices that combine high solid-state luminescence, low efficiency roll-off, and a large luminescence asymmetry factor.

[0010] In some preferred embodiments, the circularly polarized luminescent material based on nitrogen-containing fused ring derivatives in this application has a structural formula selected from any of the following structural formulas: and .

[0011] This application also provides a method for preparing the above-mentioned nitrogen-containing fused-ring derivatives, including the following S: S1: 2-Iodobiphenyl and 2-iodoaniline are reacted via a Buchwald-Hartwig aromatic amination reaction in the presence of palladium acetate catalyst to obtain 9. H -Tribenzo[ b,d,f Azazopyroxene (i.e., compound 1); ; Compound 1; S2: 9 H -Tribenzo[ b,d,f Azaphene and 2,2'-dibromo-1,1'-biphenyl were reacted via a Buchwald-Hartwig aromatic amination reaction in the presence of palladium acetate catalyst to produce 15 b -azapentabenzo[ a,c,ef,h,jHeptacycloene (i.e., compound 2); ; Compound 2; S3: 15 b -azapentabenzo[ a,c,ef,h,j Heptacycloene reacts with 4-fluorobenzoyl chloride via a Friedel-Crafts acylation reaction in the presence of aluminum trichloride catalyst to yield 15 b -azapentabenzo[ a,c,ef,h,j Heptacycloben-18-yl-4-fluorophenyl ketone (i.e., compound 3); ; Compound 3; S4: The 15 obtained from S3 b -azapentabenzo[ a,c,ef,h,j Heptacyclopenten-18-yl-4-fluorophenyl ketone and 10 H -Phenoxazine and 9,9-dimethyl-9 H -Acridine, under the action of potassium tert-butoxide, undergoes a nucleophilic substitution reaction of the aromatic ring to prepare the target product (4-(10)). H -Phenoxazine-10-yl)phenyl)(15 b -azapentabenzo[ a,c,ef,h,j Heptacyclopenten-18-yl) methyl ketone and (15) b -azapentabenzo[ a,c,ef,h,j Heptacyclopenten-18-yl)(4-(9,9-dimethyl-9 H -Acridine-10-yl)phenyl)methyl ketone (i.e., compound 4 or compound 5); ; Compound 4; or ; Compound 5.

[0012] Preferably, in step S1, the molar ratio of 2-iodobiphenyl and 2-iodoaniline is 1 ~ 2: 1 ~ 2; More preferably, the molar ratio of 2-iodobiphenyl and 2-iodoaniline in step S1 is 1:1.5.

[0013] Preferably, the Buchwald-Hartwig aromatic amination reaction in step S1 is catalyzed by a palladium catalyst; the catalyst is palladium acetate.

[0014] Preferably, the solvent for the Buchwald-Hartwig aromatic amination reaction in step S1 is... N , N -Dimethylformamide.

[0015] Preferably, the Buchwald-Hartwig aromatic amination reaction in step S1 is performed under reflux protection with an inert gas.

[0016] Preferably, the inert gas in step S1 is nitrogen, argon, or helium; More preferably, the inert gas in step S1 is nitrogen.

[0017] Preferably, the reaction temperature in step S1 is 140~150 ℃, and the reaction time is 10~14 h; More preferably, the reaction temperature is 140 °C and the reaction time is 12 h.

[0018] Preferably, the treatment S in step S1 involves cooling, extraction, drying, concentration, and separation. After cooling the reaction solution to room temperature, the resulting mixture is extracted three times with ethyl acetate, and the organic phases 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 the crude product. Finally, silica gel column chromatography is performed using dichloromethane and petroleum ether as eluents to separate 9... H -Tribenzo[ b,d,f Nitrogen-containing polymorphon.

[0019] Preferably, the 9 in step S2 H -Tribenzo[ b,d,f The ratio of azirconium to 2,2'-dibromo-1,1'-biphenyl is 1~2:1~2; More preferably, the search in step S2 is... H -Tribenzo[ b,d,f The ratio of azirconium to 2,2'-dibromo-1,1'-biphenyl is 1:1.

[0020] Preferably, the Buchwald-Hartwig aromatic amination reaction in step S2 is catalyzed by a palladium catalyst; the catalyst is palladium acetate.

[0021] Preferably, the solvent for the reaction in step S2 is anhydrous toluene.

[0022] Preferably, the Buchwald-Hartwig aromatic amination reaction in step S2 is performed under reflux protection with an inert gas.

[0023] Preferably, the inert gas in step S2 is nitrogen, argon, or helium; More preferably, the inert gas in step S2 is nitrogen.

[0024] Preferably, the reaction temperature in step S2 is 110 ~ 120 ℃, and the reaction time is 24 ~ 36 h; More preferably, the reaction temperature in step S2 is 70 °C and the reaction time is 24 h.

[0025] Preferably, the cooling, extraction, drying, concentration, and separation steps in step S2 are as follows: After cooling the reaction solution to room temperature, the resulting mixture is extracted three times with ethyl acetate, 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 the crude product; finally, silica gel column chromatography is performed using dichloromethane and petroleum ether as eluents to separate 15... b -azapentabenzo[ a,c,ef,h,j Heptacycloene.

[0026] Preferably, the 15 in step S3 b -azapentabenzo[ a,c,ef,h,j The molar ratio of heptacycloene, 4-fluorobenzoyl chloride, and aluminum trichloride is 1 ~ 1.5 : 0.8 ~ 1.2 : 1.2 ~ 1.4; More preferably, in step S3, 15 b -azapentabenzo[ a,c,ef,h,j The molar ratio of heptacycloene, 4-fluorobenzoyl chloride, and aluminum trichloride is 1: 0.8: 1.2.

[0027] Preferably, the Friedel-Crafts acylation reaction in step S3 is catalyzed by a Lewis acid; the catalyst is aluminum trichloride.

[0028] Preferably, the solvent for the Friedel-Crafts acylation reaction in step S3 is anhydrous dichloromethane.

[0029] Preferably, the Friedel-Crafts acylation reaction in step S3 is performed under reflux protection with an inert gas.

[0030] Preferably, the inert gas in step S3 is nitrogen, argon, or helium; More preferably, the inert gas in step S3 is nitrogen.

[0031] Preferably, the reaction temperature is 15-25°C; the reaction time is 2-3 hours. More preferably, the reaction temperature is 25 °C and the reaction time is 3 h.

[0032] Preferably, the treatment in step S3 involves extraction, drying, concentration, and separation. The reaction solution 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, silica gel column chromatography is performed using dichloromethane and petroleum ether as eluents to separate 15... b -azapentabenzo[ a,c, ef,h,j Heptacycloene-18-yl-4-fluorophenyl methyl ketone.

[0033] Preferably, the 15 in step S4 b -azapentabenzo[ a,c,ef,h,j Heptacyclopenten-18-yl-4-fluorophenyl ketone, 10 H -Phenoxazine or 9,9-dimethyl-9 H The molar ratio of acridine to potassium tert-butoxide is 1 ~ 1.5 : 1.2 ~ 2 : 1.5 ~ 2.0; More preferably, the 15 mentioned in step S4 b -azapentabenzo[ a,c,ef,h,j Heptacyclopenten-18-yl-4-fluorophenyl ketone, 10 H -Phenoxazine or 9,9-dimethyl-9 H The molar ratio of acridine to potassium tert-butoxide is 1:1.2:1.5.

[0034] Preferably, the solvent for the reaction in step S4 is N , N -Dimethylformamide.

[0035] Preferably, the nucleophilic substitution reaction of the aromatic ring in step S4 is carried out under reflux protection with an inert gas.

[0036] Preferably, the inert gas in step S4 is nitrogen, argon, or helium; More preferably, the inert gas in step S4 is nitrogen.

[0037] Preferably, the reaction temperature in step S4 is 110-120 °C, and the reaction time is 10-14 h. More preferably, the reaction temperature in step S4 is 120 °C and the reaction time is 12 h.

[0038] Preferably, the treatment in step S4 involves cooling, extraction, washing, drying, concentration, separation, drying, and sublimation purification. After cooling the reaction solution to room temperature, the resulting mixture is extracted three times with ethyl acetate, and the organic phases 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 the crude product. Finally, silica gel column chromatography is performed using dichloromethane and petroleum ether as eluents, and the crude product is dried overnight in a vacuum drying oven. Finally, the compound (4-(10) is separated using a vacuum thermal sublimation separator. H -Phenoxazine-10-yl)phenyl)(15 b -azapentabenzo[ a,c,ef,h,j Heptacyclopenten-18-yl) methyl ketone and compound (15) b -azapentabenzo[ a,c,ef,h,j Heptacyclopenten-18-yl)(4-(9,9-dimethyl-9H -Acridine-10-yl)phenyl)methyl ketone.

[0039] The above-mentioned circularly polarized light-emitting materials based on nitrogen-containing fused ring derivatives are used as light-emitting devices or smart materials.

[0040] Compared with the prior art, the beneficial effects of this application are: The nitrogen-containing fused-ring derivatives provided in this application exhibit excellent solid-state luminescence efficiency and can serve as novel CP-OLED luminescent molecules with high performance and low cost. These nitrogen-containing fused-ring derivatives have significant economic value in applications such as the preparation of luminescent materials, luminescent devices, or smart materials, and show great promise for applications in full-color displays and solid-state lighting.

[0041] Meanwhile, the preparation process of the compound described in this application is simple, convenient, and can be prepared in large-scale batches, which is conducive to industrial production and the promotion of its application. Attached Figure Description

[0042] Figure 1 shows the compound (4-(10)) obtained in Example 1. H -Phenoxazine-10-yl)phenyl)(15 b -azapentabenzo[ a, c,ef,h,j Heptacyclopenten-18-yl)methyl ketone 1 HMNR diagram.

[0043] Figure 2 shows the compound (15) obtained in Example 2. b -azapentabenzo[ a,c,ef,h,j Heptacyclopenten-18-yl)(4-(9,9-dimethyl-9 H -acrid-10-yl)phenyl)methyl ketone 1 HMNR diagram.

[0044] Figure 3 shows the compound (4-(10)) obtained in Example 1. H -Phenoxazine-10-yl)phenyl)(15 b -azapentabenzo[ a, c,ef,h,j Mass spectrum of heptacycloene-18-yl)methyl ketone.

[0045] Figure 4 shows the compound (15) obtained in Example 2. b -azapentabenzo[ a,c,ef,h,j Heptacyclopenten-18-yl)(4-(9,9-dimethyl-9 H Mass spectrum of 1,0-acridin-1,0-yl)phenyl)methyl ketone.

[0046] Figure 5 shows the UV-Vis absorption spectra of the compounds prepared in Examples 1 and 2 in toluene solution.

[0047] Figure 6 shows the fluorescence emission spectra of the compounds prepared in Examples 1 and 2 in toluene solution.

[0048] Figure 7 shows the EL spectrum of the compound prepared in Example 1 and a physical image of the device (inset).

[0049] Figure 8 shows the (15) prepared in Example 2. b -azapentabenzo[ a,c,ef,h,j Heptacyclopenten-18-yl)(4-(9,9-dimethyl-9 H CD spectrum of 1,0-acridin-1,0-yl)phenyl)methyl ketone in toluene solution.

[0050] Figure 9 shows the (15) prepared in Example 2. b -azapentabenzo[ a,c,ef,h,j Heptacyclopenten-18-yl)(4-(9,9-dimethyl-9 H -Acridine-10-yl)phenyl)methyl ketone in toluene solution g PL curve.

[0051] Figure 10 shows the (15) prepared in Example 2. b -azapentabenzo[ a,c,ef,h,j Heptacyclopenten-18-yl)(4-(9,9-dimethyl-9 H CPPL curve of 1,0-acridin-1,0-yl)phenyl)methyl ketone in toluene solution. Detailed Implementation

[0052] The embodiments of this 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 considered as limiting the scope of this application. Unless otherwise 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.

[0053] It should be noted that: Unless otherwise specified, all embodiments and preferred embodiments mentioned herein can be combined to form new technical solutions.

[0054] In this application, unless otherwise specified, percentage (%) or parts refer to weight percentage or parts relative to the composition.

[0055] Unless otherwise specified, the components or preferred components involved in this application may be combined to form new technical solutions.

[0056] In this application, unless otherwise stated, the numerical range "a~b" represents a shortened representation 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 in this document, and "1~5" is simply a shortened representation of these numerical combinations.

[0057] The “scope” disclosed in this 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.

[0058] In this application, unless otherwise stated, the various reactions or operations S may be performed sequentially or in a particular order. In some preferred embodiments, the reaction methods described herein are performed sequentially.

[0059] 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 application.

[0060] In their research, the applicant discovered an organic light-emitting molecule that combines aggregation-induced emission (AIE) and aggregation-induced delayed fluorescence (AIDF) effects, attracting widespread attention. This type of molecule has a distorted spatial structure, and in its aggregated state, there are no strong π-π interactions between molecules. Based on this type of molecule, it is hoped that high-efficiency, low-efficiency roll-off, simple device structure, and undoped CP-OLED devices can be developed.

[0061] This application provides a circularly polarized luminescent material based on a nitrogen-containing fused ring derivative, which can be used in organic small molecule optoelectronic functional materials, and has the following general structural formula as described in any of formulas I to III: ; Equation (I); Equation (II); Equation (III); R can be independently chosen as H, alkyl, alkoxy, aryl, aromatic heterocyclic, or halogen atom, provided that R contains at least one independent substituent of the following: ; Where R1~R 10 The atom can be independently and freely chosen to be H, alkyl, alkoxy, aryl, aromatic heterocyclic, or halogen.

[0062] This application utilizes 15 with axial helicity. b -azapentabenzo[ a,c,ef,h,j Heptacycloene, as a chiral perturbation unit, links an electron-withdrawing carbonyl group and an electron-donating 10-hydroxyl group. H -Phenoxazine or 9,9-dimethyl-9 H-Acridine and its derivatives can produce molecules that simultaneously possess aggregation-induced emission and aggregation-induced delayed fluorescence properties, enabling the fabrication of circularly polarized organic electroluminescent devices that combine high solid-state luminescence, low efficiency roll-off, and a large luminescence asymmetry factor.

[0063] In some preferred embodiments, the circularly polarized luminescent material based on nitrogen-containing fused ring derivatives in this application has a structural formula selected from any of the following structural formulas: and .

[0064] This application also provides a method for preparing the above-mentioned nitrogen-containing fused-ring derivatives, including the following S: S1: 2-Iodobiphenyl and 2-iodoaniline are reacted via a Buchwald-Hartwig aromatic amination reaction in the presence of palladium acetate catalyst to obtain 9. H -Tribenzo[ b,d,f Azazopyroxene (i.e., compound 1); ; Compound 1; S2: 9 H -Tribenzo[ b,d,f Azaphene and 2,2'-dibromo-1,1'-biphenyl were reacted via a Buchwald-Hartwig aromatic amination reaction in the presence of palladium acetate catalyst to produce 15 b -azapentabenzo[ a,c,ef,h,j Heptacycloene (i.e., compound 2); ; Compound 2; S3: 15 b -azapentabenzo[ a,c,ef,h,j Heptacycloene reacts with 4-fluorobenzoyl chloride via a Friedel-Crafts acylation reaction in the presence of aluminum trichloride catalyst to yield 15 b -azapentabenzo[ a,c,ef,h,j Heptacycloben-18-yl-4-fluorophenyl ketone (i.e., compound 3); ; Compound 3; S4: The 15 obtained from S3 b -azapentabenzo[ a,c,ef,h,j Heptacyclopenten-18-yl-4-fluorophenyl ketone and 10 H -Phenoxazine and 9,9-dimethyl-9 H -Acridine, under the action of potassium tert-butoxide, undergoes a nucleophilic substitution reaction of the aromatic ring to prepare the target product (4-(10)). H -Phenoxazine-10-yl)phenyl)(15 b-azapentabenzo[ a,c,ef,h,j Heptacyclopenten-18-yl) methyl ketone and (15) b -azapentabenzo[ a,c,ef,h,j Heptacyclopenten-18-yl)(4-(9,9-dimethyl-9 H -Acridine-10-yl)phenyl)methyl ketone (i.e., compound 4 or compound 5); ; Compound 4; or ; Compound 5.

[0065] In some preferred embodiments, the molar ratio of 2-iodobiphenyl and 2-iodoaniline in step S1 is 1 ~ 2: 1 ~ 2.

[0066] In some preferred embodiments, the molar ratio of 2-iodobiphenyl and 2-iodoaniline in step S1 is 1:1.5.

[0067] In some preferred embodiments, the Buchwald-Hartwig aromatic amination reaction in step S1 is catalyzed by a palladium catalyst; the catalyst is palladium acetate.

[0068] In some preferred embodiments, the solvent for the Buchwald-Hartwig aromatic amination reaction in step S1 is N , N -Dimethylformamide.

[0069] In some preferred embodiments, the Buchwald-Hartwig aromatic amination reaction in step S1 is performed under reflux protection with an inert gas.

[0070] In some preferred embodiments, the inert gas in step S1 is nitrogen, argon, or helium.

[0071] In some preferred embodiments, the inert gas in step S1 is nitrogen.

[0072] In some preferred embodiments, the reaction temperature in step S1 is 140-150°C, and the reaction time is 10-14 hours.

[0073] In some preferred embodiments, the reaction temperature is 140°C and the reaction time is 12 h.

[0074] In some preferred embodiments, the treatment S in step S1 includes cooling, extraction, drying, concentration, and separation. After cooling the reaction solution to room temperature, the resulting mixture is extracted three times with ethyl acetate, and the organic phases 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 the crude product. Finally, silica gel column chromatography is performed using dichloromethane and petroleum ether as eluents to separate 9... H -Tribenzo[ b,d,f Nitrogen-containing polymorphon.

[0075] In some preferred embodiments, the 9 in step S2 H -Tribenzo[ b,d,f The ratio of azirconium to 2,2'-dibromo-1,1'-biphenyl is 1 ~ 2: 1 ~ 2.

[0076] In some preferred embodiments, the search step S2 is described as follows: H -Tribenzo[ b,d,f The ratio of azirconium to 2,2'-dibromo-1,1'-biphenyl is 1:1.

[0077] In some preferred embodiments, the Buchwald-Hartwig aromatic amination reaction in step S2 is catalyzed by a palladium catalyst; the catalyst is palladium acetate.

[0078] In some preferred embodiments, the solvent for the reaction in step S2 is anhydrous toluene.

[0079] In some preferred embodiments, the Buchwald-Hartwig aromatic amination reaction in step S2 is performed under reflux protection with an inert gas.

[0080] In some preferred embodiments, the inert gas in step S2 is nitrogen, argon, or helium.

[0081] In some preferred embodiments, the inert gas in step S2 is nitrogen.

[0082] In some preferred embodiments, the reaction temperature in step S2 is 110-120°C, and the reaction time is 24-36 hours. In some preferred embodiments, the reaction temperature in step S2 is 70 °C and the reaction time is 24 h.

[0083] In some preferred embodiments, the cooling, extraction, drying, concentration, and separation steps in step S2 are as follows: After cooling the reaction solution to room temperature, the resulting mixture is extracted three times with ethyl acetate, 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 the crude product; finally, silica gel column chromatography is performed using dichloromethane and petroleum ether as eluents to separate 15... b-azapentabenzo[ a,c,ef,h,j Heptacycloene.

[0084] In some preferred embodiments, the 15 in step S3 b -azapentabenzo[ a,c,ef,h,j The molar ratio of heptacycloene, 4-fluorobenzoyl chloride, and aluminum trichloride is 1 ~ 1.5 : 0.8 ~ 1.2 : 1.2 ~ 1.4.

[0085] In some more preferred embodiments, 15 in step S3 b -azapentabenzo[ a,c,ef,h,j The molar ratio of heptacycloene, 4-fluorobenzoyl chloride, and aluminum trichloride is 1: 0.8: 1.2.

[0086] In some preferred embodiments, the Friedel-Crafts acylation reaction in step S3 is catalyzed by a Lewis acid; the catalyst is aluminum trichloride.

[0087] In some preferred embodiments, the solvent for the Friedel-Crafts acylation reaction in step S3 is anhydrous dichloromethane.

[0088] In some preferred embodiments, the Friedel-Crafts acylation reaction in step S3 is performed under reflux protection with an inert gas.

[0089] In some preferred embodiments, the inert gas in step S3 is nitrogen, argon, or helium.

[0090] In some preferred embodiments, the inert gas in step S3 is nitrogen.

[0091] In some preferred embodiments, the reaction temperature is 15 ~ 25 °C; the reaction time is 2 ~ 3 h.

[0092] In some preferred embodiments, the reaction temperature is 25 °C and the reaction time is 3 h.

[0093] In some preferred embodiments, the treatment in step S3 is extraction, drying, concentration, and separation. The reaction solution 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, silica gel column chromatography is performed using dichloromethane and petroleum ether as eluents to separate 15 b -azapentabenzo[ a,c,ef,h,j Heptacycloene-18-yl-4-fluorophenyl methyl ketone.

[0094] In some preferred embodiments, the 15 in step S4 b -azapentabenzo[ a,c,ef,h,j Heptacyclopenten-18-yl-4-fluorophenyl ketone, 10 H-Phenoxazine or 9,9-dimethyl-9 H The molar ratio of acridine to potassium tert-butoxide is 1 ~ 1.5:1.2 ~ 2:1.5 ~ 2.0.

[0095] In some preferred embodiments, the 15 in step S4 b -azapentabenzo[ a,c,ef,h,j Heptacyclopenten-18-yl-4-fluorophenyl ketone, 10 H -Phenoxazine or 9,9-dimethyl-9 H The molar ratio of acridine to potassium tert-butoxide is 1:1.2:1.5.

[0096] In some preferred embodiments, the solvent for the reaction in step S4 is N , N -Dimethylformamide.

[0097] In some preferred embodiments, the nucleophilic substitution reaction of the aromatic ring in step S4 is performed under reflux protection with an inert gas.

[0098] In some preferred embodiments, the inert gas in step S4 is nitrogen, argon, or helium.

[0099] In some preferred embodiments, the inert gas in step S4 is nitrogen.

[0100] In some preferred embodiments, the reaction temperature in step S4 is 110-120 °C, and the reaction time is 10-14 h. In some preferred embodiments, the reaction temperature in step S4 is 120 °C and the reaction time is 12 h.

[0101] In some preferred embodiments, the treatment in step S4 includes cooling, extraction, washing, drying, concentration, separation, drying, and sublimation purification. After cooling the reaction solution to room temperature, the resulting mixture is extracted three times with ethyl acetate, and the organic phases 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 the crude product. Finally, silica gel column chromatography is performed using dichloromethane and petroleum ether as eluents, and the crude product is dried overnight in a vacuum drying oven. Finally, the compound (4-(10) is separated using a vacuum thermal sublimation separator. H -Phenoxazine-10-yl)phenyl)(15 b -azapentabenzo[ a,c,ef,h,j Heptacyclopenten-18-yl) methyl ketone and compound (15) b -azapentabenzo[ a,c,ef,h,j Heptacyclopenten-18-yl)(4-(9,9-dimethyl-9 H -Acridine-10-yl)phenyl)methyl ketone.

[0102] This application also provides the application of the above-mentioned circularly polarized light-emitting materials based on nitrogen-containing fused ring derivatives as light-emitting devices or smart materials.

[0103] The preparation method of the circularly polarized luminescent material compound (I) based on nitrogen-containing fused ring derivatives will be described in detail below.

[0104] Example 1 (4-(10) H -Phenoxazine-10-yl)phenyl)(15 b -azapentabenzo[ a,c,ef,h,j Preparation of heptacycloene-18-yl)methyl ketone S1: 9 H -Tribenzo[ b,d,f Preparation of azidophene (i.e., compound 1): 2-Iodobiphenyl (2.80 g, 10 mmol), 2-iodoaniline (3.28 g, 15 mmol), and palladium acetate (0.06 g, 0.5 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, 40 mL of [amount missing] was added. N , N Dimethylformamide was stirred at 140 °C for 12 h. After the reaction was complete, the mixture was extracted with saturated brine and ethyl acetate. The solid was then distilled under reduced pressure to obtain a black solid. Using silica gel as the stationary phase and petroleum ether / dichloromethane as the eluent, 1.28 g of a pale yellow powder (53% yield) was obtained by column chromatography.

[0105] The reaction equation is as follows: ; S2:15 b -azapentabenzo[ a,c,ef,h,j Preparation of heptacycloene (i.e., compound 2): 9 H -Tribenzo[ b,d,f Azapyrrolizidine (2.43 g, 10 mmol), 2,2'-dibromo-1,1'-biphenyl (3.10 g, 10 mmol), and palladium acetate (0.06 g, 0.5 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, 40 mL of anhydrous toluene was added, and the mixture was stirred at 110 °C for 12 h. After the reaction was complete, the mixture was extracted with saturated brine and ethyl acetate. The solid was distilled under reduced pressure to obtain a black solid. Using silica gel as the stationary phase and petroleum ether / dichloromethane as the eluent, 1.88 g of a white powder (48% yield) was obtained by column chromatography.

[0106] The reaction equation is as follows: ; S3:15 b -azapentabenzo[ a,c,ef,h,j Preparation of heptacycloene-18-yl-4-fluorophenyl ketone (i.e., compound 3): 15 b -azapentabenzo[ a,c,ef,h,j Heptacycloene (3.93 g, 10 mmol), 4-fluorobenzoyl chloride (1.27 g, 8 mmol), and aluminum trichloride (1.59 g, 12 mmol) were sequentially added to a 100 mL necked flask. The flask was evacuated under vacuum and purged three times with dry nitrogen. Then, 40 mL of dichloromethane was added. The mixture was heated to reflux and stirred at 25 °C for 3 h. Extraction was performed using saturated brine and dichloromethane. The solid was distilled under reduced pressure to obtain a yellow solid. Using silica gel as the stationary phase and petroleum ether / dichloromethane as the eluent, column chromatography was used to obtain 3.24 g of a pale yellow powder (63% yield).

[0107] The reaction equation is as follows: ; S4:(4-(10 H -Phenoxazine-10-yl)phenyl)(15 b -azapentabenzo[ a,c,ef,h,j Preparation of heptacycloen-18-yl)methyl ketone (i.e., compound 4) 15 b -azapentabenzo[ a,c,ef,h,j Heptacyclopenten-18-yl-4-fluorophenyl ketone (0.51 g, 1 mmol), 10 H β-Phenyrazine (0.22 g, 1.2 mmol) and potassium tert-butoxide (0.17 g, 1.5 mmol) were added sequentially to a 50 mL two-necked flask. The flask was evacuated under vacuum and purged three times with dry nitrogen. Then, 15 mL of [amount missing] was added. N , N -Dimethylformamide. The reaction mixture was heated under reflux and stirred at 120 °C for 12 h. Extraction was performed using saturated brine and ethyl acetate. Vacuum distillation was carried out to obtain a yellow solid. Using silica gel powder as the stationary phase and petroleum ether / dichloromethane as the eluent, 0.54 g of a yellow powder (80% yield) was obtained by column chromatography.

[0108] The reaction equation is as follows: ; Compound (4-(10) H -Phenoxazine-10-yl)phenyl)(15 b -azapentabenzo[ a,c,ef,h,jThe NMR spectrum of heptacyclopenten-18-yl)methyl ketone is as follows: Figure 1 As shown. From Figure 1 It can be seen that its characteristic wavenumber (ppm) is 1 H NMR (400 MHz, DMSO)δ 8.07, 8.06, 7.99, 7.97, 7.97, 7.74, 7.72, 7.71, 7.70, 7.69, 7.68, 7.66,7.65, 7.63, 7.61, 7.60, 7.60, 7.59, 7.58, 7.56, 7.54, 7.54, 7.52, 7.50, 7.49,7.47, 7.34, 7.32, 7.30, 7.22, 7.20, 7.19, 6.77, 6.77, 6.75, 6.75, 6.72, 6.72,6.70, 6.70, 6.68, 6.68, 6.67, 6.66, 6.65, 6.64, 6.64, 6.62, 6.59, 6.58, 5.96, 5.96, 5.94, 5.94, 5.33, 5.32, 5.31, peak energy and 15 b -azapentabenzo[ a,c,ef,h,j Heptacycloene, 10 H The hydrogen atoms on the aromatic ring of the phenoxazine are in a one-to-one correspondence, and the number is reasonable. This indicates that the (4-(10) H -Phenoxazine-10-yl)phenyl)(15 b -azapentabenzo[ a,c,ef,h,j Heptacycloene-18-yl) methyl ketone compounds have a simple structure and high purity.

[0109] Example 2 (15) b -azapentabenzo[ a,c,ef,h,j Heptacyclopenten-18-yl)(4-(9,9-dimethyl-9 H Preparation of 1,0-acridin-1,0-yl)phenyl)methyl ketone Example 1S3 prepared 15 b -azapentabenzo[ a,c,ef,h,j Heptacycloene-18-yl-4-fluorophenyl ketone can also be used in (15) b -azapentabenzo[ a,c,ef,h,j Heptacyclopenten-18-yl)(4-(9,9-dimethyl-9 H Preparation of 1,0-acridin-1,0-yl)phenyl)methyl ketone.

[0110] S4:(15 b -azapentabenzo[ a,c,ef,h,j Heptacyclopenten-18-yl)(4-(9,9-dimethyl-9 HPreparation of 1,0-acridin-1,0-yl)phenyl)methyl ketone (i.e., compound 4) 15 b -azapentabenzo[ a,c,ef,h,j Heptacyclopenten-18-yl-4-fluorophenyl ketone (0.51 g, 1 mmol), 9,9-dimethyl-9 H Acridine (0.25 g, 1.2 mmol) and potassium tert-butoxide (0.17 g, 1.5 mmol) were added sequentially to a 50 mL two-necked flask. The flask was evacuated under vacuum and purged three times with dry nitrogen. Then, 15 mL of [amount missing] was added. N , N -Dimethylformamide. The reaction mixture was heated under reflux and stirred at 120 °C for 12 h. Extraction was performed using saturated brine and ethyl acetate. Vacuum distillation was carried out to obtain a yellow solid. Using silica gel powder as the stationary phase and petroleum ether / dichloromethane as the eluent, 0.47 g of a yellow powder (67% yield) was obtained by column chromatography.

[0111] The reaction equation is as follows: ; Compound (15) b -azapentabenzo[ a,c,ef,h,j Heptacyclopenten-18-yl)(4-(9,9-dimethyl-9 H The NMR spectrum of 1,10-acridin-1,10-yl)phenyl)methyl ketone is as follows: Figure 2 As shown. From Figure 2 It can be seen that its characteristic wavenumber (ppm) is 1 H NMR (400MHz, DMSO) δ 8.09, 8.03, 8.00, 7.74, 7.72, 7.65, 7.60, 7.59, 7.58, 7.54,7.54, 7.52, 7.51, 7.49, 7.32, 7.30, 7.23, 7.20, 7.18, 7.00, 6.98, 6.95, 6.94,6.92, 6.91, 6.63, 6.61, 6.58, 6.24, 6.21, 5.33, 5.32, 5.31, 2.03, 2.01, 1.99,1.97, 0.87, 0.85, 0.83, peak energy and 15 b -azapentabenzo[ a,c,ef,h,j Heptacycloene, 19,9-dimethyl-9 H The hydrogen atoms on the aromatic ring of acridine are in a one-to-one correspondence, and the number is reasonable. This indicates that the (15) b -azapentabenzo[ a,c,ef,h,j Heptacyclopenten-18-yl)(4-(9,9-dimethyl-9 H-Acridine-10-yl)phenyl)methyl ketone compounds have a simple structure and high purity.

[0112] Figure 1 and Figure 2 Molecules (4-(10) were measured using a Bruker 400 MHz superconducting nuclear magnetic resonance spectrometer. H -Phenoxazine-10-yl)phenyl)(15 b -azapentabenzo[ a,c,ef,h,j Heptacyclopenten-18-yl) methyl ketone and (15) b -azapentabenzo[ a,c,ef,h, j Heptacyclopenten-18-yl)(4-(9,9-dimethyl-9 H 1H NMR spectrum of 1-acridin-10-yl)phenyl)methyl ketone, solvent: deuterated dimethyl sulfoxide. Figure 3 and Figure 4 Molecules (4-(10) were analyzed using a Thermo Fisher ultra-high performance liquid chromatography-tandem triple quadrupole mass spectrometer* / TSQ Endura. H -Phenoxazine-10-yl)phenyl)(15 b -azapentabenzo[ a,c,ef,h,j Heptacyclopenten-18-yl) methyl ketone and (15) b -azapentabenzo[ a,c,ef,h,j Heptacyclopenten-18-yl)(4-(9,9-dimethyl-9 H Mass spectrometry of 10-acridinylphenyl methyl ketone.

[0113] Example 3 Characterization and Performance Testing Compounds (4-(10) prepared according to Examples 1 and 2 H -Phenoxazine-10-yl)phenyl)(15 b -azapentabenzo[ a,c,ef,h,j Heptacyclopenten-18-yl) methyl ketone and (15) b -azapentabenzo[ a,c,ef,h,j Heptacyclopenten-18-yl)(4-(9,9-dimethyl-9 H Using 10-acridinylphenyl methyl ketone as the test object, its photophysical properties were tested, and the test results are as follows: Figure 5 and Figure 6 As shown. Where ABH-PXZ is (4-(10) H -Phenoxazine-10-yl)phenyl)(15 b -azapentabenzo[ a,c,ef,h,j Heptacyclopenten-18-yl) methyl ketone, ABH-DMAC is (15 b -azapentabenzo[ a,c,ef,h,j Heptacyclopenten-18-yl)(4-(9,9-dimethyl-9 H-Acridine-10-yl)phenyl)methyl ketone.

[0114] Figure 5 The molecular (4-(10) was measured by the Shimadzu UV-2700 UV-Vis spectrophotometer. H -Phenoxazine-10-yl)phenyl)(15 b -azapentabenzo[ a,c,ef,h,j Heptacyclopenten-18-yl) methyl ketone and (15) b -azapentabenzo[ a,c,ef,h,j Heptacyclopenten-18-yl)(4-(9,9-dimethyl-9 H Absorption spectrum of 1,0-acridin-1,0-yl)phenyl)methyl ketone in toluene solution.

[0115] Figure 6 The molecular (4-(10) obtained by testing with the Edinburgh FLS980 at an excitation wavelength of 375 nm H -Phenoxazine-10-yl)phenyl)(15 b -azapentabenzo[ a,c,ef,h,j Heptacyclopenten-18-yl) methyl ketone and (15) b -azapentabenzo[ a,c,ef, h,j Heptacyclopenten-18-yl)(4-(9,9-dimethyl-9 H The normalized emission spectra of 1,10-acridin-phenyl methyl ketone in toluene solution show emission at 561 nm and 510 nm, respectively.

[0116] Figure 7 This is an EQE brightness characteristic diagram of the compound device prepared based on Example 1. From Figure 7 As can be seen from the data, even at a relatively high doping concentration of 30 wt%, the compound still maintains good EQE characteristics, indicating that it has excellent resistance to device efficiency roll-off and good resistance to ACQ effects at high doping concentrations.

[0117] Figure 8 It is the (15) prepared in Example 2 b -azapentabenzo[ a,c,ef,h,j Heptacyclopenten-18-yl)(4-(9,9-dimethyl-9 H CD spectrum of 1,10-acridin-1,10-yl)phenyl)methyl ketone in toluene solution. Figure 8 The results show that the CD signals of the two enantiomers of the compound are perfectly symmetrical and have high signal intensity, indicating that the two enantiomers of the compound do indeed have chiral characteristics and that their peak positions are consistent with those of the ultraviolet absorption signal peak of the chiral perturbation unit 15b-azapentabenzo[a,c,ef,h,j]heptacycloene.

[0118] Figure 9It is the (15) prepared in Example 2 b -azapentabenzo[ a,c,ef,h,j Heptacyclopenten-18-yl)(4-(9,9-dimethyl-9 H -Acridine-10-yl)phenyl)methyl ketone in toluene solution g PL Line graph. From Figure 9 As can be seen from the data, the CD signals of the two enantiomers of this compound exhibit good symmetry and high signal intensity, indicating that the two enantiomers of this compound do indeed have chiral characteristics and that their peak positions are consistent with those of the compound's fluorescence spectrum.

[0119] Figure 10 It is the (15) prepared in Example 2 b -azapentabenzo[ a,c,ef,h,j Heptacyclopenten-18-yl)(4-(9,9-dimethyl-9 H CPPL curve of 1,10-acridin-1,10-yl)phenyl)methyl ketone in toluene solution. Figure 10 From the above, it can be seen that at 510 nm, the compound... g PL = +3.32×10 -3 / -2.47×10 -3 This indicates that the compound has a large asymmetry factor.

[0120] In summary, this application provides a circularly polarized luminescent material based on a nitrogen-containing fused ring derivative, its preparation, and its application. This circularly polarized luminescent material based on a nitrogen-containing fused ring derivative utilizes a 15-membered spiral chiral structure. b -azapentabenzo[ a,c,ef, h,j Heptacycloene, as a chiral perturbation unit, connects an electron-withdrawing carbonyl group and an electron-donating 10-hydroxyl group. H -Phenoxazine or 9,9-dimethyl-9 H -Acridine and its derivatives were used to construct circularly polarized luminescent molecules with a twisted spatial structure. Due to the presence of the twisted spatial structure, these circularly polarized materials can effectively suppress strong long-range π-π interactions between molecules in the aggregated state. At high concentrations, they can effectively resist aggregation-induced quenching effects and have good aggregation-induced emission and aggregation-induced delayed fluorescence enhancement as well as excellent circularly polarized luminescence characteristics.

[0121] Circularly polarized luminescent materials based on the nitrogen-containing fused ring derivatives provided in this application can be prepared with high-efficiency solid-state luminescence, low efficiency roll-off, and a large luminescence asymmetry factor. g lumThis is a high-performance circularly polarized electroluminescent device. This nitrogen-containing heterocyclic derivative has significant economic value in the preparation of luminescent materials, luminescent devices, and smart materials, and shows great promise for applications in full-color displays and solid-state lighting.

[0122] Furthermore, this application demonstrates that the circularly polarized luminescent material can be used to fabricate circularly polarized electroluminescent devices with high solid-state luminescence, low efficiency roll-off, and a large luminescence asymmetry factor. Therefore, this nitrogen-containing heterocyclic derivative has significant economic value in applications such as the preparation of luminescent materials, luminescent devices, or smart materials, and shows great promise for applications in full-color displays and solid-state lighting.

[0123] 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 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.

[0124] Although several embodiments of this application have been shown and described, those skilled in the art will understand that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of this application, the scope of which is defined by the claims and their equivalents.

Claims

1. A circularly polarized luminescent material based on nitrogen-containing fused ring derivatives, which can be used in organic small molecule optoelectronic functional materials, characterized in that, It has the following general structural formulas as described in any of Equations I to III: ； Equation (I); Equation (II); Equation (III); R can be independently chosen as H, alkyl, alkoxy, aryl, aromatic heterocyclic, or halogen atom, provided that R contains at least one independent substituent of the following: ； Where R1~R 10 The atom can be independently and freely chosen to be H, alkyl, alkoxy, aryl, aromatic heterocyclic, or halogen.

2. The circularly polarized luminescent material based on nitrogen-containing fused ring derivatives according to claim 1, characterized in that, Its structural formula is selected from any of the following structural formulas: and .

3. The method for preparing the circularly polarized luminescent material based on nitrogen-containing fused ring derivatives according to claims 1-2, characterized in that, Including the following S: S1: 2-Iodobiphenyl and 2-iodoaniline were reacted via a Buchwald-Hartwig aromatic amination reaction to obtain 9. H -Tribenzo[ b,d,f Nitrogen-containing polymorphon; S2: 9 H -Tribenzo[ b,d,f Azapyrrolizidine and 2,2'-dibromo-1,1'-biphenyl were reacted via the Buchwald-Hartwig arylation reaction to produce 15 b -azapentabenzo[ a,c,ef,h,j Heptacycloene; S3: 15 b -azapentabenzo[ a,c,ef,h,j Heptacycloene reacts with 4-fluorobenzoyl chloride via Friedel-Crafts acylation to yield 15 b -azapentabenzo[ a,c,ef,h,j Heptacyclopenten-18-yl-4-fluorophenyl ketone; S4: The 15 obtained from S3 b -azapentabenzo[ a,c,ef,h,j Heptacyclopenten-18-yl-4-fluorophenyl ketone and 10 H -Phenoxazine or 9,9-dimethyl-9 H -Acridine, under the action of potassium tert-butoxide, undergoes a nucleophilic substitution reaction of the aromatic ring to prepare the target product (4-(10)). H -Phenoxazine-10-yl)phenyl)(15 b -azapentabenzo[ a,c,ef,h,j Heptacyclopenten-18-yl) methyl ketone and (15) b -azapentabenzo[ a,c,ef,h,j Heptacyclopenten-18-yl)(4-(9,9-dimethyl-9 H -Acridine-10-yl)phenyl)methyl ketone.

4. The method for preparing circularly polarized luminescent materials based on nitrogen-containing fused ring derivatives according to claim 3, characterized in that, In step S1, the catalyst for the Buchwald-Hartwig reaction is palladium acetate, and the molar ratio of 2-iodobiphenyl, 2-iodoaniline, and palladium acetate is (1.0 ~ 2.0):(1.0 ~ 2.0):(0.05 ~ 0.1). The reaction temperature is 140 ~ 150 ℃, and the reaction time is 10 ~ 14 h.

5. The method for preparing circularly polarized luminescent materials based on nitrogen-containing fused ring derivatives according to claim 4, characterized in that, The solvent for the Buchwald-Hartwig aromatic amination reaction in step S1 is N , N -Dimethylformamide, and refluxed under the protection of an inert gas.

6. The method for preparing circularly polarized luminescent materials based on nitrogen-containing fused ring derivatives according to claim 3, characterized in that, The catalyst in step S2 is palladium acetate, 9 H -Tribenzo[ b,d,f The molar ratio of azirconium, 2,2'-dibromo-1,1'-biphenyl, and palladium acetate was (1.0 ~ 2.0): (1.0 ~ 2.0): (0.05 ~ 0.1), the reaction temperature was 110 ~ 120 ℃, and the reaction time was 24 ~ 36 h.

7. The method for preparing the circularly polarized luminescent material based on nitrogen-containing fused ring derivatives according to claim 6, characterized in that, The solvent for the reaction in step S2 is anhydrous toluene, and the Buchwald-Hartwig aromatic amination reaction is carried out under reflux protection with an inert gas.

8. The method for preparing circularly polarized luminescent materials based on nitrogen-containing fused ring derivatives according to claim 3, characterized in that, The catalyst for the Friedel-Crafts acylation reaction in step S3 is aluminum trichloride, 15 b -azapentabenzo[ a,c,ef,h,j The molar ratio of heptacycloene, 4-fluorobenzoyl chloride, and aluminum trichloride was (1.0 ~ 1.5): (0.8 ~ 1.2): (1.2 ~ 1.4), the reaction temperature was 15 ~ 25 ℃, and the reaction time was 2 ~ 3 h.

9. The method for preparing circularly polarized luminescent materials based on nitrogen-containing fused ring derivatives according to claim 3, characterized in that, The deprotonating base for the nucleophilic substitution reaction of the aromatic ring in step S4 is potassium tert-butoxide, 15 b -azapentabenzo[ a,c,ef, h,j Heptacyclopenten-18-yl-4-fluorophenyl ketone, 10 H- Phenoxazine or 9,9-dimethyl-9 H The molar ratio of acridine to potassium tert-butoxide is (1.0 ~ 1.5):(1.2 ~ 2.0):(1.5 ~ 2.0), the reaction temperature is 110 ~ 120 ℃, and the reaction time is 10 ~ 14 h.

10. The application of the nitrogen-containing fused ring derivative of claim 1 or 2 in the preparation of circularly polarized light-emitting materials, light-emitting devices, or smart materials.

Images