Dinitrogen heteroaromatic fused ring compound, preparation method and light-emitting device

Abstract

The invention relates to a dinitrogen heteroaromatic fused ring compound, a preparation method and a light-emitting device, and belongs to the field of organic light-emitting materials. The technical problem that the half-peak width of an existing thermal activation delayed fluorescent material is large is solved. According to the invention, a dinitrogen heteroaromatic fused ring unit is used as a luminescent material, on one hand, the relaxation degree of an excited state structure is reduced by using a rigid skeleton structure of the dinitrogen heteroaromatic fused ring compound, so that a narrower half-peak width is realized; on the other hand, separation of HOMO and LUMO is achieved through the resonance effect between electron-deficient groups and nitrogen atoms, and therefore small delta EST and TADF effects are achieved, and then high luminous efficiency is achieved. Meanwhile, by changing the types of aromatic rings or heteroaromatic rings contained in the fused ring compound, the delayed fluorescence lifetime and the half-peak width can be further adjusted. The dinitrogen heteroaromatic fused ring compound disclosed by the invention not only can realize narrow electroluminescent half-peak width under the condition that an optical filter and a microcavity structure are not needed, but also can realize high external quantum efficiency of a device.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic light-emitting materials, and particularly relates to a diazaaromatic fused-ring compound, a preparation method thereof, and a light-emitting device. Background Art

[0002] Organic light-emitting devices (OLEDs) have the characteristics of rich colors, thin thickness, wide viewing angles, fast response, and the ability to fabricate flexible devices, and are considered to be the most promising next-generation flat-panel display and solid-state lighting technologies. OLEDs are usually composed of an ITO anode, a hole injection layer (HIL), a hole transport layer (HTL), a light-emitting layer (EL), a hole blocking layer (HBL), an electron transport layer (ETL), an electron injection layer (EIL), and a cathode. One or two organic layers can be omitted as needed. By combining holes (Hole) and electrons (Electron) injected from the positive and negative electrodes on the organic thin film to form excitons (Exciton), when the excitons return from the excited state to the stable ground state, energy is released in the form of light, thus emitting light.

[0003] Based on the spin statistics theory, 25% singlet excitons and 75% triplet excitons will be generated in the organic light-emitting material under electro-driven. Traditional fluorescent materials can only utilize singlet excitons to return to the ground state (S 1 →S 0 ) through radiative transition to emit light, while triplet excitons are usually deactivated by non-radiative transition. Therefore, the maximum value of the internal quantum efficiency (IQE) in its device is 25%. Phosphorescent metal complexes have a strong spin-orbit coupling effect due to the introduction of heavy metal atoms, significantly promoting the intersystem crossing process between singlet and triplet states, and can make full use of 25% singlet excitons and 75% triplet excitons to achieve 100% internal quantum conversion efficiency. However, phosphorescent metal complexes often contain heavy metal atoms such as iridium, platinum, and europium, and have problems such as high price, high toxicity, and environmental pollution.

[0004] Thermally activated delayed fluorescence (TADF) materials are the third generation of organic light-emitting materials after traditional fluorescent and phosphorescent materials. Such materials generally have a small singlet-triplet energy level difference (ΔE ST) By utilizing the thermally activated reverse intersystem crossing (RISC) process, triplet excitons are transferred to singlet excitons to emit fluorescence, thereby achieving the full utilization of singlet and triplet excitons and realizing a 100% internal quantum efficiency. At the same time, such materials should also have a high photoluminescence quantum yield (PLQY) to promote the decay of singlet excitons in the form of light and improve the device efficiency. Currently, the main implementation approach for TADF molecules is to introduce electron donor (D) and electron acceptor (A) units, causing the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) to be separated, thereby achieving a small ΔE ST . However, due to the obvious vibrational relaxation of its excited state, this D-A structure exhibits a large Stokes shift, and the emission spectrum is relatively wide, with a full width at half maximum (FWHM) generally in the range of 70 - 100 nm. In practical applications, it is usually necessary to use a filter or construct an optical microcavity to improve the color purity, which not only increases the device assembly cost but also has an adverse effect on the device performance.

[0005] Therefore, how to develop a luminescent material that not only has the TADF effect but also has the narrow full width at half maximum spectral characteristic through reasonable chemical structure design to solve the defect of the wide full width at half maximum of the above materials has become one of the problems that many forward-looking researchers in the field urgently need to solve. Summary of the Invention

[0006] The present invention aims to solve the technical problem of the wide full width at half maximum of thermally activated delayed fluorescence materials in the prior art, and provides a diazaaromatic fused ring compound, a preparation method, and a light-emitting device. The diazaaromatic fused ring compound of the present invention not only has the TADF effect but also has the narrow full width at half maximum spectral characteristic.

[0007] To solve the above technical problems, the technical solution of the present invention is specifically as follows:

[0008] A diazaaromatic fused ring compound, whose structure is shown in formula (Ⅰ):

[0009]

[0010] X 1 and X 2 independently selected from a single bond (i.e., Ar 1 is directly connected to Ar 3 , Ar 2 is directly connected to Ar 4 by a single bond), O, S, Se, Te, N(R 1 ), B(R 1 ), C(R 1 R 2 ), Si(R 1 R 2 ), C=O, O=S=O or (R 1)P = O;

[0011] Y 1 、Y 2 、Y 3 and Y 4 are independently selected from O, S, N(R 1 ), C(R 1 R 2 ), or one of the following structures:

[0012]

[0013] wherein, R a ~R d are independently selected from H, D, C1 - C30 linear alkyl, C3 - C30 branched alkyl, C1 - C30 ether chain, C1 - C30 thioether chain, C1 - C30 ester group chain or C3 - C30 cycloalkyl;

[0014] a, b, c and d are independently integers from 0 to 3;

[0015] Ar 1 ~Ar 4 are independently selected from C6 - C60 aryl or C5 - C60 heteroaryl, and the heteroatoms in the heteroaryl are selected from one or more of Si, Ge, N, P, O, S and Se;

[0016] R 1 、R 2 、R 3 and R 4 are independently selected from H, D, F, Cl, Br, I, -CN, -NO 2 、

[0017] C3 - C30 cycloalkyl, C3 - C30 cycloalkenyl, C2 - C30 heterocycloalkyl, C2 - C30 heterocycloalkenyl, C6 - C60 aryl or C5 - C60 heteroaryl, and the heteroatoms in the heterocycloalkyl, heterocycloalkenyl and heteroaryl are selected from one or more of Si, Ge, N, P, O, S and Se;

[0018] Said R 1 、R 2 and R 3 are independently selected from H, D, F, Cl, Br, I, CN, OH, SH, NH 2, a C1-C30 straight-chain alkyl group, a C3-C30 branched-chain alkyl group, a C1-C30 ether chain, a C1-C30 thioether chain, a C1-C30 ester group chain, a C3-C30 cycloalkyl group, a C3-C30 cycloalkenyl group, a C2-C30 heterocycloalkyl group, a C2-C30 heterocycloalkenyl group, a C6-C60 aryl group or a C4-C60 heteroaryl group; the heteroatoms in the heterocycloalkyl group, heterocycloalkenyl group and heteroaryl group are selected from one or more of Si, Ge, N, P, O, S and Se; or R 1 and R 2 are bridged by a single bond or a heteroatom, and the heteroatom is selected from one of Si, Ge, N, P, O, S and Se.

[0019] In the above technical solution, preferably, the Ar 1 ~Ar 4 are independently selected from one of the groups shown in A1-A20:

[0020]

[0021] Among them, L 1 , L 2 and L 3 are independently selected from H, D, F, Cl, Br, I, CN, OH, SH, NH 2 , a C1-C30 straight-chain alkyl group, a C3-C30 branched-chain alkyl group, a C1-C30 ether chain, a C1-C30 thioether chain, a C1-C30 ester group chain, a C3-C30 cycloalkyl group, a C3-C30 cycloalkenyl group, a C2-C30 heterocycloalkyl group, a C2-C30 heterocycloalkenyl group, a C6-C60 aryl group or a C4-C60 heteroaryl group; the heteroatoms in the heterocycloalkyl group, heterocycloalkenyl group and heteroaryl group are selected from one or more of Si, Ge, N, P, O, S and Se.

[0022] In the above technical solution, preferably, X 1 and X 2 are independently selected from a single bond (that is, Ar 1 is directly connected to Ar 3 , Ar 2 is directly connected to Ar 4 by a single bond), O, S, Se, N(R 1 ), C(R 1 R 2 ), Si(R 1 R 2 ).

[0023] In the above technical solution, preferably, the Y 1 , Y 2 , Y 3 and Y 4 are independently selected from one of the following structures:

[0024]

[0025] In the above technical solution, preferably, the diazaaromatic fused-ring compound has any one of the structures shown in Formula (A) to Formula (C):

[0026]

[0027]

[0028]

[0029]

[0030] A preparation method of a diazaaromatic fused-ring compound includes the following steps:

[0031] When Y 1 ~Y 4 are independently selected from O, the preparation method includes the following steps:

[0032] Under an argon atmosphere, place M-1 in a reaction flask, add dichloromethane and stir, then dropwise add oxalyl chloride and N,N-dimethylformamide to the reaction solution drop by drop. After the addition is complete, heat the reaction solution to reflux; after the reaction is completed, cool the reaction solution to room temperature, dropwise add tin tetrachloride to the reaction solution, and heat to reflux; after the reaction is completed, cool the reaction to room temperature, pour the reaction solution into ice water, and add sodium hydroxide solution to adjust the pH to 10, then extract with dichloromethane. The organic phase is washed with water and saturated sodium chloride solution respectively, the obtained organic phase is dried with anhydrous sodium sulfate, filtered by suction, and the solvent is removed by rotary evaporation under reduced pressure. The obtained crude product is purified by a chromatography column to obtain the diazaaromatic fused-ring compound shown in Formula (I) (such as the diazaaromatic fused-ring compounds shown in Formula (A) to Formula (B) exemplified above in the present invention);

[0033] When Y 1 ~Y 4 are independently selected from S, the preparation method includes the following steps:

[0034] Place the diazaaromatic fused-ring compound shown in Formula (I) prepared when Y 1 ~Y 4 are independently selected from O and Lawesson's reagent in a reaction flask, add toluene and stir to dissolve, bubble air into the reaction vessel, then heat the reaction solution to reflux. After the reaction is completed, cool to room temperature, and remove the reaction solvent by rotary evaporation under reduced pressure. The obtained crude product is purified by a chromatography column to obtain the diazaaromatic fused-ring compound shown in Formula (I) (such as the diazaaromatic fused-ring compounds shown in Formula (C-1) to Formula (C-6) exemplified above in the present invention);

[0035] When Y 1 ~Y 4 is independently selected from N(R 1 ) or C(R 1 R 2 ), the preparation method comprises the following steps:

[0036] Under an argon atmosphere, the diazaaromatic fused-ring compound represented by formula (I) prepared when Y 1 ~Y 4 is independently selected from O and R 1 -NH 2 or CH 2 (R 1 R 2 ) are placed in a reaction flask, a solvent is added and stirred to dissolve, an organic base is added to the reaction solution, then titanium tetrachloride is added dropwise under an ice-water bath condition. After the addition is complete, the temperature is raised to room temperature for reaction. After the reaction is completed, it is quenched with dilute sodium hydroxide solution, extracted with dichloromethane, the organic phase is dried with anhydrous sodium sulfate, and the crude product obtained by suction filtration is purified by a chromatography column to obtain the diazaaromatic fused-ring compound represented by formula (I) (such as the diazaaromatic fused-ring compounds represented by formula (C-7) to formula (C-18) exemplified above in the present invention);

[0037] When Y 1 ~Y 4 is independently selected from the following structures:

[0038]

[0039] The diazaaromatic fused-ring compound represented by formula (I) prepared when Y 1 ~Y 4 is independently selected from O and the compounds represented by formula (N-1) to (N-6) are respectively placed in a reaction flask, glacial acetic acid and acetic anhydride are added as a mixed solvent, the reaction is heated to reflux, after the reaction is completed, glacial acetic acid and acetic anhydride are removed by rotary evaporation under reduced pressure, the solid remaining in the reaction flask is dissolved in dichloromethane, then washed with water and saturated sodium chloride solution respectively, and the obtained crude product is purified by a chromatography column to obtain the diazaaromatic fused-ring compound represented by formula (I) (such as the diazaaromatic fused-ring compounds represented by formula (C-19) to formula (C-25) exemplified above in the present invention);

[0040]

[0041]

[0042] wherein all codes are as defined above.

[0043] In the above technical solution, preferably,

[0044] When Y1 ~Y 4 When Y is independently selected from O, the temperature of the reaction system is 35 - 45 °C, and the reaction duration is 18 - 24 h;

[0045] When Y 1 ~Y 4 is independently selected from S, the temperature of the reaction system is 100 - 120 °C, and the reaction duration is 0.5 - 3 h;

[0046] When Y 1 ~Y 4 is independently selected from N(R 1 ) or C(R 1 R 2 ), the temperature of the reaction system is 0 - 40 °C, and the reaction duration is 10 - 24 h;

[0047] When Y 1 ~Y 4 is independently selected from the following structures:

[0048]

[0049] the temperature of the reaction system is 110 - 150 °C, and the reaction duration is 8 - 24 h.

[0050] The present invention also provides an application of a diaza - aromatic fused - ring compound as a luminescent material, especially in an organic electroluminescent device.

[0051] The present invention has no particular limitation on the structure of the organic electroluminescent device. A conventional organic electroluminescent device well - known to those skilled in the art can be used. Those skilled in the art can select and adjust according to the application situation, quality requirements, and product requirements. For example, the organic electroluminescent device of the present invention includes an anode, a cathode, and an organic thin - film layer located between the anode and the cathode; the organic thin - film layer includes the diaza - aromatic fused - ring compound of the present invention. Further, the organic thin - film layer includes a light - emitting layer; the light - emitting layer includes the diaza - aromatic fused - ring compound of the present invention. The structure of the organic electroluminescent device of the present invention preferably specifically includes: a substrate; an anode disposed on the substrate; an organic thin - film layer disposed on the anode; and a cathode disposed on the organic thin - film layer.

[0052] The thickness of the substrate is preferably 0.3 - 0.7 mm, more preferably 0.4 - 0.6 mm; the present invention has no special limitation on the selection of the substrate. A substrate of a conventional organic electroluminescent device well - known to those skilled in the art can be used. Those skilled in the art can select and adjust according to the application situation, quality requirements, and product requirements. In the present invention, the substrate is preferably glass or plastic.

[0053] According to the present invention, the anode is preferably a material that is easy for hole injection, more preferably a conductive metal or a conductive metal oxide, and still more preferably indium tin oxide.

[0054] The organic thin film layer can be one layer or multiple layers, and at least one layer is a light-emitting layer; in the present invention, the organic thin film layer preferably includes a light-emitting layer; for example, the light-emitting layer includes the diazaaromatic condensed ring compounds represented by the above formulas (A) to (C); the diazaaromatic condensed ring compounds represented by the formulas (A) to (C) provided by the present invention directly form an organic electroluminescent layer as a light-emitting material.

[0055] The cathode is preferably a metal, including but not limited to calcium, magnesium, barium, aluminum, and silver, and preferably aluminum.

[0056] In order to improve the performance and efficiency of the device, the organic thin film layer between the anode and the light-emitting layer preferably further includes one or more of a hole injection layer, a hole transport layer, and an electron blocking layer. The organic thin film layer between the light-emitting layer and the cathode preferably further includes one or more of a hole blocking layer, an electron injection layer, and an electron transport layer. The present invention has no particular limitation on the materials and thicknesses of the hole injection layer, the hole transport layer, the electron blocking layer, the organic electroluminescent layer, the hole blocking layer, the electron injection layer, and the electron transport layer, and they can be selected and adjusted according to the materials and thicknesses well-known to those skilled in the art. The present invention has no particular limitation on the preparation processes of the electrodes, the hole injection layer, the hole transport layer, the electron blocking layer, the organic electroluminescent layer, the hole blocking layer, the electron injection layer, and the electron transport layer, and preferably vacuum evaporation, solution spin coating, solution blade coating, inkjet printing, offset printing, and stereolithography processes are used for preparation.

[0057] The present invention has no special limitation on the preparation method of the organic electroluminescent device, and it can be carried out according to the following method: forming an anode on the substrate; forming one or more organic thin film layers on the anode, which includes a light-emitting layer; forming a cathode on the organic thin film layer. For example, the light-emitting layer includes the diazaaromatic condensed ring compounds represented by (A) to (C).

[0058] The present invention can correspond the structures and materials of the organic electroluminescent device in the above preparation method, as well as the corresponding preferred principles, to the corresponding materials and structures, and the corresponding preferred principles in the foregoing organic electroluminescent device, and will not be elaborated herein one by one.

[0059] First, an anode is formed on a substrate. There are no special restrictions on the formation method of the anode in the present invention, and it can be formed according to the methods well-known to those skilled in the art. There are no special restrictions on the formation methods of the light-emitting layer and the organic thin-film layers below and above the light-emitting layer, and they can be formed on the anode by vacuum evaporation, solution spin coating, solution blade coating, inkjet printing, offset printing, or stereolithography. After the organic thin-film layer is formed, a cathode is prepared on its surface. There are no special restrictions on the formation method of the cathode in the present invention, and it is preferably a method well-known to those skilled in the art, including but not limited to vacuum deposition.

[0060] The beneficial effects of the present invention are as follows:

[0061] The diazaaromatic-fused ring compound provided by the present invention is shown in formula (I). Compared with the prior art, the present invention uses a diazaaromatic-fused ring unit as a light-emitting material. On the one hand, the rigid backbone structure of the diazaaromatic-fused ring compound can be used to reduce the degree of excited-state structural relaxation, thereby achieving a narrower full width at half maximum; on the other hand, the resonance effect between the electron-deficient group and the nitrogen atom is also used to achieve the separation of HOMO and LUMO, thereby achieving a smaller ΔE. ST and the TADF effect, and then achieving a high luminous efficiency. At the same time, by changing the types of aromatic rings or heteroaromatic rings contained in the fused-ring compound, the delayed fluorescence lifetime and the full width at half maximum can be further adjusted.

[0062] Experimental results show that when the diazaaromatic-fused ring compound of the present invention is used as the light-emitting layer of an electroluminescent device, a narrow electroluminescent full width at half maximum can be achieved without a filter and a microcavity structure, and a high external quantum efficiency of the device can also be achieved. Detailed implementation manners

[0063] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0064] All reagents used in the following examples are commercially available.

[0065] Example 1

[0066]

[0067]

[0068] In a 500 mL two-necked flask, add 1-1 (10.0 g, 34.2 mmol), 230 mL of pyridine and 100 mL of deionized water. Heat the reaction to 120 °C and add potassium permanganate (48.00 g, 303.00 mmol) in batches. React at 120 °C for 2 days. When the reaction temperature drops to about 80 °C, perform hot filtration while it is hot. Wash the filter residue several times with hot water at 80 °C. Evaporate the solvent from the obtained filtrate under reduced pressure. Immediately place the obtained solid and sodium hydroxide (20.00 g, 500.00 mmol) in a 250 mL two-necked flask, add 100 mL of deionized water, heat to reflux. After all the solids in the reaction flask have dissolved, add potassium permanganate (48.00 g, 303.00 mmol) in batches. Lower the reaction temperature to 90 °C and stir for 1 day. After the reaction is completed, cool to room temperature, slowly add 25 mL of absolute ethanol dropwise to the reaction flask to quench the unreacted potassium permanganate. Then filter the reaction mixture. Acidify the filtrate with 300 mL of 5 M hydrochloric acid solution and evaporate the solvent under reduced pressure. Subsequently, add 100 mL of acetone, stir at room temperature for 1 day, filter again, and concentrate the filtrate under reduced pressure to obtain the white solid product 1-2 (9.17 g, yield: 66%).

[0069] Elemental analysis of its structure (C 10 H 4 Br 2 O 8 ): Theoretical values: C, 29.16; H, 0.98; O, 31.07; Measured values: C, 29.15; H, 0.99; O, 31.05.

[0070] MALDI-TOF-MS: Theoretical value 409.7; Experimental value 409.8.

[0071] In a 500 mL two-necked flask, add 1-2 (9.17 g, 22.38 mmol), 190 mL of methanol and 38 mL of concentrated sulfuric acid. Stir at 65 °C for 1 week, and white solid will gradually form in the reaction flask. After the reaction is completed, cool the reaction to room temperature. Then filter the reaction mixture and wash it with cold methanol. The filter residue is the product 1-3. Evaporate a part of the methanol in the filtrate under reduced pressure, add dichloromethane and water for extraction. Wash the organic phase three times with deionized water (250 mL × 3), dry it with anhydrous sodium sulfate, filter, remove the solvent, and purify the obtained crude product by column chromatography. Finally, obtain the white solid product 1-3 (5.63 g, yield: 54%).

[0072] Elemental analysis of its structure (C 14 H 12 Br 2 O 8):Theoretical values: C, 35.93; H, 2.58; O, 27.35; Measured values: C, 35.92; H, 2.56; O, 27.35.

[0073] MALDI-TOF-MS: Theoretical value 465.9; Experimental value 465.8.

[0074] Under an argon atmosphere, 1-4 (4.00 g, 23.94 mmol), 1-3 (5.07 g, 10.88 mmol), anhydrous potassium carbonate (3.61 g, 26.11 mmol), copper(I) iodide (1.24 g, 6.53 mmol) and 30 mL of o-dichlorobenzene were added to a 100 mL two-necked flask. After stirring at 160 °C for 36 hours, it was cooled to room temperature. The reaction mixture was filtered by suction and washed several times with dichloromethane. Subsequently, the filtrate was concentrated under reduced pressure. The crude product obtained was purified by a chromatography column to obtain product 1-5 (1.81 g, yield: 26%).

[0075] Elemental analysis of its structure (C 38 H 28 N 2 O 8 ):Theoretical values: C, 71.24; H, 4.41; N, 4.37; O, 19.98; Measured values: C, 71.25 H, 4.42; N, 4.34; O, 19.99.

[0076] MALDI-TOF-MS: Theoretical value 640.1; Experimental value 640.2.

[0077] 1-5 (1.81 g, 2.83 mmol), 35 mL of tetrahydrofuran, 17 mL of methanol, 17 mL of water and sodium hydroxide (1.35 g, 33.96 mmol) were added to a 250 mL single-necked flask. After stirring at 80 °C for 16 hours, the reaction system changed from a suspension to a clear liquid. The reaction mixture was cooled to room temperature, the solvent was removed by rotary evaporation, and then 50 mL of water was added to suspend the solid in water. The pH was adjusted to 1 with concentrated hydrochloric acid. The suspension was filtered by suction and washed with 100 mL of deionized water. The filter cake was dried in a vacuum oven to obtain a yellow solid product 1-6 (1.65 g, yield: 100%), which was directly used in the next step without purification.

[0078] Under an argon atmosphere, 1-6 (1.65 g, 2.83 mmol) and 50 mL of dichloromethane were added to a 250 mL two-necked flask. Subsequently, oxalyl chloride (11.22 mL, 132.59 mmol) and N,N-dimethylformamide (2.85 mL, 36.81 mmol) were added dropwise in sequence. After the addition was complete, the mixture was stirred at 45 °C for 3 hours. The reaction was cooled to room temperature, and tin(IV) chloride (6.62 mL, 56.60 mmol) was added dropwise. After the addition was complete, the mixture was stirred at 45 °C for 21 hours. The reaction was cooled to room temperature, and under ice-water bath conditions, the pH was adjusted to 10 with 2 M sodium hydroxide solution. Then, 100 mL of dichloromethane was added for dilution, and it was washed three times with deionized water (100 mL × 3). After that, it was dried over anhydrous sodium sulfate. The concentrated solution obtained after removing the solvent from the organic phase was purified by a chromatography column to obtain product 1-7 (1.10 g, yield: 76%) (i.e., compound A-1).

[0079] Elemental analysis of its structure (C 34 H 12 N 2 O 4 ): Theoretical values: C, 79.69; H, 2.36; N, 5.47; O, 12.49; Measured values: C, 79.68; H, 2.38; N, 5.46; O, 12.48.

[0080] MALDI-TOF-MS: Theoretical value 512.1; Experimental value 512.1.

[0081] Example 2

[0082]

[0083] Under an argon atmosphere, 2-1 (4.00 g, 14.33 mmol), 1-3 (3.03 g, 6.51 mmol), anhydrous potassium carbonate (2.16 g, 15.62 mmol), copper(I) iodide (0.74 g, 3.91 mmol) and 30 mL of o-dichlorobenzene were added to a 100 mL two-necked flask. After stirring at 160 °C for 36 hours, it was cooled to room temperature. The reaction solution was filtered by suction and washed repeatedly with dichloromethane. Subsequently, the filtrate was concentrated under reduced pressure. The crude product obtained was purified by a chromatography column to obtain product 2-2 (1.63 g, yield: 29%).

[0084] Elemental analysis of its structure (C 54 H 60 N 2 O 8 ): Theoretical values: C, 74.98; H, 6.99; N, 3.24; O, 14.80; Measured values: C, 74.99; H, 6.98; N, 3.25; O, 14.79.

[0085] MALDI-TOF-MS: Theoretical value 864.3; Experimental value 864.4.

[0086] Add 2-2 (1.63 g, 1.89 mmol), 35 mL of tetrahydrofuran, 17 mL of methanol, 17 mL of water, and sodium hydroxide (0.91 g, 22.68 mmol) into a 250 mL single-necked flask. Stir at 80 °C for 16 hours. The reaction system changes from a suspension to a clear liquid. Cool the reaction solution to room temperature, rotary evaporate the solvent, then add 50 mL of water to suspend the solid in water, and adjust the pH to 1 with concentrated hydrochloric acid. Filter the suspension and wash it with 100 mL of deionized water. The filter cake is dried in a vacuum oven to obtain a yellow solid product 2-3 (1.53 g, Yield: 100%), which is directly used for the next step without purification.

[0087] Under an argon atmosphere, add 2-3 (1.53 g, 1.89 mmol) and 50 mL of dichloromethane into a 250 mL two-necked flask. Then, dropwise add oxalyl chloride (7.51 mL, 88.83 mmol) and N,N-dimethylformamide (1.69 mL, 24.57 mmol) successively drop by drop. After the addition, stir at 45 °C for 3 hours. Cool the reaction to room temperature, and dropwise add tin(IV) chloride (4.42 mL, 37.80 mmol). After the addition, stir at 45 °C for 21 hours. Cool the reaction to room temperature. Under an ice-water bath condition, adjust the pH to 10 with 2 M sodium hydroxide solution, then add 100 mL of dichloromethane for dilution, and wash with deionized water three times (100 mL × 3). Then dry with anhydrous sodium sulfate. The concentrated solution obtained after removing the solvent from the organic phase is purified by a chromatography column to obtain product 2-4 (1.11 g, Yield: 80%) (i.e., compound A-2).

[0088] Elemental analysis of its structure (C 50 H 44 N 2 O 4 ): Theoretical values: C, 81.50; H, 6.02; N, 3.80; O, 8.68; Measured values: C, 81.52; H, 6.04; N, 3.78; O, 8.66.

[0089] MALDI-TOF-MS: Theoretical value 736.3; Experimental value 736.3.

[0090] 1 1H NMR (400 MHz, CDCl 3 ): δ ppm 9.14 (s, 2H), 8.55 (s, 2H), 7.65 (s, 2H), 7.55 (s, 2H), 1.45 (s, 36H).

[0091] Example 3

[0092]

[0093] Under an argon atmosphere, 3-1 (4.00 g, 9.28 mmol), 1-3 (1.97 g, 4.22 mmol), anhydrous potassium carbonate (1.40 g, 10.13 mmol), copper(I) iodide (0.48 g, 2.53 mmol) and 30 mL of o-dichlorobenzene were added to a 100 mL two-necked flask. After stirring at 160 °C for 36 hours, it was cooled to room temperature. The reaction solution was filtered by suction and washed several times with dichloromethane. Subsequently, the filtrate was concentrated under reduced pressure. The obtained crude product was purified by a chromatography column to obtain product 3-2 (1.23 g, yield: 25%).

[0094] Elemental analysis of its structure (C 78 H 76 N 2 O 8 ): Theoretical values: C, 80.11; H, 6.55; N, 2.40; O, 10.94; Measured values: C, 80.10; H, 6.53; N, 2.42; O, 10.95.

[0095] MALDI-TOF-MS: Theoretical value 1168.6; Experimental value 1168.5.

[0096] 3-2 (1.23 g, 1.05 mmol), 35 mL of tetrahydrofuran, 17 mL of methanol, 17 mL of water and sodium hydroxide (0.51 g, 12.63 mmol) were added to a 250 mL single-necked flask. After stirring at 80 °C for 16 hours, the reaction system changed from a suspension to a clear liquid. The reaction solution was cooled to room temperature, the solvent was removed by rotary evaporation, and then 50 mL of water was added to suspend the solid in water. The pH was adjusted to 1 with concentrated hydrochloric acid. The suspension was filtered by suction and washed with 100 mL of deionized water. The filter cake was dried in a vacuum oven to obtain a yellow solid product 3-3 (1.17 g, yield: 100%), which was directly used for the next step without purification.

[0097] Under an argon atmosphere, 3-3 (1.17 g, 1.05 mmol) and 40 mL of dichloromethane were added to a 250 mL two-necked flask. Subsequently, oxalyl chloride (4.18 mL, 49.35 mmol) and N,N-dimethylformamide (0.94 mL, 13.65 mmol) were added dropwise in sequence. After the addition was completed, the mixture was stirred at 45 °C for 3 hours. The reaction was cooled to room temperature, and stannic chloride (2.46 mL, 21.00 mmol) was added dropwise. After the addition was completed, the mixture was stirred at 45 °C for 21 hours. The reaction was cooled to room temperature, and under the condition of an ice-water bath, the pH was adjusted to 10 with 2 M sodium hydroxide solution. Then, it was diluted with 100 mL of dichloromethane and washed three times with deionized water (100 mL × 3). After that, it was dried over anhydrous sodium sulfate. The concentrated solution obtained after removing the solvent from the organic phase was purified by a chromatography column to obtain the product 3-4 (0.82 g, yield: 75%) (i.e., compound A-3).

[0098] Elemental analysis of its structure (C 74 H 60 N 2 O 4 ): Theoretical values: C, 85.36; H, 5.81; N, 2.69; O, 6.15; Measured values: C, 85.35; H, 5.82; N, 2.67; O, 6.17.

[0099] MALDI-TOF-MS: Theoretical value 1040.5; Experimental value 1040.4.

[0100] Example 4

[0101]

[0102] Under an argon atmosphere, 4-1 (4.00 g, 19.69 mmol), 1-3 (4.17 g, 8.95 mmol), anhydrous potassium carbonate (2.97 g, 21.48 mmol), copper(I) iodide (1.02 g, 5.37 mmol) and 60 mL of o-dichlorobenzene were added to a 100 mL two-necked flask. After stirring at 160 °C for 36 hours, it was cooled to room temperature. The reaction solution was filtered by suction and washed multiple times with dichloromethane. Subsequently, the filtrate was concentrated under reduced pressure. The crude product obtained was purified by a chromatography column to obtain the product 4-2 (1.91 g, yield: 30%).

[0103] Elemental analysis of its structure (C 38 H 24 F 4 N 2 O 8 ): Theoretical values: C, 64.05; H, 3.39; N, 3.93; O, 17.96; Measured values: C, 64.03; H, 3.41; N, 3.95; O, 17.97.

[0104] MALDI-TOF-MS: Theoretical value 712.0; Experimental value 712.1.

[0105] Add 4-2 (1.91 g, 2.68 mmol), 70 mL of tetrahydrofuran, 34 mL of methanol, 34 mL of water and sodium hydroxide (1.29 g, 32.16 mmol) into a 250 mL single-necked flask. Stir at 80 °C for 16 hours. The reaction system changes from a suspension to a clear liquid. Cool the reaction solution to room temperature, rotary evaporate the solvent, then add 100 mL of water to suspend the solid in water, and adjust the pH to 1 with concentrated hydrochloric acid. Filter the suspension and wash it with 200 mL of deionized water. The filter residue is dried in a vacuum oven to obtain a yellow solid product 4-3 (1.76 g, Yield: 100%). This product is directly used for the next step without purification.

[0106] Under an argon atmosphere, add 4-3 (1.76 g, 2.68 mmol) and 80 mL of dichloromethane into a 250 mL two-necked flask. Then, dropwise add oxalyl chloride (10.66 mL, 125.96 mmol) and N,N-dimethylformamide (2.70 mL, 34.84 mmol) successively. After the addition is complete, stir at 45 °C for 3 hours. Cool the reaction to room temperature, and dropwise add stannic chloride (6.27 mL, 53.60 mmol). After the addition is complete, stir at 45 °C for 21 hours. Cool the reaction to room temperature. Under ice-water bath conditions, adjust the pH to 10 with 2 M sodium hydroxide solution, then add 200 mL of dichloromethane for dilution, and wash with deionized water three times (100 mL × 3). Then dry with anhydrous sodium sulfate. The concentrated solution obtained after removing the solvent from the organic phase is purified by a chromatography column to obtain product 4-4 (1.25 g, Yield: 80%) (i.e., compound A-5).

[0107] Elemental analysis of its structure (C 34 H 8 F 4 N 2 O 4 ): Theoretical values: C, 69.87; H, 1.38; N, 4.79; O, 10.95; Measured values: C, 69.85; H, 1.39; N, 4.77; O, 10.96.

[0108] MALDI-TOF-MS: Theoretical value 584.0; Experimental value 580.4.

[0109] Example 5

[0110]

[0111] Under an argon atmosphere, 5-1 (4.00 g, 23.66 mmol), 1-3 (5.01 g, 10.75 mmol), anhydrous potassium carbonate (3.57 g, 25.8 mmol), copper(I) iodide (1.23 g, 6.45 mmol) and 30 mL of o-dichlorobenzene were added to a 100 mL two-necked flask. After stirring at 160 °C for 36 hours, the reaction mixture was cooled to room temperature. The reaction solution was filtered by suction and washed several times with dichloromethane. Subsequently, the filtrate was concentrated under reduced pressure. The crude product obtained was purified by column chromatography to give product 5-2 (1.80 g, yield: 26%).

[0112] Elemental analysis of its structure (C 34 H 24 N 6 O 8 ): Theoretical values: C, 36.35; H, 3.75; N, 13.04; O, 19.86; Measured values: C, 36.36; H, 37.74; N, 13.05; O, 19.85.

[0113] MALDI-TOF-MS: Theoretical value 644.2; Experimental value 644.2.

[0114] 5-2 (1.80 g, 2.79 mmol), 35 mL of tetrahydrofuran, 17 mL of methanol, 17 mL of water and sodium hydroxide (1.34 g, 33.48 mmol) were added to a 250 mL single-necked flask. After stirring at 80 °C for 16 hours, the reaction system changed from a suspension to a clear liquid. The reaction solution was cooled to room temperature, and the solvent was removed by rotary evaporation. Then 50 mL of water was added to suspend the solid in water, and the pH was adjusted to 1 with concentrated hydrochloric acid. The suspension was filtered by suction and washed with 100 mL of deionized water. The filter cake was dried in a vacuum oven to obtain a yellow solid product 5-3 (1.64 g, yield: 100%), which was directly used in the next step without purification.

[0115] Under an argon atmosphere, 5-3 (1.64 g, 2.79 mmol) and 40 mL of dichloromethane were added to a 250 mL two-necked flask. Subsequently, oxalyl chloride (11.09 mL, 131.13 mmol) and N,N-dimethylformamide (2.46 mL, 36.27 mmol) were added dropwise in sequence. After the addition was complete, the mixture was stirred at 45 °C for 3 hours. The reaction was cooled to room temperature, and tin(IV) chloride (6.53 mL, 55.8 mmol) was added dropwise. After the addition was complete, the mixture was stirred at 45 °C for 21 hours. The reaction was cooled to room temperature, and under an ice-water bath condition, the pH was adjusted to 10 with 2 M sodium hydroxide solution. Then, it was diluted with 100 mL of dichloromethane and washed three times with deionized water (100 mL × 3). After that, it was dried over anhydrous sodium sulfate. The concentrated solution obtained after removing the solvent from the organic phase was purified by a chromatography column to obtain the product 5-4 (1.14 g, yield: 79%). (That is, compound A-9)

[0116] Elemental analysis of its structure (C 30 H 8 N 6 O 4 ): Theoretical values: C, 69.77; H, 1.56; N, 16.28; O, 12.39; Measured values: C, 69.78; H, 1.57; N, 16.27; O, 12.38.

[0117] MALDI-TOF-MS: Theoretical value 516.1; Experimental value 516.2.

[0118] Example 6

[0119]

[0120] Under an argon atmosphere, 6-1 (4.00 g, 14.98 mmol), 1-3 (3.17 g, 6.81 mmol), anhydrous potassium carbonate (2.26 g, 16.34 mmol), copper(I) iodide (0.78 g, 4.09 mmol) and 30 mL of o-dichlorobenzene were added to a 100 mL two-necked flask. After stirring at 160 °C for 36 hours, it was cooled to room temperature. The reaction solution was filtered by suction and washed multiple times with dichloromethane. Subsequently, the filtrate was concentrated under reduced pressure. The crude product obtained was purified by a chromatography column to obtain the product 6-2 (1.37 g, yield: 24%).

[0121] Elemental analysis of its structure (C 54 H 36 N 2 O 8 ): Theoretical values: C, 77.13; H, 4.32; N, 3.33; O, 15.22; Measured values: C, 77.14; H, 4.31; N, 3.32; O, 15.23.

[0122] MALDI-TOF-MS: Theoretical value 840.3; Experimental value 840.2.

[0123] Add 6-2 (1.37 g, 1.63 mmol), 35 mL of tetrahydrofuran, 17 mL of methanol, 17 mL of water, and sodium hydroxide (0.78 g, 19.56 mmol) into a 250 mL single-necked flask. Stir at 80 °C for 16 hours. The reaction system changes from a suspension to a clear liquid. Cool the reaction solution to room temperature, rotary evaporate the solvent, then add 50 mL of water to suspend the solid in water, and adjust the pH to 1 with concentrated hydrochloric acid. Filter the suspension and wash it with 100 mL of deionized water. The filter cake is dried in a vacuum oven to obtain a yellow solid product 6-3 (1.23 g, Yield: 100%), and this product is directly used for the next step without purification.

[0124] Under an argon atmosphere, add 6-3 (1.23 g, 1.63 mmol) and 40 mL of dichloromethane into a 250 mL two-necked flask. Then, dropwise add oxalyl chloride (6.48 mL, 76.61 mmol) and N,N-dimethylformamide (1.63 mL, 21.19 mmol) sequentially. After the addition is complete, stir at 45 °C for 3 hours. Cool the reaction to room temperature, dropwise add tin(IV) chloride (3.81 mL, 32.6 mmol). After the addition is complete, stir at 45 °C for 21 hours. Cool the reaction to room temperature. Under ice-water bath conditions, adjust the pH to 10 with 2 M sodium hydroxide solution, then add 100 mL of dichloromethane for dilution, and wash with deionized water three times (100 mL × 3). Then dry with anhydrous sodium sulfate. The concentrated solution obtained after removing the solvent from the organic phase is purified by a chromatography column to obtain product 6-4 (0.89 g, Yield: 77%) (i.e., compound A-12).

[0125] Elemental analysis of its structure (C 50 H 20 N 2 O 4 ): Theoretical values: C, 84.26; H, 2.83; N, 3.93; O, 8.98; Test values: C, 84.27; H, 2.82; N, 3.94; O, 8.99.

[0126] MALDI-TOF-MS: Theoretical value 712.1; Experimental value 712.2.

[0127] Example 7

[0128]

[0129] Under an argon atmosphere, 7-1 (4.00 g, 10.02 mmol), 1-3 (2.08 g, 4.55 mmol), anhydrous potassium carbonate (1.51 g, 10.92 mmol), copper(I) iodide (0.52 g, 2.73 mmol) and 30 mL of o-dichlorobenzene were added to a 100 mL two-necked flask. After stirring at 160 °C for 36 hours, the reaction mixture was cooled to room temperature. The reaction solution was filtered by suction and washed several times with dichloromethane. Subsequently, the filtrate was concentrated under reduced pressure. The crude product obtained was purified by column chromatography to obtain product 7-2 (1.26 g, yield: 25%).

[0130] Elemental analysis of its structure (C 72 H 56 N 2 O 8 ): Theoretical values: C, 80.42; H, 5.47; N, 2.53; O, 11.58; Measured values: C, 80.43; H, 5.47; N, 2.52; O, 11.58.

[0131] MALDI-TOF-MS: Theoretical value 1104.4; Experimental value 1104.3.

[0132] 7-2 (1.26 g, 1.14 mmol), 35 mL of tetrahydrofuran, 17 mL of methanol, 17 mL of water and sodium hydroxide (0.58 g, 13.68 mmol) were added to a 250 mL single-necked flask. After stirring at 80 °C for 16 hours, the reaction system changed from a suspension to a clear liquid. The reaction solution was cooled to room temperature, and the solvent was removed by rotary evaporation. Then 50 mL of water was added to suspend the solid in water, and the pH was adjusted to 1 with concentrated hydrochloric acid. The suspension was filtered by suction and washed with 100 mL of deionized water. The filter cake was dried in a vacuum oven to obtain a yellow solid product 7-3 (1.20 g, yield: 100%). This product was used directly in the next step without purification.

[0133] Under an argon atmosphere, 7-3 (1.20 g, 1.14 mmol) and 40 mL of dichloromethane were added to a 250 mL two-necked flask. Subsequently, oxalyl chloride (4.53 mL, 53.58 mmol) and N,N-dimethylformamide (1.02 mL, 14.82 mmol) were added dropwise in sequence. After the addition was complete, the mixture was stirred at 45 °C for 3 hours. The reaction was cooled to room temperature, and tin(IV) chloride (2.67 mL, 22.8 mmol) was added dropwise. After the addition was complete, the mixture was stirred at 45 °C for 21 hours. The reaction was cooled to room temperature, and under ice-water bath conditions, the pH was adjusted to 10 with 2 M sodium hydroxide solution. Then, 100 mL of dichloromethane was added for dilution, and it was washed three times with deionized water (100 mL × 3). After that, it was dried over anhydrous sodium sulfate. The concentrated solution obtained after removing the solvent from the organic phase was purified by a chromatography column to obtain the product 7-4 (0.88 g, yield: 79%) (i.e., compound A-18).

[0134] Elemental analysis of its structure (C 70 H 44 N 2 O 4 ): Theoretical values: C, 86.04; H, 4.54; N, 2.87; O, 6.55; Measured values: C, 86.05; H, 4.53; N, 2.884; O, 6.54.

[0135] MALDI-TOF-MS: Theoretical value 976.3; Experimental value 976.3.

[0136] Example 8

[0137]

[0138] Under an argon atmosphere, 8-1 (4.00 g, 21.97 mmol), 1-3 (4.65 g, 9.99 mmol), anhydrous potassium carbonate (3.31 g, 23.78 mmol), copper(I) iodide (1.14 g, 5.99 mmol) and 30 mL of o-dichlorobenzene were added to a 100 mL two-necked flask. After stirring at 160 °C for 36 hours, it was cooled to room temperature. The reaction solution was filtered by suction and washed repeatedly with dichloromethane. Subsequently, the filtrate was concentrated under reduced pressure. The crude product obtained was purified by a chromatography column to obtain the product 8-2 (1.95 g, yield: 29%).

[0139] Elemental analysis of its structure (C 38 H 28 N 2 O 10 ): Theoretical values: C, 67.85; H, 4.20; N, 4.16; O, 23.79; Measured values: C, 67.64; H, 4.21; N, 4.15; O, 23.80.

[0140] MALDI-TOF-MS: Theoretical value 672.2; Experimental value 672.2.

[0141] Add 8-2 (1.95 g, 2.90 mmol), 35 mL of tetrahydrofuran, 17 mL of methanol, 17 mL of water and sodium hydroxide (0.93 g, 23.37 mmol) into a 250 mL single-necked flask, stir at 80 °C for 16 hours. The reaction system changes from a suspension to a clear liquid. Cool the reaction solution to room temperature, rotary evaporate the solvent, then add 50 mL of water to suspend the solid in water, and adjust the pH to 1 with concentrated hydrochloric acid. Filter the suspension and wash it with 100 mL of deionized water. The filter residue is dried in a vacuum oven to obtain a yellow solid product 8-3 (1.79 g, yield: 100%). This product is directly used for the next step without purification.

[0142] Under an argon atmosphere, add 8-3 (1.79 g, 2.90 mmol) and 40 mL of dichloromethane into a 250 mL two-necked flask. Then, dropwise add oxalyl chloride (11.55 mL, 136.55 mmol) and N,N-dimethylformamide (2.59 mL, 37.7 mmol) successively. After the addition is completed, stir at 45 °C for 3 hours. Cool the reaction to room temperature, dropwise add stannic chloride (6.78 mL, 58.00 mmol). After the addition is completed, stir at 45 °C for 21 hours. Cool the reaction to room temperature. Under ice-water bath conditions, adjust the pH to 10 with 2 M sodium hydroxide solution, then add 100 mL of dichloromethane for dilution, and wash with deionized water three times (100 mL × 3). Then dry with anhydrous sodium sulfate. The concentrated solution obtained after removing the solvent from the organic phase is purified by a chromatography column to obtain product 8-4 (1.17 g, yield: 74%) (i.e., compound B-1).

[0143] Elemental analysis of its structure (C 34 H 12 N 2 O 6 ): Theoretical values: C, 70.00; H, 2.22; N, 5.15; O, 17.63; Test values: C, 70.01; H, 2.21; N, 5.14; O, 17.74.

[0144] MALDI-TOF-MS: Theoretical value 544.1; Experimental value 544.0.

[0145] Example 9

[0146]

[0147] Under argon atmosphere, 9-1 (4.00 g, 19.13 mmol), 1-3 (4.05 g, 8.69 mmol), anhydrous potassium carbonate (2.88 g, 20.86 mmol), cuprous iodide (0.99 g, 5.21 mmol) and 30 mL of o-dichlorobenzene were added to a 100 mL two-necked bottle. The mixture was stirred at 160 ° C for 36 hours and then cooled to room temperature. The reaction solution was filtered and washed with dichloromethane several times. The filtrate was then concentrated under reduced pressure. The crude product was purified by chromatography to obtain product 9-2 (1.83 g, yield: 29%).

[0148] Elemental analysis of its structure (C 44 H 40 N 2 O 8 ): Theoretical value: C, 72.91; H, 5.56; N, 3.87; O, 17.66; Test value: C, 72.92; H, 5.55; N, 3.88; O, 17.65.

[0149] MALDI-TOF-MS: theoretical value 724.3; experimental value 724.3.

[0150] 9-2 (1.83 g, 2.52 mmol), 35 mL of tetrahydrofuran, 17 mL of methanol, 17 mL of water and sodium hydroxide (1.21 g, 30.24 mmol) were added to a 250 mL single-mouth bottle and stirred at 80 ° C for 16 hours. The reaction system changed from a suspension to a clear liquid. The reaction solution was cooled to room temperature, the solvent was spun out, and 50 mL of water was added to suspend the solid in the water, and the pH was adjusted to 1 with concentrated hydrochloric acid. The suspension was filtered and washed with 100 mL of deionized water, and the filter residue was dried in a vacuum oven to obtain a yellow solid product 9-3 (1.62 g, yield: 100%), which was directly used in the next step without purification.

[0151] Under an argon atmosphere, 9-3 (1.62 g, 2.52 mmol) and 40 mL of dichloromethane were added to a 250 mL two-necked flask. Subsequently, oxalyl chloride (10.02 mL, 118.44 mmol) and N,N-dimethylformamide (2.25 mL, 32.76 mmol) were added dropwise in sequence. After the addition was complete, the mixture was stirred at 45 °C for 3 hours. The reaction was cooled to room temperature, and tin(IV) chloride (5.89 mL, 50.40 mmol) was added dropwise. After the addition was complete, the mixture was stirred at 45 °C for 21 hours. The reaction was cooled to room temperature, and under ice-water bath conditions, the pH was adjusted to 10 with 2 M sodium hydroxide solution. Then, 100 mL of dichloromethane was added for dilution, and it was washed three times with deionized water (100 mL × 3). After that, it was dried over anhydrous sodium sulfate. The concentrated solution obtained after removing the solvent from the organic phase was purified by a chromatography column to obtain the product 9-4 (1.14 g, yield: 76%) (i.e., compound B-5).

[0152] Elemental analysis of its structure (C 40 H 24 N 2 O 4 ): Theoretical values: C, 80.52; H, 4.05; N, 4.70; O, 10.73; Measured values: C, 80.53; H, 4.04; N, 4.71; O, 10.74.

[0153] MALDI-TOF-MS: Theoretical value 596.2; Experimental value 596.1.

[0154] Example 10

[0155]

[0156] Under an argon atmosphere, 10-1 (4.00 g, 20.51 mmol), 1-3 (4.34 g, 9.32 mmol), anhydrous potassium carbonate (3.09 g, 22.37 mmol), copper(I) iodide (1.06 g, 5.59 mmol) and 30 mL of o-dichlorobenzene were added to a 100 mL two-necked flask. After stirring at 160 °C for 36 hours, it was cooled to room temperature. The reaction solution was filtered by suction and washed multiple times with dichloromethane. Subsequently, the filtrate was concentrated under reduced pressure. The crude product obtained was purified by a chromatography column to obtain the product 10-2 (1.69 g, yield: 26%).

[0157] Elemental analysis of its structure (C 40 H 28 N 2 O 10 ): Theoretical values: C, 68.96; H, 4.05; N, 4.02; O, 22.97; Measured values: C, 68.97; H, 4.04; N, 4.03; O, 22.96.

[0158] MALDI-TOF-MS: Theoretical value 696.2; Experimental value 696.2.

[0159] Add 10-2 (1.69 g, 2.42 mmol), 35 mL of tetrahydrofuran, 17 mL of methanol, 17 mL of water, and sodium hydroxide (1.21 g, 30.36 mmol) into a 250 mL single-necked flask. Stir at 80 °C for 16 hours. The reaction system changes from a suspension to a clear liquid. Cool the reaction solution to room temperature, rotary evaporate the solvent, then add 50 mL of water to suspend the solid in water, and adjust the pH to 1 with concentrated hydrochloric acid. Filter the suspension and wash it with 100 mL of deionized water. The filter cake is dried in a vacuum oven to obtain the yellow solid product 10-3 (1.76 g, yield: 100%), which is directly used for the next step without purification.

[0160] Under an argon atmosphere, add 10-3 (1.76 g, 2.53 mmol) and 40 mL of dichloromethane into a 250 mL two-necked flask. Then, dropwise add oxalyl chloride (10.06 mL, 118.91 mmol) and N,N-dimethylformamide (2.26 mL, 32.89 mmol) successively. After the addition is complete, stir at 45 °C for 3 hours. Cool the reaction to room temperature, dropwise add tin(IV) chloride (5.92 mL, 50.6 mmol). After the addition is complete, stir at 45 °C for 21 hours. Cool the reaction to room temperature. Under ice-water bath conditions, adjust the pH to 10 with 2 M sodium hydroxide solution, then add 100 mL of dichloromethane for dilution, and wash with deionized water three times (100 mL × 3). Then dry with anhydrous sodium sulfate. The concentrated solution obtained after removing the solvent from the organic phase is purified by a chromatography column to obtain the product 10-4 (1.03 g, yield: 75%) (i.e., compound B-7).

[0161] Elemental analysis of its structure (C 36 H 12 N 2 O 6 ): Theoretical values: C, 76.06; H, 2.31; N, 4.94; O, 16.89; Measured values: C, 76.07; H, 2.30; N, 4.95; O, 16.90.

[0162] MALDI-TOF-MS: Theoretical value 568.1; Experimental value 568.2.

[0163] Example 11

[0164]

[0165] Under an argon atmosphere, 11-1 (4.00 g, 15.50 mmol), 1-3 (3.25 g, 6.97 mmol), anhydrous potassium carbonate (2.29 g, 16.56 mmol), copper(I) iodide (0.79 g, 4.18 mmol) and 30 mL of o-dichlorobenzene were added to a 100 mL two-necked flask. After stirring at 160 °C for 36 hours, the mixture was cooled to room temperature. The reaction solution was filtered by suction and washed several times with dichloromethane. Subsequently, the filtrate was concentrated under reduced pressure. The crude product obtained was purified by column chromatography to obtain product 11-2 (1.49 g, yield: 26%).

[0166] Elemental analysis of its structure (C 50 H 28 N 4 O 8 ): Theoretical values: C, 72.98; H, 4.65; N, 6.81; O, 15.55; Measured values: C, 72.95; H, 4.65; N, 8.04; O, 15.55.

[0167] MALDI-TOF-MS: Theoretical value 822.3; Experimental value 822.2.

[0168] 11-2 (1.49 g, 1.81 mmol), 35 mL of tetrahydrofuran, 17 mL of methanol, 17 mL of water and sodium hydroxide (0.87 g, 21.74 mmol) were added to a 250 mL single-necked flask. After stirring at 80 °C for 16 hours, the reaction system changed from a suspension to a clear liquid. The reaction solution was cooled to room temperature, the solvent was removed by rotary evaporation, and then 50 mL of water was added to suspend the solid in water. The pH was adjusted to 1 with concentrated hydrochloric acid. The suspension was filtered by suction and washed with 100 mL of deionized water. The filter cake was dried in a vacuum oven to obtain a yellow solid product 11-3 (1.39 g, yield: 100%). This product was used directly in the next step without purification.

[0169] Under an argon atmosphere, 11-3 (1.39 g, 1.81 mmol) and 40 mL of dichloromethane were added to a 250 mL two-necked flask. Subsequently, oxalyl chloride (7.20 mL, 85.07 mmol) and N,N-dimethylformamide (1.62 mL, 25.53 mmol) were added dropwise in sequence. After the addition was complete, the mixture was stirred at 45 °C for 3 hours. The reaction was cooled to room temperature, and tin(IV) chloride (4.24 mL, 36.20 mmol) was added dropwise. After the addition was complete, the mixture was stirred at 45 °C for 21 hours. The reaction was cooled to room temperature, and under an ice-water bath condition, the pH was adjusted to 10 with 2 M sodium hydroxide solution. Then, 100 mL of dichloromethane was added for dilution, and the mixture was washed three times with deionized water (100 mL × 3). After that, it was dried over anhydrous sodium sulfate. The concentrated solution obtained after removing the solvent from the organic phase was purified by a chromatography column to obtain the product 11-4 (0.94 g, yield: 75%) (i.e., compound B-10).

[0170] Elemental analysis of its structure (C 46 H 22 N 4 O 4 ): Theoretical values: C, 79.53; H, 3.19; N, 8.06; O, 9.21; Measured values: C, 79.52.; H, 3.17; N, 9.85; O, 9.20.

[0171] MALDI-TOF-MS: Theoretical value 694.2; Experimental value 694.2.

[0172] Example 12

[0173]

[0174] Under an argon atmosphere, 12-1 (4.00 g, 12.08 mmol), 1-3 (2.56 g, 5.49 mmol), anhydrous potassium carbonate (1.82 g, 13.18 mmol), copper(I) iodide (0.63 g, 3.30 mmol) and 30 mL of o-dichlorobenzene were added to a 100 mL two-necked flask. After stirring at 160 °C for 36 hours, it was cooled to room temperature. The reaction solution was filtered by suction and washed multiple times with dichloromethane. Subsequently, the filtrate was concentrated under reduced pressure. The crude product obtained was purified by a chromatography column to obtain the product 12-2 (1.54 g, yield: 23%).

[0175] Elemental analysis of its structure (C 64 H 44 N 2 O 8 ): Theoretical values: C, 79.32; H, 4.58; N, 2.89; O, 13.21; Measured values: C, 79.31; H, 4.59; N, 2.88; O, 13.22.

[0176] MALDI-TOF-MS: Theoretical value 968.3; Experimental value 968.2.

[0177] Add 12-2 (1.28 g, 1.32 mmol), 35 mL of tetrahydrofuran, 17 mL of methanol, 17 mL of water, and sodium hydroxide (0.63 g, 15.86 mmol) to a 250 mL single-necked flask. Stir at 80 °C for 16 hours. The reaction system changes from a suspension to a clear liquid. Cool the reaction solution to room temperature, rotary evaporate the solvent, then add 50 mL of water to suspend the solid in water, and adjust the pH to 1 with concentrated hydrochloric acid. Filter the suspension by suction and wash with 100 mL of deionized water. The filter cake is dried in a vacuum oven to obtain a yellow solid product 12-3 (1.20 g, Yield: 100%), which is directly used for the next step without purification.

[0178] Under an argon atmosphere, add 12-3 (1.20 g, 1.32 mmol) and 40 mL of dichloromethane to a 250 mL two-necked flask. Then, dropwise add oxalyl chloride (5.25 mL, 62.04 mmol) and N,N-dimethylformamide (1.18 mL, 17.16 mmol) sequentially. After the addition is complete, stir at 45 °C for 3 hours. Cool the reaction to room temperature, dropwise add tin(IV) chloride (3.09 mL, 26.40 mmol). After the addition is complete, stir at 45 °C for 21 hours. Cool the reaction to room temperature. Under an ice-water bath condition, adjust the pH to 10 with 2 M sodium hydroxide solution, then add 100 mL of dichloromethane for dilution, and wash with deionized water three times (100 mL × 3). Then dry with anhydrous sodium sulfate. The concentrated solution obtained after removing the solvent from the organic phase is purified by a chromatography column to obtain product 12-4 (1.11 g, Yield: 78%) (i.e., compound B-12).

[0179] Elemental analysis of its structure (C 60 H 28 N 2 O 4 ): Theoretical values: C, 85.70; H, 3.36; N, 3.33; O, 7.61; Measured values: C, 85.71; H, 3.35; N, 3.34; O, 7.60.

[0180] MALDI-TOF-MS: Theoretical value 840.2; Experimental value 840.2.

[0181] Example 13

[0182]

[0183] 1-7 (2.00 g, 3.91 mmol) and Lawson's reagent (5.00 g, 12.36 mmol) were dissolved in 100 mL of toluene. The reaction solution was degassed with argon for 30 minutes, and then heated to 110 °C and stirred for 1 h. After the reaction was completed, it was cooled to room temperature, and the solvent was removed under vacuum. The crude product was purified by column chromatography to obtain product 13-1 (1.53 g, yield: 68%) (i.e., compound C-1).

[0184] Elemental analysis of its structure (C 34 H 12 N 2 S 4 ): Theoretical values: C, 70.81; H, 2.09; N, 4.86; S, 22.24; Measured values: C, 70.80; H, 2.08; N, 4.87; S, 22.25.

[0185] MALDI-TOF-MS: Theoretical value 576.0; Experimental value 576.1.

[0186] Example 14

[0187]

[0188] 9-4 (2.00 g, 3.35 mmol) and Lawson's reagent (4.29 g, 10.60 mmol) were dissolved in 100 mL of toluene. The reaction solution was degassed with argon for 30 minutes, and then heated to 110 °C and stirred for 1 h. After the reaction was completed, it was cooled to room temperature, and the solvent was removed under vacuum. The crude product was purified by column chromatography to obtain product 14-1 (1.50 g, yield: 68%) (i.e., compound C-6).

[0189] Elemental analysis of its structure (C 40 H 24 N 2 S 4 ): Theoretical values: C, 72.70; H, 3.66; N, 4.24; S, 19.40; Measured values: C, 72.72; H, 3.68; N, 4.20; S, 19.40.

[0190] MALDI-TOF-MS: Theoretical value 660.1; Experimental value 660.1.

[0191] Example 15

[0192]

[0193] In a 100 mL round-bottom flask, 1-7 (2.00 g, 3.91 mmol) and 15-1 (1.75 g, 18.79 mmol) were successively added to the solution with 40 mL of dichloromethane and triethylamine (1.19 g, 11.73 mmol). Then the reactants were cooled to 0 °C, and titanium tetrachloride (0.45 g, 2.45 mmol) was added dropwise to the solution, and the reaction mixture was stirred at room temperature until TLC showed complete conversion of 1-7. After the reaction was completed, the mixture was quenched with 10% NaOH solution and filtered. The organic layer was washed with saturated NaHCO 3 , saturated NaCl, and dried over Na 2 SO 4 . The organic layer was concentrated under reduced pressure, and the crude mixture was purified by column chromatography on silica gel (treated with Et 3 N) to give the product 15-2 (2.25 g, yield: 71%) (i.e., compound C-7).

[0194] Elemental analysis of its structure (C 58 H 32 N 6 ): Theoretical values: C, 85.69; H, 3.97; N, 10.34;; Measured values: C, 85.68; H, 3.98; N, 10.34.

[0195] MALDI-TOF-MS: Theoretical value 812.3; Experimental value 812.2.

[0196] Example 16

[0197]

[0198] In a 100 mL round-bottom flask, 1-7 (2.00 g, 3.91 mmol) and malononitrile (1.25 g, 18.79 mmol) were successively added to the solution with 40 mL of DCM and triethylamine (1.19 g, 11.73 mmol). Then the reactants were cooled to 0 °C, titanium tetrachloride (0.45 g, 2.45 mmol) was added dropwise to the solution, and the reaction mixture was stirred at room temperature until TLC showed complete conversion of 1-7. After the reaction was completed, the mixture was quenched with 10% NaOH solution and filtered. The organic layer was washed with saturated NaHCO 3 , saturated NaCl, and dried over Na 2 SO 4 . The organic layer was concentrated under reduced pressure, and the crude mixture was purified by column chromatography on silica gel (treated with Et 3 N) to give the product 16-1 (1.90 g, yield: 68%) (i.e., compound C-8).

[0199] Elemental analysis of its structure (C 46 H12 N 10 ): Theoretical values: C, 78.41; H, 1.71; N, 19.88;; Measured values: C, 78.42; H, 1.71; N, 19.87.

[0200] MALDI-TOF-MS: Theoretical value 704.1; Experimental value 704.1.

[0201] Example 17

[0202]

[0203] In a 100 mL round-bottom flask, 4-4 (2.00 g, 3.42 mmol) and malononitrile (0.54 g, 8.21 mmol) were successively added to the solution with 40 mL of DCM and triethylamine (1.04 g, 10.26 mmol). Then the reaction mixture was cooled to 0 °C, and titanium tetrachloride (0.39 g, 2.05 mmol) was added dropwise to the solution, and the reaction mixture was stirred at room temperature until TLC showed complete conversion of 4-4. After the reaction was completed, the mixture was quenched with 10% NaOH solution and filtered. The organic layer was washed with saturated NaHCO 3 , saturated NaCl, and dried over Na 2 SO 4 . The organic layer was concentrated under reduced pressure, and the crude mixture was purified by silica gel (treated with Et 3 N) column chromatography to obtain product 17-1 (1.83 g, yield: 69%) (i.e., compound C-9).

[0204] Elemental analysis of its structure (C 46 H 8 F 4 N 10 ): Theoretical values: C, 71.14; H, 1.04; N, 18.04; Measured values: C, 71.15; H, 1.03; N, 18.06.

[0205] MALDI-TOF-MS: Theoretical value 776.1; Experimental value 776.2.

[0206] Example 18

[0207]

[0208] In a 100 mL round-bottom flask, 9-4 (2.00 g, 3.35 mmol) and malononitrile (1.07 g, 16.25 mmol) were successively added to the solution with 40 mL of DCM and triethylamine (1.40 mL, 10.05 mmol). Then the reactants were cooled to 0 °C, and titanium tetrachloride (0.39 g, 2.10 mmol) was added dropwise to the solution, and the reaction mixture was stirred at room temperature until TLC showed complete conversion of 9-4. After the reaction was completed, the mixture was quenched with 10% NaOH solution and filtered. The organic layer was washed with saturated NaHCO 3 , saturated NaCl, and dried over Na 2 SO 4 . The organic layer was concentrated under reduced pressure, and the crude mixture was purified by column chromatography on silica gel (treated with Et 3 N) to give product 18-1 (1.80 g, yield: 68%). (i.e., compound C-13)

[0209] Elemental analysis of its structure (C 52 H 24 N 10 ): Theoretical values: C, 79.18; H, 3.07; N, 17.76;; Test values C, 79.19; H, 3.08; N, 17.74.

[0210] MALDI-TOF-MS: Theoretical value 788.2; Experimental value 788.2.

[0211] Example 19

[0212]

[0213] In a 100 mL round-bottom flask, 1-7 (2.00 g, 3.91 mmol) and ethyl cyanoacetate (2.13 g, 18.79 mmol) were successively added to the solution with 40 mL of DCM and triethylamine (1.19 g, 11.73 mmol). Then the mixture was cooled to 0 °C, and titanium tetrachloride (0.45 g, 2.45 mmol) was added dropwise to the solution, and the reaction mixture was stirred at room temperature until TLC showed complete conversion of ethyl cyanoacetate. After the reaction was completed, the mixture was quenched with 10% NaOH solution and filtered. The organic layer was washed with saturated NaHCO 3 , saturated NaCl, and dried over Na 2 SO 4 . The organic layer was concentrated under reduced pressure, and the crude mixture was purified by column chromatography on silica gel (treated with Et 3 N) to give product 19-1 (2.37 g, yield: 68%) (i.e., compound C-17).

[0214] Elemental analysis of its structure (C54 H 32 N 6 O 8 ):Theoretical values: C, 72.64; H, 3.61; N, 9.42; O, 14.33;; Measured values: C, 72.65; H, 3.60; N, 9.43; O, 14.32.

[0215] MALDI-TOF-MS: Theoretical value 892.2; Experimental value 892.3.

[0216] Example 20

[0217]

[0218] In a 250 mL round-bottom flask, 1-7 (2.00 g, 3.91 mmol) and 20-1 (7.32 g, 46.92 mmol) were successively dissolved in 80 mL of acetic acid and 80 mL of acetic anhydride and refluxed overnight. Acetic acid and acetic anhydride were removed under vacuum, and the crude mixture was dissolved in DCM, washed twice with water, and once with saturated sodium bicarbonate. The product 20-2 (2.16 g, yield: 51%) (i.e., compound C-19) was obtained by purification.

[0219] Elemental analysis of its structure (C 54 H 32 N 6 O 4 S 8 ):Theoretical values: C, 59.76; H, 2.97; N, 7.74; O, 5.90; S, 23.63; Measured values: C, 59.77; H, 2.96; N, 7.73; O, 5.90; S, 23.64.

[0220] MALDI-TOF-MS: Theoretical value 1084.0; Experimental value 1084.1.

[0221] Example 21

[0222]

[0223] Compound 21-1 was synthesized according to Example 8, except that compound 8-1 was replaced with

[0224] In a 250 mL round-bottom flask, 21-1 (2.00 g, 3.47 mmol) and 21-2 (6.08 g, 41.64 mmol) were successively dissolved in 80 mL of acetic acid and 80 mL of acetic anhydride and refluxed overnight. Acetic acid and acetic anhydride were removed under vacuum, and the crude mixture was dissolved in DCM, washed twice with water, and once with saturated sodium bicarbonate. The product 21-3 (2.08 g, yield: 55%) (i.e., compound C-24) was obtained by purification.

[0225] Elemental analysis of its structure (C 70 H 28 N 2 O 8 S 2 ): Theoretical values: C, 77.20; H, 2.59; N, 2.57; O, 11.75; S, 5.89; Measured values: C, 77.21; H, 2.60; N, 2.57; O, 11.73; S, 5.91.

[0226] MALDI-TOF-MS: Theoretical value 1088.1; Experimental value 1088.1.

[0227] See Table 1. Table 1 shows the photophysical properties of the diazaaromatic-fused ring compounds prepared in the examples of the present invention.

[0228] Table 1 Photophysical properties of the diazaaromatic-fused ring compounds prepared in the examples of the present invention

[0229]

[0230] Note: The delayed fluorescence lifetime in the table was obtained by doping the compound in polystyrene at a concentration of 1 wt% to make the test sample and measuring it with a time-resolved fluorescence spectrometer. The test instrument was Edinburgh fluorescencespectrometer (FLS-1000, UK).

[0231] As can be seen from Table 1, the diazaaromatic-fused ring compounds in the examples provided by the present invention exhibit a delayed fluorescence effect, and their delayed fluorescence lifetimes are in the range of 48 - 85 μs.

[0232] Device example

[0233] The process of preparing the device with the organic light-emitting layer by vacuum evaporation is as follows: On indium tin oxide loaded on a glass substrate, 4×10 -4Under a vacuum of Pa, TAPC, TCTA, EML (the invented luminescent compound is co-evaporated with SIMCP2 and DPAc-DtCzBN in a mass ratio of 1:2:7), TmPyPB, and LiF / Al cathode are sequentially deposited to obtain an organic electroluminescent device, where TAPC and TmPyPB serve as the hole transport layer and the electron transport layer respectively, and TCTA is the exciton blocking layer, and its structural formula is shown as follows:

[0234]

[0235] The specific device structure (device structure A) of the device prepared by the vacuum evaporation process is:

[0236] ITO / TAPC(50nm) / TCTA(5nm) / EML(30nm) / TmPyPB(30nm) / LiF(0.8nm) / Al(100nm).

[0237] The process of preparing the device with the organic light-emitting layer by solution processing is as follows: Poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid) (PEDOT:PSS) is spin-coated on indium tin oxide loaded on a glass substrate and annealed at 120 °C for 30 minutes. Subsequently, a toluene solution of the invented luminescent compound mixed with SIMCP2 and DPAc-DtCzBN in a mass ratio of 1:2:7 is spin-coated at a speed of 1500 rpm for 1 minute and annealed at 80 °C for 30 minutes. Then, under a vacuum of 4×10 -4 Pa, TSPO1, TmPyPB, and LiF / Al cathode are sequentially deposited to obtain an organic electroluminescent device, where TSPO1 and TmPyPB serve as the hole blocking layer, the electron transport layer, and the host material respectively, and its structural formula is shown as follows:

[0238]

[0239] The specific device structure (device structure B) of the device prepared by the solution processing is:

[0240] ITO / PEDOT:PSS(40nm) / EML(30nm) / TSPO1(8nm) / TmPyPB(42nm) / LiF(1nm) / Al(100nm).

[0241] Example 22

[0242] Taking the diazaaromatic fused ring compound A-1 as the implementation object, the diazaaromatic fused ring compound A-1, SIMCP2, and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. The organic light-emitting layer adopts the solution processing technology, and an organic electroluminescent device is prepared using the structure described in "device structure B", and the obtained device is tested.

[0243] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with the diazaaromatic fused-ring compound A-1 provided by the present invention.

[0244] Example 23

[0245] Using the diazaaromatic fused-ring compound A-2 as the implementation object, the diazaaromatic fused-ring compound A-2, IMCP2, and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. The organic light-emitting layer is prepared by a vacuum evaporation process, and an organic electroluminescent device is prepared using the structure described in "Device Structure A", and the obtained device is tested.

[0246] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with the diazaaromatic fused-ring compound A-2 provided by the present invention.

[0247] Example 24

[0248] Using the diazaaromatic fused-ring compound A-3 as the implementation object, the diazaaromatic fused-ring compound A-3, IMCP2, and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. The organic light-emitting layer is prepared by a vacuum evaporation process, and an organic electroluminescent device is prepared using the structure described in "Device Structure A", and the obtained device is tested.

[0249] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with the diazaaromatic fused-ring compound A-3 provided by the present invention.

[0250] Example 25

[0251] Using the diazaaromatic fused-ring compound A-5 as the implementation object, the diazaaromatic fused-ring compound A-5, IMCP2, and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. The organic light-emitting layer is prepared by a solution processing process, and an organic electroluminescent device is prepared using the structure described in "Device Structure B", and the obtained device is tested.

[0252] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with the diazaaromatic fused-ring compound A-5 provided by the present invention.

[0253] Example 26

[0254] Using the diazaaromatic fused-ring compound A-9 as the implementation object, the diazaaromatic fused-ring compound A-9, SIMCP2, and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. The organic light-emitting layer is prepared by a vacuum evaporation process, and an organic electroluminescent device is prepared using the structure described in "Device Structure A", and the obtained device is tested.

[0255] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with the diazaaromatic fused-ring compound A-9 provided by the present invention.

[0256] Example 27

[0257] Taking the diazaaromatic fused-ring compound A-12 as the implementation object, the diazaaromatic fused-ring compound A-12, SIMCP2 and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. The organic light-emitting layer adopts a solution processing technology, and an organic electroluminescent device is prepared by using the structure described in "Device Structure B", and the obtained device is tested.

[0258] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with the diazaaromatic fused-ring compound A-12 provided by the present invention.

[0259] Example 28

[0260] Taking the diazaaromatic fused-ring compound A-18 as the implementation object, the diazaaromatic fused-ring compound A-18, SIMCP2 and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, and an organic electroluminescent device is prepared by using the structure described in "Device Structure A", and the obtained device is tested.

[0261] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with the diazaaromatic fused-ring compound A-18 provided by the present invention.

[0262] Example 29

[0263] Taking the diazaaromatic fused-ring compound B-1 as the implementation object, the diazaaromatic fused-ring compound B-1, SIMCP2 and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. The organic light-emitting layer adopts a solution processing technology, and an organic electroluminescent device is prepared by using the structure described in "Device Structure B", and the obtained device is tested.

[0264] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with the diazaaromatic fused-ring compound B-1 provided by the present invention.

[0265] Example 30

[0266] Taking the diazaaromatic fused-ring compound B-5 as the implementation object, the diazaaromatic fused-ring compound B-5, SIMCP2 and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, and an organic electroluminescent device is prepared by using the structure described in "Device Structure A", and the obtained device is tested.

[0267] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent device prepared with the diazaaromatic fused-ring compound B-5 provided by the present invention.

[0268] Example 31

[0269] Taking the diazaaromatic fused-ring compound B-7 as the object of implementation, the diazaaromatic fused-ring compound B-7, SIMCP2 and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, and an organic electroluminescent device is prepared by using the structure described in "Device Structure A", and the obtained device is tested.

[0270] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent device prepared with the diazaaromatic fused-ring compound B-7 provided by the present invention.

[0271] Example 32

[0272] Taking the diazaaromatic fused-ring compound B-10 as the object of implementation, the diazaaromatic fused-ring compound B-10, SIMCP2 and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, and an organic electroluminescent device is prepared by using the structure described in "Device Structure A", and the obtained device is tested.

[0273] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent device prepared with the diazaaromatic fused-ring compound B-10 provided by the present invention.

[0274] Example 33

[0275] Taking the diazaaromatic fused-ring compound B-12 as the object of implementation, the diazaaromatic fused-ring compound B-12, SIMCP2 and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, and an organic electroluminescent device is prepared by using the structure described in "Device Structure A", and the obtained device is tested.

[0276] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent device prepared with the diazaaromatic fused-ring compound B-12 provided by the present invention.

[0277] Example 34

[0278] Taking the diazaaromatic fused-ring compound C-1 as the object of implementation, the diazaaromatic fused-ring compound C-1, SIMCP2 and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. The organic light-emitting layer adopts a solution processing process, and an organic electroluminescent device is prepared by using the structure described in "Device Structure B", and the obtained device is tested.

[0279] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with the diazaaromatic-fused ring compound C-1 provided by the present invention.

[0280] Example 35

[0281] Taking the diazaaromatic-fused ring compound C-6 as the implementation object, the diazaaromatic-fused ring compound C-6, SIMCP2 and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, and an organic electroluminescent device is prepared by using the structure described in "Device Structure A", and the obtained device is tested.

[0282] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with the diazaaromatic-fused ring compound C-6 provided by the present invention.

[0283] Example 36

[0284] Taking the diazaaromatic-fused ring compound C-7 as the implementation object, the diazaaromatic-fused ring compound C-7, SIMCP2 and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. The organic light-emitting layer adopts a solution processing process, and an organic electroluminescent device is prepared by using the structure described in "Device Structure B", and the obtained device is tested.

[0285] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with the diazaaromatic-fused ring compound C-7 provided by the present invention.

[0286] Example 37

[0287] Taking the diazaaromatic-fused ring compound C-8 as the implementation object, the diazaaromatic-fused ring compound C-8, SIMCP2 and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. The organic light-emitting layer adopts a solution processing process, and an organic electroluminescent device is prepared by using the structure described in "Device Structure B", and the obtained device is tested.

[0288] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with the diazaaromatic-fused ring compound C-8 provided by the present invention.

[0289] Example 38

[0290] Taking the diazaaromatic-fused ring compound C-9 as the implementation object, the diazaaromatic-fused ring compound C-9, SIMCP2 and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. The organic light-emitting layer adopts a solution processing process, and an organic electroluminescent device is prepared by using the structure described in "Device Structure B", and the obtained device is tested.

[0291] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with the diazaaromatic fused-ring compound C-9 provided by the present invention.

[0292] Example 39

[0293] Taking the diazaaromatic fused-ring compound C-13 as the implementation object, the diazaaromatic fused-ring compound C-13, SIMCP2, and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. The organic light-emitting layer adopts a solution processing technology, and an organic electroluminescent device is prepared using the structure described in "Device Structure B", and the obtained device is tested.

[0294] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with the diazaaromatic fused-ring compound C-13 provided by the present invention.

[0295] Example 40

[0296] Taking the diazaaromatic fused-ring compound C-17 as the implementation object, the diazaaromatic fused-ring compound C-17, SIMCP2, and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. The organic light-emitting layer adopts a solution processing technology, and an organic electroluminescent device is prepared using the structure described in "Device Structure B", and the obtained device is tested.

[0297] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with the diazaaromatic fused-ring compound C-17 provided by the present invention.

[0298] Example 41

[0299] Taking the diazaaromatic fused-ring compound C-19 as the implementation object, the diazaaromatic fused-ring compound C-19, SIMCP2, and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. The organic light-emitting layer adopts a solution processing technology, and an organic electroluminescent device is prepared using the structure described in "Device Structure B", and the obtained device is tested.

[0300] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with the diazaaromatic fused-ring compound C-19 provided by the present invention.

[0301] Example 42

[0302] Taking the diazaaromatic fused-ring compound C-24 as the implementation object, the diazaaromatic fused-ring compound C-24, SIMCP2, and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. The organic light-emitting layer adopts a solution processing technology, and an organic electroluminescent device is prepared using the structure described in "Device Structure B", and the obtained device is tested.

[0303] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent device prepared with the diazaaromatic fused-ring compound C-24 provided by the present invention.

[0304] Table 2 Performance Parameters of the Electroluminescent Device Prepared with the Diazaaromatic Fused-ring Compound Provided by the Present Invention

[0305]

[0306]

[0307] Note: The turn-on voltage in the table is the driving voltage of the device when the brightness is 1 cd m -2 ; The maximum external quantum efficiency is obtained according to the calculation method described in the literature (Jpn. J. Appl. Phys. 2001, 40, L783) based on the current-voltage curve and electroluminescent spectrum of the device; The full width at half maximum is the peak width at half of the peak height of the electroluminescent spectrum at room temperature, that is, a straight line parallel to the peak bottom is drawn through the midpoint of the peak height, and the distance between the two intersection points of this straight line and both sides of the peak.

[0308] As can be seen from Table 2, the device prepared with the diazaaromatic fused-ring compound provided by the present invention has a very narrow electroluminescent spectrum, with a full width at half maximum of less than 50 nm, overcoming the problem of the relatively wide electroluminescent spectrum (70 - 100 nm) of the traditional D-A structure TADF compound. At the same time, the devices prepared with the diazaaromatic fused-ring compound provided by the present invention all have relatively high device efficiency, and the maximum external quantum efficiency reaches 35.9%.

[0309] Obviously, the above embodiments are merely examples for clear illustration and are not limitations on the implementation manners. For those of ordinary skill in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to enumerate all implementation manners here. And the obvious changes or modifications derived therefrom are still within the protection scope of the present invention.

Claims

1. A diazaaromatic fused ring compound, characterized in that: Its structure is shown in formula (I): X1 and X2 are independently selected from a single bond, O, S, Se, Te, N(R 1 )、B(R 1 )、C(R 1 R 2 )、Si(R 1 R 2 ), C=O, O=S=O or (R 1 )P=O; Y1, Y2, Y3 and Y4 are independently selected from O, S, N (R 1 )、C(R 1 R 2 ) or one of the following structures: Among them, R a ~R d Independently selected from H, D, C1-C30 straight chain alkyl, C3-C30 branched chain alkyl, C1-C30 ether chain, C1-C30 thioether chain, C1-C30 ester chain or C3-C30 cycloalkyl; a, b, c and d are independently integers from 0 to 3; Ar1 to Ar4 are independently selected from C6 to C60 aromatic groups or C5 to C60 heteroaromatic groups, and the heteroatoms in the heteroaromatic groups are selected from one or more of Si, Ge, N, P, O, S and Se; R1, R2, R3 and R4 are independently selected from H, D, F, Cl, Br, I, -CN, -NO2, C3-C30 cycloalkyl, C3-C30 cycloalkenyl, C2-C30 heterocycloalkyl, C2-C30 heterocycloalkenyl, C6-C60 aromatic or C5-C60 heteroaromatic, wherein the heteroatoms in the heterocycloalkyl, heterocycloalkenyl and heteroaromatic are selected from one or more of Si, Ge, N, P, O, S and Se; The R 1 , R 2 and R 3 R is independently selected from H, D, F, Cl, Br, I, CN, OH, SH, NH2, C1-C30 straight chain alkyl, C3-C30 branched chain alkyl, C1-C30 ether chain, C1-C30 thioether chain, C1-C30 ester chain, C3-C30 cycloalkyl, C3-C30 cycloalkenyl, C2-C30 heterocycloalkyl, C2-C30 heterocycloalkenyl, C6-C60 aromatic or C4-C60 heteroaromatic; the heteroatoms in the heterocycloalkyl, heterocycloalkenyl and heteroaromatic are selected from one or more of Si, Ge, N, P, O, S and Se; or R 1 and R 2 The bridging is performed through a single bond or a heteroatom, and the heteroatom is selected from one of Si, Ge, N, P, O, S and Se.

2. The diazaaromatic fused ring compound according to claim 1, characterized in that: The Ar1 to Ar4 are independently selected from one of the groups represented by A1 to A20: Wherein, L1, L2 and L3 are independently selected from H, D, F, Cl, Br, I, CN, OH, SH, NH2, C1-C30 straight chain alkyl, C3-C30 branched chain alkyl, C1-C30 ether chain, C1-C30 thioether chain, C1-C30 ester chain, C3-C30 cycloalkyl, C3-C30 cycloalkenyl, C2-C30 heterocycloalkyl, C2-C30 heterocycloalkenyl, C6-C60 aromatic or C4-C60 heteroaromatic; the heteroatoms in the heterocycloalkyl, heterocycloalkenyl and heteroaromatic groups are selected from one or more of Si, Ge, N, P, O, S and Se.

3. The diazaaromatic fused ring compound according to claim 1, characterized in that: X1 and X2 are independently selected from a single bond, O, S, Se, N(R 1 )、C(R 1 R 2 )、Si(R 1 R 2 ).

4. The diazaaromatic fused ring compound according to claim 1, characterized in that: The Y1, Y2, Y3 and Y4 are independently selected from one of the following structures:

5. The bis-azaaromatic fused ring compound according to claim 1, characterized in that: The diazaaromatic fused ring compound has any one of the structures shown in formula (A) to formula (C):

6. A method for preparing the diazaaromatic fused ring compound according to any one of claims 1 to 5, characterized in that: The following steps are involved: When Y1 to Y4 in formula (I) are independently selected from O, the preparation method comprises the following steps: Under an argon atmosphere, M-1 is placed in a reaction bottle, dichloromethane is added and stirred, and then oxalyl chloride and N,N-dimethylformamide are added dropwise to the reaction solution, and the reaction solution is heated to reflux after the addition is completed; after the reaction is completed, the reaction solution is cooled to room temperature, tin tetrachloride is added dropwise to the reaction solution, and the temperature is raised to reflux; after the reaction is completed, the reaction solution is cooled to room temperature, the reaction solution is poured into ice water, and sodium hydroxide solution is added to adjust the pH to 10, followed by extraction with dichloromethane, the organic phase is washed with water and a saturated sodium chloride solution, respectively, the obtained organic phase is dried over anhydrous sodium sulfate, filtered, and the solvent is removed by reduced pressure rotary evaporation, and the obtained crude product is purified by chromatography to obtain a diazaaromatic condensed ring compound represented by formula (Ⅰ); When Y1 to Y4 in formula (I) are independently selected from S, the preparation method comprises the following steps: The diazaaromatic fused ring compound of formula (I) prepared when Y1 to Y4 are independently selected from O and Law's reagent are placed in a reaction bottle, toluene is added and stirred to dissolve, air is blown into the reaction container, and then the reaction solution is heated to reflux. After the reaction is completed, the reaction solution is cooled to room temperature, and the reaction solvent is removed by rotary evaporation under reduced pressure. The obtained crude product is purified by chromatography to obtain the diazaaromatic fused ring compound of formula (I); When Y1 to Y4 are independently selected from N(R 1 ) or C(R 1 R 2 ), the preparation method comprises the following steps: Under an argon atmosphere, the diazaaromatic fused ring compound represented by formula (I) prepared when Y1 to Y4 are independently selected from O and R 1 -NH2 or CH2(R 1 R 2 ) is placed in a reaction bottle, a solvent is added and stirred to dissolve, an organic base is added to the reaction solution, and then titanium tetrachloride is added dropwise in an ice-water bath. After the addition is complete, the temperature is raised to room temperature for reaction. After the reaction is completed, quenching is performed with a 10% sodium hydroxide solution, and the mixture is extracted with dichloromethane. The organic phase is dried over anhydrous sodium sulfate, and the crude product obtained by filtration is purified by a chromatography column to obtain a diazaaromatic fused ring compound represented by formula (I); When Y1 to Y4 are independently selected from the following structures: The diazaaromatic fused ring compound of formula (I) prepared when Y1 to Y4 are independently selected from O and the compounds having the structures of formulas (N-1) to (N-6) are placed in a reaction flask, glacial acetic acid and acetic anhydride are added as a mixed solvent, the reaction temperature is raised to reflux, and after the reaction is completed, the glacial acetic acid and acetic anhydride are removed by vacuum rotary evaporation, and the remaining solid in the reaction flask is dissolved in dichloromethane, followed by washing with water and saturated sodium chloride solution, and the obtained crude product is purified by chromatography to obtain the diazaaromatic fused ring compound of formula (I); Wherein, all codes are the same as defined in claims 1-5.

7. The method for preparing the diazaaromatic fused ring compound according to claim 6, characterized in that: When Y1-Y4 are independently selected from O, the reaction system temperature is 35-45°C and the reaction time is 18-24h; When Y1-Y4 are independently selected from S, the reaction system temperature is 100-120°C, and the reaction time is 0.5-3h; When Y1 to Y4 are independently selected from N(R 1 ) or C(R 1 R 2 ), the reaction system temperature is 0-40°C, and the reaction time is 10-24h; When Y1 to Y4 are independently selected from the following structures: The reaction system temperature is 110-150°C and the reaction time is 8-24h.

8. An organic electroluminescent device, comprising an anode, a cathode and an organic thin film layer located between the anode and the cathode; characterized in that: The organic thin film layer comprises the diazaaromatic condensed ring compound according to any one of claims 1 to 5.

9. The organic electroluminescent device according to claim 8, characterized in that: The organic thin film layer includes a light-emitting layer; the light-emitting layer includes the diazaaromatic condensed ring compound according to any one of claims 1 to 5.

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