Organic micromolecular luminescent material based on dibenzoxepin derivative and preparation and application thereof

Abstract

The invention discloses an organic small molecular luminescent material based on a dibenzoxepin derivative as well as preparation and application of the organic small molecular luminescent material. A dibenzoxepin derivative is used as an acceptor core unit, and the molecular weight, charge transfer degree, light-emitting wavelength and other characteristics of the material can be effectively adjusted by changing the conjugate length of the acceptor core unit and the type and size of a connecting unit. The bipolar photoelectric material connected with the donor and the acceptor can form a large torsion angle between the donor and the acceptor, so that the non-planarity of the structure is improved, the accumulation degree of the material is reduced, aggregation quenching of the material is effectively inhibited, the problem of unbalanced carriers of the unipolar organic photoelectric material is avoided, and the photoelectric efficiency is improved. Meanwhile, the conjugate length of molecules can be effectively controlled, the horizontal molecular orientation is improved, and the simplification of the device structure and the improvement of the device performance are realized.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic photoelectric materials, and specifically relates to an organic small molecule luminescent material based on a dibenzoxepin derivative as an acceptor core unit, and the preparation and application thereof. Background Art

[0002] Organic electroluminescent (OLED) devices have attracted widespread attention due to their applications in solid-state lighting and flexible displays. Commonly used luminescent materials for OLEDs can be divided into two material systems: organic small molecules and organic polymer luminescent materials. Compared with polymer luminescent materials, organic small molecules have the advantages of simple synthesis and preparation, clear and stable structure, and high material purity, thus achieving higher device performance and stability. Currently, red, green and blue primary color display devices developed and prepared based on organic small molecule luminescence have been successfully commercialized. However, due to the high cost of material preparation and insufficient device performance, the development of new high-efficiency and low-cost luminescent materials has become an important issue in the field of organic electroluminescence.

[0003] In recent years, luminescent materials based on thermally activated delayed fluorescence (TADF) have been widely used in OLED devices. Due to their small singlet-triplet energy gap, these materials effectively overcome the low exciton utilization efficiency of traditional fluorescent materials. By utilizing the 25% probability of generating singlet excitons and 75% probability of generating triplet excitons under electroinduced conditions, they can significantly improve the luminous efficiency of OLEDs. Currently, the luminous efficiency of blue and green TADF-based luminescent materials is approaching commercial levels, but the efficiency of red luminescent materials is still far from the level of commercially available second-generation precious metal complex luminescent materials. Therefore, the development of pure organic luminescent materials with high efficiency and high stability is of great significance for reducing the cost of OLEDs. Summary of the Invention

[0004] In order to address the shortcomings and deficiencies of the prior art, the primary purpose of the present invention is to provide a series of organic small molecule luminescent materials with high quantum efficiency and high carrier transport performance based on dibenzoxepin derivatives as acceptor core units.

[0005] Using dibenzoxepin derivatives as the acceptor core unit, by varying the conjugation length of the acceptor core unit and the type and size of the linker unit, the material's molecular weight, charge transfer degree, luminescence wavelength, and other properties can be effectively tuned. This type of donor-acceptor linked bipolar optoelectronic material can form a large torsion angle between the donor and acceptor, thereby increasing the structural non-planarity and reducing the material's stacking degree. This effectively suppresses aggregation quenching and avoids the carrier imbalance problem of unipolar organic optoelectronic materials. Furthermore, it effectively controls the molecular conjugation length and improves horizontal molecular orientation, simplifying the device structure and improving device performance.

[0006] The dibenzoxepin derivatives developed by this invention exhibit thermally activated delayed fluorescence. These small organic molecules have a simple structure, a defined molecular weight, and are easily purified. They can also be formed into organic thin films through vacuum deposition or spin coating and applied to organic optoelectronic devices, including organic light-emitting diodes. This is crucial for the development of low-cost, high-performance organic optoelectronic materials.

[0007] Another object of the present invention is to provide a method for preparing the above-mentioned organic small molecule luminescent material based on a dibenzoxepin derivative as an acceptor core unit. The preparation method of this type of material uses a dibenzoxepin dione derivative as a raw material and obtains the target compound through a series of simple reactions.

[0008] Another object of the present invention is to provide an application of the above-mentioned organic small molecule luminescent material based on dibenzoxepin derivatives in the preparation of organic optoelectronic devices such as organic light-emitting diodes.

[0009] The purpose of the present invention is achieved through the following technical solutions:

[0010] The organic small molecule material based on a dibenzoxepin derivative as a receptor core unit has at least one of the following structural formulas:

[0011]

[0012] Wherein R is identical or different and is at least one of an aromatic ring composed of electron-donating vinylene carbon and hydrogen atoms, an aromatic heterocycle composed of carbon, nitrogen and hydrogen atoms, an aromatic heterocycle composed of carbon, nitrogen, oxygen and hydrogen atoms, an aromatic heterocycle composed of carbon, sulfur and hydrogen atoms, and an aromatic heterocycle composed of carbon, silicon and hydrogen atoms.

[0013] Preferably, the R is the same or different and is at least one of the following structures:

[0014]

[0015] Preferably, the organic small molecule material based on a dibenzoxepin derivative as a receptor core unit has at least one of the structural formulas shown in 1 to 50:

[0016]

[0017]

[0018] More preferably, the organic small molecule material based on a dibenzoxepin derivative as a receptor core unit has at least one of the following structures:

[0019]

[0020] The preparation method of the above-mentioned organic small molecule material based on dibenzoxepin derivatives as receptor core units comprises the following steps:

[0021] (1) a dibenzoxetyl-diketone derivative is subjected to a ring-forming reaction to obtain an electron-withdrawing intermediate;

[0022] (2) The dibenzoxetine derivatives are subjected to Suzuki coupling, Buchwald-Hartwig coupling or copper-catalyzed amination reaction of aryl halides to obtain organic small molecule materials based on the dibenzoxetine derivatives as the receptor core unit.

[0023] Preferably, the cyclization reaction in step (1) is specifically: heating and cyclizing at least one of the dibenzoxadione derivatives M1 to M5 with at least one of the compounds m3 to m7 to obtain an electron-withdrawing intermediate;

[0024] The compound M1 is M2 is M3 is M4 is M5 is m3 is 3,6-dibromophenanthrene-9,10-diamine; compound m4 is Compound m5 is 4,5-dibromo-o-phenylenediamine; Compound m6 is Compound m7 is

[0025] The molar ratio of at least one of the dibenzoxepin-dione derivatives M1 to M5 to at least one of the compounds m3 to m7 is 1:1 to 1.2, more preferably 1:1.

[0026] The heating cyclization reaction condition is heating under reflux for 8 to 24 hours, and the heating under reflux temperature is not lower than the boiling point of the solvent.

[0027] Preferably, the halogen atom in the electron-withdrawing intermediate in step (2) and triphenylamine-4-boric acid are reacted by Suzuki coupling reaction in a molar ratio of 1:1 to 1.5 to obtain an organic small molecule material based on a dibenzoxepin derivative as a receptor core unit.

[0028] The Suzuki coupling reaction is carried out in the presence of a palladium catalyst and a base, and the amount of the palladium catalyst used is 1 to 10% of the molar amount of the electron-withdrawing intermediate, and more preferably 5%.

[0029] The temperature of the Suzuki coupling reaction is 80-90° C., and the reaction time is 8-24 hours.

[0030] The base is a 1-3 mol / L K2CO3 aqueous solution; the molar ratio of its volume to the charge-withdrawing intermediate is 20 mL:1.5 mmol.

[0031] Preferably, the halogen atom in the electron-withdrawing intermediate in step (2) reacts with at least one of 9,9-dimethyl-9,10-dihydroacridine and phenoxazine in a molar ratio of 1:1 to 1.5 through a Buchwald-Hartwig coupling reaction to obtain an organic small molecule material based on a dibenzoxepin derivative as an acceptor core unit.

[0032] The Buchwald-Hartwig coupling reaction is carried out in the presence of a palladium catalyst and a base, and the amount of the palladium catalyst used is 1 to 10% of the molar amount of the electron-withdrawing intermediate, and more preferably 5%.

[0033] The temperature of the Buchwald-Hartwig coupling reaction is 80-90° C., and the reaction time is 8-24 hours.

[0034] The base is potassium tert-butoxide, and its usage is 1 to 2 times of the molar amount of the electricity-absorbing unit.

[0035] Preferably, the reactions in steps (1) and (2) are carried out under an inert gas atmosphere, wherein the inert gas is at least one of nitrogen, argon and helium.

[0036] Preferably, the solvent medium for the cyclization reaction in step (1) is acetic acid; and the solvent medium for the Suzuki coupling, Buchwald-Hartwig coupling or copper-catalyzed amination of aryl halides in step (2) is at least one of toluene, dioxane and ethanol.

[0037] Application of the above-mentioned organic small molecule luminescent material based on dibenzoxepin derivatives as acceptor core units in the preparation of organic optoelectronic devices.

[0038] Preferably, the organic small molecule luminescent material based on the dibenzoxepin derivative as the acceptor core unit is used to prepare the luminescent layer of an organic optoelectronic device, and accounts for 1 to 5 wt% of the mass of the luminescent layer.

[0039] Preferably, the organic photoelectric device is an organic light emitting diode.

[0040] An organic light emitting diode, the structure of which comprises, from bottom to top, a transparent substrate, a transparent anode layer, one or more organic light emitting layer units, and a cathode layer;

[0041] The organic light-emitting layer unit includes a hole injection layer, a hole transport layer, one or more light-emitting layers, and an electron transport layer;

[0042] The light-emitting layer includes the above-mentioned organic small molecule light-emitting material based on the dibenzoxepin derivative as the acceptor core unit.

[0043] Preferably, the method for preparing the light-emitting layer comprises at least one of thermal evaporation, spin coating, brush coating, spray coating, dip coating, roller coating, printing and inkjet printing.

[0044] Preferably, the organic small molecule luminescent material based on the dibenzoxepin derivative as the acceptor core unit accounts for 1 to 5 wt% of the mass of the luminescent layer; more preferably 3 wt%.

[0045] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0046] (1) The organic small molecule material of the present invention using dibenzoxepin derivatives as the receptor core unit has a simple structure, a certain molecular weight, is easy to purify, has good electrochemical stability, and is easy to study its structure-activity relationship.

[0047] (2) The organic small molecule material of the present invention with a dibenzoxepin derivative as the receptor core unit has a large molecular level orientation, a high fluorescence quantum yield, and exhibits the property of thermally activated delayed fluorescence while achieving a low efficiency roll-off.

[0048] (3) The present invention uses dibenzoxepin derivatives as the acceptor core unit to couple aromatic amines. By adjusting different conjugation lengths, the luminescence characteristics of the material can be further adjusted and the luminescence mechanism of the material can be deeply studied to optimize the material performance.

[0049] (4) The present invention uses a dibenzoxepin derivative as the acceptor core unit, and can also effectively control the light color and efficiency of the material by changing the type and size of the donor unit coupled thereto, thereby meeting the needs of organic optoelectronic devices.

[0050] (5) The donor-acceptor connected bipolar optoelectronic material of the present invention can form a large torsion angle between the donor and the acceptor, thereby improving the non-planarity of the structure and reducing the degree of stacking of the material, thereby effectively suppressing the aggregation quenching of the material and avoiding the problem of carrier imbalance in unipolar organic optoelectronic materials. At the same time, it can effectively control the conjugation length of the molecules, improve the horizontal molecular orientation, and achieve the simplification of the device structure and the improvement of the device performance. DETAILED DESCRIPTION

[0051] The present invention will be further described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto.

[0052] In the examples of the present invention, if the specific conditions are not specified, the experiments were carried out according to conventional conditions or the conditions recommended by the manufacturer. All raw materials and reagents used without specifying the manufacturer are conventional products that can be purchased from the market.

[0053] Example 1

[0054] In this example, intermediate M1 was prepared, and its structure and synthesis route are shown below:

[0055]

[0056] The specific reaction steps are as follows: m1 (10 mmol) and catalyst 3-benzyl-5-(2-hydroxyethyl)-4-methylthiazole chloride (2 mmol) are taken into a clean and dry two-necked round-bottom flask. After vacuuming, fill with argon (2-3 cycles), add dry THF (80 ml) with a syringe, and then add 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU, 1.2 equivalents, 12 mmol) dropwise, and then stir at room temperature for 30 minutes. Water is added to the product mixture (400 mL), extracted with ethyl acetate, washed with brine (100 ml), and the organic phase is dried over anhydrous Na2SO4 and filtered. The filtrate is concentrated on a rotary evaporator under reduced pressure and purified by column method to obtain M1. Product molecular formula: C 14 H8O3; molecular weight m / z: 224.05.

[0057] Example 2

[0058] This example prepares intermediate M2, whose structure and synthesis route are shown below:

[0059]

[0060] The specific reaction steps are as follows: Compared with Example 1, the difference is that m1 is replaced with an equivalent amount of m2. The other raw materials and steps are the same as Example 1, and the product M2 is finally obtained. The product molecular formula is: C 14 H6Cl2O3; molecular weight m / z: 291.97.

[0061] Example 3

[0062] This example prepares intermediate M3, whose structure and synthesis route are shown below:

[0063]

[0064] The specific reaction steps are as follows: A mixture of M2 (4 mmol), Zn(CN)2 (10 mmol), and catalyst Pd(PPh3)4 (0.08 mmol) is dissolved in 80 mL of DMF under an argon atmosphere and then heated to 150°C for 12 hours. After cooling to room temperature, the resulting mixture is filtered to remove the solvent, and the crude product is purified by silica gel column chromatography and dried under vacuum to obtain the product intermediate M3 with a yield of 83%. Product molecular formula: C 16H6N2O3; molecular weight m / z: 274.04.

[0065] Example 4

[0066] In this example, intermediate M4 was prepared, and its structure and synthesis route are shown below:

[0067]

[0068] The specific reaction steps are as follows: intermediate M2 (3mmol) and p-cyanophenylboronic acid (8mmol) are dissolved in a 250mL round-bottom flask containing 60mL toluene, 25mL ethanol and 20mL K2CO3 aqueous solution (2mol / L). After ventilating with argon for 15 minutes, the catalyst Pd(PPh3)4 (1mol% of the electric absorption unit) is quickly added, and then ventilated with argon for another 10 minutes. The reaction is then heated to 85°C and stirred vigorously for 12 hours. After the reaction system is cooled to room temperature, the solvent is removed by a vacuum rotary evaporator, and the mixture is extracted 3 times with dichloromethane (DCM). The collected organic phase is further washed 3 times with deionized water, and finally the organic phase is dried over anhydrous magnesium sulfate (MgSO4). The next step of purification is carried out by silica gel column chromatography to finally obtain the product compound 1 with a yield of 80%. Product molecular formula: C 28 H 14 N2O3; molecular weight m / z: 426.10.

[0069] Example 5

[0070] This example prepares intermediate M5, whose structure and synthesis route are shown below:

[0071]

[0072] The specific reaction steps are as follows: Compared with Example 4, the difference is that p-cyanophenylboronic acid is replaced with an equivalent amount of pyridine-3-boronic acid. The other raw materials and steps are the same as Example 4, and the intermediate product M5 is finally obtained. The product molecular formula is: C 24 H 14 N2O3; molecular weight m / z: 378.10.

[0073] Example 6

[0074] In this example, intermediate A1 was prepared, and its structural formula and synthetic route are shown below:

[0075]

[0076] The specific reaction steps are as follows: A mixture of 3,6-dibromophenanthrene-9,10-diamine m3 (8 mmol) and M1 (8 mmol) is dissolved in 80 mL of acetic acid under an argon atmosphere, and then heated to 120°C for 8 hours. After cooling to room temperature, the resulting mixture is filtered to remove the solvent, and the crude product is then purified by silica gel column chromatography and dried under vacuum to obtain the product intermediate A1 with a yield of 76%. Product molecular formula: C 28 H 14 Br2N2O; molecular weight m / z: 553.95.

[0077] Example 7

[0078] This example prepares intermediate A2, whose structural formula and synthetic route are as follows:

[0079]

[0080] The specific reaction steps are as follows: Compared with Example 6, the difference is that M1 is replaced with an equivalent amount of M2. The other raw materials and steps are the same as Example 6. Finally, the intermediate A2 product is obtained with a yield of 73%. Product molecular formula: C 28 H 12 Br2Cl2N2O; molecular weight m / z: 621.87.

[0081] Example 8

[0082] In this example, intermediate A3 was prepared, and its structural formula and synthetic route are shown below:

[0083]

[0084] The specific reaction steps are as follows: Compared with Example 6, the difference is that M1 is replaced with an equivalent amount of M3. The other raw materials and steps are the same as Example 6. The intermediate M8 product is finally obtained with a yield of 72%. Product molecular formula: C 30 H 12 Br2N4O; molecular weight m / z: 603.94.

[0085] Example 9

[0086] In this example, intermediate A4 was prepared, and its structural formula and synthetic route are shown below:

[0087]

[0088] The specific reaction steps are as follows: Compared with Example 6, the difference is that M1 is replaced with an equivalent amount of M4. The other raw materials and steps are the same as Example 6. Finally, the intermediate A4 product is obtained with a yield of 76%. Product molecular formula: C 42 H 20Br2N4O; molecular weight m / z: 756.00.

[0089] Example 10

[0090] In this example, intermediate A5 was prepared, and its structural formula and synthetic route are shown below:

[0091]

[0092] The specific reaction steps are as follows: Compared with Example 6, the difference is that M1 is replaced with an equivalent amount of M5. The other raw materials and steps are the same as Example 6. Finally, the intermediate A5 product is obtained with a yield of 76%. Product molecular formula: C 38 H 20 Br2N4O; molecular weight m / z: 708.00.

[0093] Example 11

[0094] In this example, intermediate A6 was prepared, and its structural formula and synthetic route are shown below:

[0095]

[0096] The specific reaction steps are as follows: Compared with Example 6, the difference is that m3 is replaced with an equivalent amount of m4. The other raw materials and steps are the same as Example 6. Finally, the intermediate A6 product is obtained with a yield of 56%. Product molecular formula: C 26 H 12 Br2N4O; molecular weight m / z: 555.94.

[0097] Example 12

[0098] In this example, intermediate A7 was prepared, and its structural formula and synthetic route are shown below:

[0099]

[0100] The specific reaction steps are as follows: Compared with Example 7, the difference is that m3 is replaced with an equivalent amount of m4. The other raw materials and steps are the same as Example 7. Finally, the intermediate A2 product is obtained with a yield of 54%. Product molecular formula: C 26 H 10 Br2Cl2N4O; molecular weight m / z: 623.86.

[0101] Example 13

[0102] In this example, intermediate A8 was prepared, and its structural formula and synthetic route are shown below:

[0103]

[0104] The specific reaction steps are as follows: Compared with Example 8, the difference is that m3 is replaced with an equivalent amount of m4. The other raw materials and steps are the same as Example 8, and the intermediate A8 product is finally obtained with a yield of 48%. Product molecular formula: C 28 H 10 Br2N6O; molecular weight m / z: 605.93.

[0105] Example 14

[0106] In this example, intermediate A9 was prepared, and its structural formula and synthetic route are shown below:

[0107]

[0108] The specific reaction steps are as follows: Compared with Example 9, the difference is that m3 is replaced with an equivalent amount of m4. The other raw materials and steps are the same as Example 9, and the intermediate A9 product is finally obtained with a yield of 63%. Product molecular formula: C 40 H 18 Br2N6O; molecular weight m / z: 757.99.

[0109] Example 15

[0110] In this example, intermediate A10 was prepared, and its structural formula and synthetic route are shown below:

[0111]

[0112] The specific reaction steps are as follows: Compared with Example 10, the difference is that m3 is replaced with an equivalent amount of m4. The other raw materials and steps are the same as Example 10, and the intermediate A10 product is finally obtained with a yield of 60%. Product molecular formula: C 36 H 18 Br2N6O; molecular weight m / z: 709.99.

[0113] Example 16

[0114] In this example, intermediate A11 was prepared, and its structural formula and synthetic route are shown below:

[0115]

[0116] The specific reaction steps are as follows: Compared with Example 6, the difference is that m3 is replaced with an equivalent amount of m5. The other raw materials and steps are the same as Example 6. Finally, the intermediate A11 product is obtained with a yield of 76%. Product molecular formula: C 20 H 10 Br2N2O; molecular weight m / z: 453.91.

[0117] Example 17

[0118] In this example, intermediate A12 was prepared, and its structural formula and synthetic route are shown below:

[0119]

[0120] The specific reaction steps are as follows: Compared with Example 7, the difference is that m3 is replaced with an equivalent amount of m5. The other raw materials and steps are the same as Example 7. Finally, the intermediate A12 product is obtained with a yield of 76%. Product molecular formula: C 20 H8Br2Cl2N2O; molecular weight m / z: 521.84.

[0121] Example 18

[0122] In this example, intermediate A13 was prepared, and its structural formula and synthetic route are shown below:

[0123]

[0124] The specific reaction steps are as follows: Compared with Example 8, the difference is that m3 is replaced with an equivalent amount of m5. The other raw materials and steps are the same as Example 8, and the intermediate A13 product is finally obtained with a yield of 68%. Product molecular formula: C 22 H8Br2N4O; molecular weight m / z: 503.90.

[0125] Example 19

[0126] In this example, intermediate A14 was prepared, and its structural formula and synthetic route are shown below:

[0127]

[0128] The specific reaction steps are as follows: Compared with Example 9, the difference is that m3 is replaced with an equivalent amount of m5. The other raw materials and steps are the same as Example 9, and the intermediate A14 product is finally obtained with a yield of 63%. Product molecular formula: C 34 H 16 Br2N4O; molecular weight m / z: 655.97.

[0129] Example 20

[0130] In this example, intermediate A5 was prepared, and its structural formula and synthetic route are shown below:

[0131]

[0132] The specific reaction steps are as follows: Compared with Example 10, the difference is that m3 is replaced with an equivalent amount of m5. The other raw materials and steps are the same as Example 10, and the intermediate A15 product is finally obtained with a yield of 60%. Product molecular formula: C 30 H 16Br2N4O; molecular weight m / z: 607.97.

[0133] Example 21

[0134] In this example, intermediate A16 was prepared, and its structural formula and synthetic route are shown below:

[0135]

[0136] The specific reaction steps are as follows: Compared with Example 6, the difference is that m3 is replaced with an equivalent amount of m6. The other raw materials and steps are the same as Example 6. Finally, the intermediate A16 product is obtained with a yield of 56%. Product molecular formula: C 22 H8Br2N4O; molecular weight m / z: 503.90.

[0137] Example 22

[0138] In this example, intermediate A17 was prepared, and its structural formula and synthetic route are shown below:

[0139]

[0140] The specific reaction steps are as follows: Compared with Example 7, the difference is that m3 is replaced with an equivalent amount of m6. The other raw materials and steps are the same as Example 7, and the intermediate A17 product is finally obtained with a yield of 54%. Product molecular formula: C 22 H6Br2Cl2N4O; molecular weight m / z: 571.83.

[0141] Example 23

[0142] In this example, intermediate A18 was prepared, and its structural formula and synthetic route are shown below:

[0143]

[0144] The specific reaction steps are as follows: Compared with Example 8, the difference is that m3 is replaced with an equivalent amount of m6. The other raw materials and steps are the same as Example 8, and the intermediate A18 product is finally obtained with a yield of 53%. Product molecular formula: C 24 H6Br2N6O; molecular weight m / z: 553.89.

[0145] Example 24

[0146] In this example, intermediate A19 was prepared, and its structural formula and synthetic route are shown below:

[0147]

[0148] The specific reaction steps are as follows: Compared with Example 9, the difference is that m3 is replaced with an equivalent amount of m6. The other raw materials and steps are the same as Example 9, and the intermediate A19 product is finally obtained with a yield of 57%. Product molecular formula: C 36 H 14 Br2N6O; molecular weight m / z: 705.96.

[0149] Example 25

[0150] In this example, intermediate A20 was prepared, and its structural formula and synthetic route are shown below:

[0151]

[0152] The specific reaction steps are as follows: Compared with Example 10, the difference is that m3 is replaced with an equivalent amount of m6. The other raw materials and steps are the same as Example 10, and the intermediate A20 product is finally obtained with a yield of 54%. Product molecular formula: C 32 H 14 Br2N6O; molecular weight m / z: 657.96.

[0153] Example 26

[0154] In this example, compound 1 was prepared, and its structural formula and synthetic route are shown below:

[0155]

[0156] The specific reaction steps are as follows: Intermediate A1 (1.5 mmol) and triphenylamine-4-boronic acid (3.6 mmol) are dissolved in a 250 mL round-bottom flask containing 80 mL toluene, 25 mL ethanol and 20 mL K2CO3 aqueous solution (2 mol / L). After venting with argon for 15 minutes, the catalyst Pd(PPh3)4 (0.08 mmol) is quickly added, and then vented with argon for another 10 minutes. The reaction is then heated to 85°C and stirred vigorously for 12 hours. After the reaction system is cooled to room temperature, the solvent is removed by a vacuum rotary evaporator, and the mixture is extracted 3 times with dichloromethane (DCM). The collected organic phase is further washed 3 times with deionized water, and finally the organic phase is dried over anhydrous magnesium sulfate (MgSO4). The next step of purification is carried out by silica gel column chromatography to finally obtain the product compound 1 with a yield of 84%. Product molecular formula: C 64 H 42 N4O; molecular weight m / z: 882.34; elemental analysis results: C, 87.05; H, 4.79; N, 6.34; O, 1.81.

[0157] Example 27

[0158] This example prepares compound 2, and its structural formula and synthetic route are shown below:

[0159]

[0160] The specific reaction steps are as follows: Compared with Example 26, the difference is that A1 is replaced with an equivalent amount of A2, 7.2 mmol of triphenylamine-4-boric acid is added, and the other raw materials and steps are the same as Example 26. Finally, the product compound 2 is obtained with a yield of 83%. The product molecular formula is: C 100 H 68 N6O; molecular weight m / z: 1369.55; elemental analysis results: C, 87.69; H, 5.00; N, 6.14; O, 1.17.

[0161] Example 28

[0162] In this example, compound 3 was prepared, and its structural formula and synthetic route are shown below:

[0163]

[0164] The specific reaction steps are as follows: Compared with Example 26, the difference is that A1 is replaced with an equivalent amount of A3. The other raw materials and steps are the same as Example 26, and the product compound 3 is finally obtained with a yield of 86%. Product molecular formula: C 66 H 40 N6O; molecular weight m / z: 932.33; elemental analysis results: C, 84.96; H, 4.32; N, 9.01; O, 1.71.

[0165] Example 29

[0166] In this example, compound 4 was prepared, and its structural formula and synthetic route are shown below:

[0167]

[0168] The specific reaction steps are as follows: Compared with Example 26, the difference is that A1 is replaced with an equivalent amount of A4. The other raw materials and steps are the same as Example 26, and the product compound 4 is finally obtained with a yield of 81%. The product molecular formula is: C 78 H 48 N6O; molecular weight m / z: 1084.39; elemental analysis results: C, 86.32; H, 4.46; N, 7.74; O, 1.47.

[0169] Example 30

[0170] In this example, compound 5 was prepared, and its structural formula and synthetic route are shown below:

[0171]

[0172] The specific reaction steps are as follows: Compared with Example 26, the difference is that A1 is replaced with an equivalent amount of A5. The other raw materials and steps are the same as Example 26, and the product compound 5 is finally obtained with a yield of 78%. Product molecular formula: C 74 H 48 N6O; molecular weight m / z: 1036.39; elemental analysis results: C, 85.69; H, 4.66; N, 8.10; O, 1.54.

[0173] Example 31

[0174] In this example, compound 6 was prepared, and its structural formula and synthetic route are shown below:

[0175]

[0176] The specific reaction steps are as follows: Intermediate A1 (1.5 mmol) and 9,9-dimethyl-9,10-dihydroacridine (3.6 mmol) are dissolved in a 250 mL round-bottom flask filled with 100 mL of toluene. After ventilating with argon for 15 minutes, palladium acetate (0.08 mmol), 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl XPhos (0.08 mmol) and 0.75 g of potassium tert-butoxide are quickly added and stirred at 110 ° C for 24 hours. After the reaction system is cooled to room temperature, the solvent is removed by a vacuum rotary evaporator, and the mixture is extracted 3 times with dichloromethane (DCM). The collected organic phase is further washed 3 times with deionized water, and finally the organic phase is dried over anhydrous magnesium sulfate (MgSO4). The next step of purification is carried out by silica gel column chromatography to finally obtain the product compound 6 with a yield of 84%. Product molecular formula: C 58 H 42 N4O; molecular weight m / z: 810.34; elemental analysis results: C, 85.90; H, 5.22; N, 6.91; O, 1.97.

[0177] Example 32

[0178] In this example, compound 7 was prepared, and its structural formula and synthetic route are shown below:

[0179]

[0180] The specific reaction steps are as follows: Compared with Example 31, the difference is that A1 is replaced with an equivalent amount of A2, 7.2 mmol of 9,9-dimethyl-9,10-dihydroacridine is added, and the other raw materials and steps are the same as Example 31. Finally, the product compound 7 is obtained with a yield of 82%. The product molecular formula is: C 88 H 68N6O; molecular weight m / z: 1224.55; elemental analysis results: C, 86.24; H, 5.59; N, 6.86; O, 1.31.

[0181] Example 33

[0182] In this example, compound 8 was prepared, and its structural formula and synthetic route are shown below:

[0183]

[0184] The specific reaction steps are as follows: Compared with Example 31, the difference is that A1 is replaced with an equivalent amount of A3. The other raw materials and steps are the same as Example 31, and the product compound 8 is finally obtained with a yield of 82%. Product molecular formula: C 60 H 40 N6O; molecular weight m / z: 860.33; elemental analysis results: C, 83.70; H, 4.68; N, 9.76; O, 1.86.

[0185] Example 34

[0186] In this example, compound 9 was prepared, and its structural formula and synthetic route are shown below:

[0187]

[0188] The specific reaction steps are as follows: Compared with Example 31, the difference is that A1 is replaced with an equivalent amount of A4. The other raw materials and steps are the same as Example 31, and the product compound 9 is finally obtained with a yield of 81%. Product molecular formula: C 72 H 48 N6O; molecular weight m / z: 1012.39; elemental analysis results: C, 85.35; H, 4.78; N, 8.29; O, 1.58.

[0189] Example 35

[0190] In this example, compound 10 was prepared, and its structural formula and synthetic route are shown below:

[0191]

[0192] The specific reaction steps are as follows: Compared with Example 31, the difference is that A1 is replaced with an equivalent amount of A5. The other raw materials and steps are the same as Example 31, and the product compound 10 is finally obtained with a yield of 80%. Product molecular formula: C 68 H 48 N6O; molecular weight m / z: 964.39; elemental analysis results: C, 84.62; H, 5.01; N, 8.71; O, 1.66.

[0193] Example 36

[0194] In this example, compound 11 was prepared, and its structural formula and synthetic route are shown below:

[0195]

[0196] The specific reaction steps are as follows: Compared with Example 26, the difference is that A1 is replaced with an equivalent amount of A6. The other raw materials and steps are the same as Example 26, and the product compound 11 is finally obtained with a yield of 82%. The product molecular formula is: C 62 H 40 N6O; molecular weight m / z: 884.33; elemental analysis results are: C, 84.14; H, 4.56; N, 9.50; O, 1.81.

[0197] Example 37

[0198] In this example, compound 12 was prepared, and its structural formula and synthetic route are shown below:

[0199]

[0200] The specific reaction steps are as follows: Compared with Example 26, the difference is that A1 is replaced with an equivalent amount of A7, 7.2 mmol of triphenylamine-4-boric acid is added, and the other raw materials and steps are the same as Example 26. Finally, the product compound 12 is obtained with a yield of 78%. The product molecular formula is: C 98 H 66 N8O; molecular weight m / z: 1370.54; elemental analysis results: C, 85.81; H, 4.85; N, 8.17; O, 1.17.

[0201] Example 38

[0202] In this example, compound 13 was prepared, and its structural formula and synthetic route are shown below:

[0203]

[0204] The specific reaction steps are as follows: Compared with Example 26, the difference is that A1 is replaced with an equivalent amount of A8. The other raw materials and steps are the same as Example 26, and the product compound 13 is finally obtained with a yield of 88%. Product molecular formula: C 64 H 38 N8O; molecular weight m / z: 934.32; elemental analysis results: C, 82.21; H, 4.10; N, 11.98; O, 1.71.

[0205] Example 39

[0206] In this example, compound 14 was prepared, and its structural formula and synthetic route are shown below:

[0207]

[0208] The specific reaction steps are as follows: Compared with Example 26, the difference is that A1 is replaced with an equivalent amount of A9. The other raw materials and steps are the same as Example 26, and the product compound 14 is finally obtained with a yield of 80%. Product molecular formula: C 76 H 46 N8O; molecular weight m / z: 1086.38; elemental analysis results: C, 83.96; H, 4.26; N, 10.31; O, 1.47.

[0209] Example 40

[0210] In this example, compound 15 was prepared, and its structural formula and synthetic route are shown below:

[0211]

[0212] The specific reaction steps are as follows: Compared with Example 26, the difference is that A1 is replaced with an equivalent amount of A10. The other raw materials and steps are the same as Example 26, and the product compound 15 is finally obtained with a yield of 77%. Product molecular formula: C 72 H 46 N8O; molecular weight m / z: 1038.38; elemental analysis results: C, 85.69; H, 4.66; N, 8.10; O, 1.54.

[0213] Example 41

[0214] In this example, compound 16 was prepared, and its structural formula and synthetic route are shown below:

[0215]

[0216] The specific reaction steps are as follows: Compared with Example 31, the difference is that A1 is replaced with an equivalent amount of A6. The other raw materials and steps are the same as Example 31, and the product compound 16 is finally obtained with a yield of 78%. Product molecular formula: C 56 H 40 N6O; molecular weight m / z: 812.33; elemental analysis results: C, 82.73; H, 4.96; N, 10.34; O, 1.97.

[0217] Example 42

[0218] In this example, compound 17 was prepared, and its structural formula and synthetic route are shown below:

[0219]

[0220] The specific reaction steps are as follows: Compared with Example 31, the difference is that A1 is replaced with an equivalent amount of A7, 7.2 mmol of 9,9-dimethyl-9,10-dihydroacridine is added, and the other raw materials and steps are the same as Example 31. Finally, the product compound 17 is obtained with a yield of 74%. The product molecular formula is: C 86 H 66 N8O; molecular weight m / z: 1226.54; elemental analysis results: C, 84.15; H, 5.42; N, 9.13; O, 1.30.

[0221] Example 43

[0222] In this example, compound 18 was prepared, and its structural formula and synthetic route are shown below:

[0223]

[0224] The specific reaction steps are as follows: Compared with Example 31, the difference is that A1 is replaced with an equivalent amount of A8. The other raw materials and steps are the same as Example 31, and the product compound 18 is finally obtained with a yield of 78%. Product molecular formula: C 58 H 38 N8O; molecular weight m / z: 862.32; elemental analysis results: C, 80.72; H, 4.44; N, 12.98; O, 1.85.

[0225] Example 44

[0226] In this example, compound 19 was prepared, and its structural formula and synthetic route are shown below:

[0227]

[0228] The specific reaction steps are as follows: Compared with Example 31, the difference is that A1 is replaced with an equivalent amount of A9. The other raw materials and steps are the same as Example 31, and the product compound 19 is finally obtained with a yield of 81%. The product molecular formula is: C 70 H 46 N8O; molecular weight m / z: 1014.38; elemental analysis results: C, 82.82; H, 4.57; N, 11.04; O, 1.58.

[0229] Example 45

[0230] In this example, compound 20 was prepared, and its structural formula and synthetic route are shown below:

[0231]

[0232] The specific reaction steps are as follows: Compared with Example 31, the difference is that A1 is replaced with an equivalent amount of A10. The other raw materials and steps are the same as Example 31, and the product compound 20 is finally obtained with a yield of 80%. Product molecular formula: C 66 H 46 N8O; molecular weight m / z: 966.38; elemental analysis results: C, 81.97; H, 4.79; N, 11.59; O, 1.65.

[0233] Example 46

[0234] In this example, compound 21 was prepared, and its structural formula and synthetic route are shown below:

[0235]

[0236] The specific reaction steps are as follows: Compared with Example 26, the difference is that A1 is replaced with an equivalent amount of A11. The other raw materials and steps are the same as Example 26, and the product compound 21 is finally obtained with a yield of 87%. Product molecular formula: C 56 H 38 N4O; molecular weight m / z: 782.30; elemental analysis results: C, 85.91; H, 4.89; N, 7.16; O, 2.04.

[0237] Example 47

[0238] In this example, compound 22 was prepared, and its structural formula and synthetic route are shown below:

[0239]

[0240] The specific reaction steps are as follows: Compared with Example 26, the difference is that A1 is replaced with an equivalent amount of A12, 7.2 mmol of triphenylamine-4-boric acid is added, and the other raw materials and steps are the same as Example 26. Finally, the product compound 22 is obtained with a yield of 78%. The product molecular formula is: C 92 H 64 N6O; molecular weight m / z: 1269.52; elemental analysis results: C, 87.04; H, 5.08; N, 6.62; O, 1.26.

[0241] Example 48

[0242] In this example, compound 23 was prepared, and its structural formula and synthetic route are shown below:

[0243]

[0244] The specific reaction steps are as follows: Compared with Example 26, the difference is that A1 is replaced with an equivalent amount of A13. The other raw materials and steps are the same as Example 26, and the product compound 23 is finally obtained with a yield of 88%. Product molecular formula: C 58 H 36 N6O; molecular weight m / z: 832.30; elemental analysis results: C, 83.63; H, 4.36; N, 10.09; O, 1.92.

[0245] Example 49

[0246] In this example, compound 24 was prepared, and its structural formula and synthetic route are shown below:

[0247]

[0248] The specific reaction steps are as follows: Compared with Example 26, the difference is that A1 is replaced with an equivalent amount of A14. The other raw materials and steps are the same as Example 26, and the product compound 24 is finally obtained with a yield of 87%. Product molecular formula: C 70 H 44 N6O; molecular weight m / z: 984.36; elemental analysis results: C, 85.34; H, 4.50; N, 8.53; O, 1.62.

[0249] Example 50

[0250] In this example, compound 25 was prepared, and its structural formula and synthetic route are shown below:

[0251]

[0252] The specific reaction steps are as follows: Compared with Example 26, the difference is that A1 is replaced with an equivalent amount of A15. The other raw materials and steps are the same as Example 26, and the product compound 25 is finally obtained with a yield of 77%. Product molecular formula: C 66 H 44 N6O; molecular weight m / z: 936.36; elemental analysis results: C, 84.59; H, 4.73; N, 8.97; O, 1.71.

[0253] Example 51

[0254] In this example, compound 26 was prepared, and its structural formula and synthetic route are shown below:

[0255]

[0256] The specific reaction steps are as follows: Compared with Example 31, the difference is that A1 is replaced with an equivalent amount of A11. The other raw materials and steps are the same as Example 31, and the product compound 26 is finally obtained with a yield of 79%. Product molecular formula: C 50 H 38 N4O; molecular weight m / z: 710.30; elemental analysis results: C, 84.48; H, 5.39; N, 7.88; O, 2.25.

[0257] Example 52

[0258] In this example, compound 27 was prepared, and its structural formula and synthetic route are shown below:

[0259]

[0260] The specific reaction steps are as follows: Compared with Example 31, the difference is that A1 is replaced with an equivalent amount of A12, 7.2 mmol of 9,9-dimethyl-9,10-dihydroacridine is added, and the other raw materials and steps are the same as Example 31. Finally, the product compound 27 is obtained with a yield of 74%. The product molecular formula is: C 80 H 64 N6O; molecular weight m / z: 1124.51; elemental analysis results: C, 85.38; H, 5.73; N, 7.47; O, 1.42.

[0261] Example 53

[0262] In this example, compound 28 was prepared, and its structural formula and synthetic route are shown below:

[0263]

[0264] The specific reaction steps are as follows: Compared with Example 31, the difference is that A1 is replaced with an equivalent amount of A13. The other raw materials and steps are the same as Example 31, and the product compound 28 is finally obtained with a yield of 78%. Product molecular formula: C 52 H 36 N6O; molecular weight m / z: 760.30; elemental analysis results: C, 82.08; H, 4.77; N, 11.05; O, 2.10.

[0265] Example 54

[0266] In this example, compound 29 was prepared, and its structural formula and synthetic route are shown below:

[0267]

[0268] The specific reaction steps are as follows: Compared with Example 31, the difference is that A1 is replaced with an equivalent amount of A14. The other raw materials and steps are the same as Example 31, and the product compound 29 is finally obtained with a yield of 74%. Product molecular formula: C 64 H 44 N6O; molecular weight m / z: 912.36; elemental analysis results: C, 84.19; H, 4.86; N, 9.20; O, 1.75.

[0269] Example 55

[0270] In this example, compound 30 was prepared, and its structural formula and synthetic route are shown below:

[0271]

[0272] The specific reaction steps are as follows: Compared with Example 31, the difference is that A1 is replaced with an equivalent amount of A15. The other raw materials and steps are the same as Example 31, and the product compound 30 is finally obtained with a yield of 72%. Product molecular formula: C 60 H 44 N6O; molecular weight m / z: 864.36; elemental analysis results are: C, 83.31; H, 5.13; N, 9.72; O, 1.85.

[0273] Example 56

[0274] In this example, compound 31 was prepared, and its structural formula and synthetic route are shown below:

[0275]

[0276] The specific reaction steps are as follows: Compared with Example 26, the difference is that A1 is replaced with an equivalent amount of A16. The other raw materials and steps are the same as Example 26, and the product compound 31 is finally obtained with a yield of 87%. The product molecular formula is: C 58 H 36 N6O; molecular weight m / z: 832.30; elemental analysis results: C, 83.63; H, 4.36; N, 10.09; O, 1.92.

[0277] Example 57

[0278] In this example, compound 32 was prepared, and its structural formula and synthetic route are shown below:

[0279]

[0280] The specific reaction steps are as follows: Compared with Example 26, the difference is that A1 is replaced with an equivalent amount of A17, 7.2 mmol of triphenylamine-4-boric acid is added, and the other raw materials and steps are the same as Example 26. Finally, the product compound 32 is obtained with a yield of 72%. The product molecular formula is: C 94 H 62 N8O; molecular weight m / z: 1319.51; elemental analysis results: C, 85.56; H, 4.74; N, 8.49; O, 1.21.

[0281] Example 58

[0282] In this example, compound 33 was prepared, and its structural formula and synthetic route are shown below:

[0283]

[0284] The specific reaction steps are as follows: Compared with Example 26, the difference is that A1 is replaced with an equivalent amount of A18. The other raw materials and steps are the same as Example 26, and the product compound 33 is finally obtained with a yield of 80%. The product molecular formula is: C 60 H 34 N8O; molecular weight m / z: 882.29; elemental analysis results: C, 81.62; H, 3.88; N, 12.69; O, 1.81.

[0285] Example 59

[0286] In this example, compound 34 was prepared, and its structural formula and synthetic route are shown below:

[0287]

[0288] The specific reaction steps are as follows: Compared with Example 26, the difference is that A1 is replaced with an equivalent amount of A19. The other raw materials and steps are the same as Example 26, and the product compound 34 is finally obtained with a yield of 85%. The product molecular formula is: C 72 H 42 N8O; molecular weight m / z: 1034.35; elemental analysis results: C, 83.54; H, 4.09; N, 10.82; O, 1.55.

[0289] Example 60

[0290] In this example, compound 35 was prepared, and its structural formula and synthetic route are shown below:

[0291]

[0292] The specific reaction steps are as follows: Compared with Example 26, the difference is that A1 is replaced with an equivalent amount of A20. The other raw materials and steps are the same as Example 26, and the product compound 35 is finally obtained with a yield of 78%. Product molecular formula: C 68 H 42 N8O; molecular weight m / z: 986.35; elemental analysis results: C, 82.74; H, 4.29; N, 11.35; O, 1.62.

[0293] Example 61

[0294] In this example, compound 36 was prepared, and its structural formula and synthetic route are shown below:

[0295]

[0296] The specific reaction steps are as follows: Compared with Example 31, the difference is that 9,9-dimethyl-9,10-dihydroacridine is replaced with an equivalent amount of phenoxazine. The other raw materials and steps are the same as Example 31, and the product compound 36 is finally obtained with a yield of 62%. Product molecular formula: C 52 H 30 N4O3; molecular weight m / z: 758.23; elemental analysis results are: C, 82.31; H, 3.99; N, 7.38; O, 6.33.

[0297] Example 62

[0298] In this example, compound 37 was prepared, and its structural formula and synthetic route are shown below:

[0299]

[0300] The specific reaction steps are as follows: Compared with Example 61, the difference is that A1 is replaced with an equivalent amount of A2, 7.2 mmol of phenoxazine is added, and the other raw materials and steps are the same as Example 61. Finally, the product compound 37 is obtained with a yield of 50%. The product molecular formula is: C 76 H 44 N6O5; molecular weight m / z: 1120.34; elemental analysis results are: C, 81.41; H, 3.96; N, 7.50; O, 7.13.

[0301] Example 63

[0302] In this example, compound 38 was prepared, and its structural formula and synthetic route are shown below:

[0303]

[0304] The specific reaction steps are as follows: Compared with Example 61, the difference is that A1 is replaced with an equivalent amount of A3. The other raw materials and steps are the same as Example 61, and the product compound 68 is finally obtained with a yield of 64%. Product molecular formula: C 54 H 28 N6O3; molecular weight m / z: 808.22; elemental analysis results are: C, 80.19; H, 3.49; N, 10.39; O, 5.93.

[0305] Example 64

[0306] In this example, compound 39 was prepared, and its structural formula and synthetic route are shown below:

[0307]

[0308] The specific reaction steps are as follows: Compared with Example 61, the difference is that A1 is replaced with an equivalent amount of A4. The other raw materials and steps are the same as Example 61, and the product compound 39 is finally obtained with a yield of 65%. Product molecular formula: C 66 H 36 N6O3; molecular weight m / z: 960.28; elemental analysis results: C, 82.49; H, 3.78; N, 8.74; O, 4.99.

[0309] Example 65

[0310] In this example, compound 40 was prepared, and its structural formula and synthetic route are shown below:

[0311]

[0312] The specific reaction steps are as follows: Compared with Example 61, the difference is that A1 is replaced with an equivalent amount of A5. The other raw materials and steps are the same as Example 61, and the product compound 40 is finally obtained with a yield of 63%. Product molecular formula: C 62 H 36 N6O3; molecular weight m / z: 912.28; elemental analysis results are: C, 81.56; H, 3.97; N, 9.20; O, 5.26.

[0313] Example 66

[0314] In this example, compound 41 was prepared, and its structural formula and synthetic route are shown below:

[0315]

[0316] The specific reaction steps are as follows: Compared with Example 61, the difference is that A1 is replaced with an equivalent amount of A6. The other raw materials and steps are the same as Example 61, and the product compound 41 is finally obtained with a yield of 50%. Product molecular formula: C 50 H 28 N6O3; molecular weight m / z: 760.22; elemental analysis results are: C, 78.94; H, 3.71; N, 11.05; O, 6.31.

[0317] Example 67

[0318] In this example, compound 42 was prepared, and its structural formula and synthetic route are shown below:

[0319]

[0320] The specific reaction steps are as follows: Compared with Example 61, the difference is that A1 is replaced with an equivalent amount of A7, 7.2 mmol of phenoxazine is added, and the other raw materials and steps are the same as Example 61. Finally, the product compound 42 is obtained with a yield of 74%. The product molecular formula is: C 74 H 42 N8O5; molecular weight m / z: 1122.33; elemental analysis results are: C, 79.13; H, 3.77; N, 9.98; O, 7.12.

[0321] Example 68

[0322] In this example, compound 43 was prepared, and its structural formula and synthetic route are shown below:

[0323]

[0324] The specific reaction steps are as follows: Compared with Example 61, the difference is that A1 is replaced with an equivalent amount of A8. The other raw materials and steps are the same as Example 61, and the final product compound 43 is obtained with a yield of 58%. Product molecular formula: C 52 H 26 N8O3; molecular weight m / z: 810.21; elemental analysis results are: C, 77.03; H, 3.23; N, 13.82; O, 5.92.

[0325] Example 69

[0326] In this example, compound 44 was prepared, and its structural formula and synthetic route are shown below:

[0327]

[0328] The specific reaction steps are as follows: Compared with Example 61, the difference is that A1 is replaced with an equivalent amount of A9. The other raw materials and steps are the same as Example 61, and the product compound 44 is finally obtained with a yield of 51%. The product molecular formula is: C 64 H 34 N8O3; molecular weight m / z: 962.28; elemental analysis results: C, 79.82; H, 3.56; N, 11.64; O, 4.98.

[0329] Example 70

[0330] In this example, compound 45 was prepared, and its structural formula and synthetic route are shown below:

[0331]

[0332] The specific reaction steps are as follows: Compared with Example 61, the difference is that A1 is replaced with an equivalent amount of A10. The other raw materials and steps are the same as Example 61, and the product compound 45 is finally obtained with a yield of 48%. Product molecular formula: C 60 H 34 N8O3; molecular weight m / z: 914.28; elemental analysis results: C, 78.76; H, 3.75; N, 12.25; O, 5.25.

[0333] Example 71

[0334] In this example, compound 46 was prepared, and its structural formula and synthetic route are shown below:

[0335]

[0336] The specific reaction steps are as follows: Compared with Example 61, the difference is that A1 is replaced with an equivalent amount of A11. The other raw materials and steps are the same as Example 61, and the final product compound 46 is obtained with a yield of 78%. Product molecular formula: C 44 H 26 N4O3; molecular weight m / z: 658.20; elemental analysis results: C, 80.23; H, 3.98; N, 8.51; O, 7.29.

[0337] Example 72

[0338] In this example, compound 47 was prepared, and its structural formula and synthetic route are shown below:

[0339]

[0340] The specific reaction steps are as follows: Compared with Example 61, the difference is that A1 is replaced with an equivalent amount of A12, 7.2 mmol of phenoxazine is added, and the other raw materials and steps are the same as Example 61. Finally, the product compound 47 is obtained with a yield of 64%. The product molecular formula is: C 68 H 40 N6O5; molecular weight m / z: 1020.31; elemental analysis results are: C, 79.99; H, 3.95; N, 8.23; O, 7.83.

[0341] Example 73

[0342] In this example, compound 48 was prepared, and its structural formula and synthetic route are shown below:

[0343]

[0344] The specific reaction steps are as follows: Compared with Example 61, the difference is that A1 is replaced with an equivalent amount of A13. The other raw materials and steps are the same as Example 61, and the final product compound 48 is obtained with a yield of 68%. Product molecular formula: C 46 H 24 N6O3; molecular weight m / z: 708.19; elemental analysis results are: C, 77.96; H, 3.41; N, 11.86; O, 6.77.

[0345] Example 74

[0346] In this example, compound 49 was prepared, and its structural formula and synthetic route are shown below:

[0347]

[0348] The specific reaction steps are as follows: Compared with Example 61, the difference is that A1 is replaced with an equivalent amount of A14. The other raw materials and steps are the same as Example 61, and the product compound 49 is finally obtained with a yield of 65%. The product molecular formula is: C 58 H 32 N6O3; molecular weight m / z: 860.25; elemental analysis results are: C, 80.92; H, 3.75; N, 9.76; O, 5.57.

[0349] Example 75

[0350] In this example, compound 50 was prepared, and its structural formula and synthetic route are shown below:

[0351]

[0352] The specific reaction steps are as follows: Compared with Example 61, the difference is that A1 is replaced with an equivalent amount of A15. The other raw materials and steps are the same as Example 61, and the product compound 50 is finally obtained with a yield of 72%. Product molecular formula: C 54 H 32 N6O3; molecular weight m / z: 812.25; elemental analysis results: C, 79.79; H, 3.97; N, 10.34; O, 5.90.

[0353] Application Example 1

[0354] The preparation and performance evaluation of organic electroluminescent devices using organic small molecule materials as acceptor units in the light-emitting layer.

[0355] The specific stacked structure of the general organic electroluminescent device in this embodiment is as follows:

[0356] Glass substrate / ITO (95nm) / TAPC (30nm) / mCP (10nm) / compound (3wt%): CBP (20nm) / TmPyPB (50nm) / LiF (1nm) / Al (100nm). ITO is the anode, TAPC is the hole injection layer, mCP is the electron blocking layer, CBP is the luminescent material doping host, TmPyPB is the electron transport layer, LiF is the electron injection layer, and Al is the cathode.

[0357] The steps for preparing the light emitting device are as follows:

[0358] The ITO transparent conductive glass was cleaned with acetone, micron-grade semiconductor detergent, deionized water, and isopropyl alcohol for 15 minutes to remove dirt on the substrate surface. It was then placed in a constant temperature oven to dry at 80 degrees Celsius for use. The dried ITO substrate was treated with an oxygen plasma ignition device for 3 minutes to further remove organic attachments on the surface. The glass with the anode ITO was placed in a vacuum chamber with a vacuum condition of approximately 4×10 -4 Majesty, The organic material layer is evaporated on the anode film at a deposition rate. In the evaporation of the light-emitting layer, CBP and the light-emitting material are placed on two evaporation sources respectively, and the mixing ratio of the two is controlled by a certain deposition rate. LiF was evaporated at a deposition rate of An Al electrode was evaporated at a deposition rate of , to obtain the organic light emitting diode device of this embodiment.

[0359] The molecular structures of TAPC, mCP, CBP and TmPyPB described in Application Example 1 are shown below:

[0360]

[0361] In this application example, compounds 27, 47, 32, and 33 were compared with previously reported materials M1, M2, M3, and M4. Compared to similar previously reported energy-absorbing units, the new energy-absorbing units in this application exhibit significant device enhancements. The structures of the reported comparative materials M1, M2, M3, and M4 are as follows:

[0362]

[0363] Table 1 Device data comparison

[0364]

[0365] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be considered as equivalent replacement methods and are included in the scope of protection of the present invention.

Claims

1. An organic small molecule material based on a dibenzoxepin derivative as a receptor core unit, characterized in that: Having at least one of the following structural formulas: Wherein R is identical or different and is at least one of an aromatic ring composed of electron-donating vinylene carbon and hydrogen atoms, an aromatic heterocycle composed of carbon, nitrogen and hydrogen atoms, an aromatic heterocycle composed of carbon, nitrogen, oxygen and hydrogen atoms, an aromatic heterocycle composed of carbon, sulfur and hydrogen atoms, and an aromatic heterocycle composed of carbon, silicon and hydrogen atoms.

2. The organic small molecule material based on a dibenzoxepin derivative as a receptor core unit according to claim 1, characterized in that: The R is the same or different and is at least one of the following structures:

3. The organic small molecule material based on a dibenzoxepin derivative as a receptor core unit according to claim 1 or 2, characterized in that: Having at least one of the structural formulas shown in 1 to 50:

4. The organic small molecule material based on a dibenzoxepin derivative as a receptor core unit according to claim 3, characterized in that: Has at least one of the following structures:

5. The method for preparing an organic small molecule material based on a dibenzoxepin derivative as an acceptor core unit according to any one of claims 1 to 4, characterized in that: The following steps are involved: (1) a dibenzoxetyl-diketone derivative is subjected to a ring-forming reaction to obtain an electron-withdrawing intermediate; (2) The dibenzoxetine derivatives are subjected to Suzuki coupling, Buchwald-Hartwig coupling or copper-catalyzed amination reaction of aryl halides to obtain organic small molecule materials based on the dibenzoxetine derivatives as the receptor core unit.

6. The method for preparing an organic small molecule material based on a dibenzoxepin derivative as an acceptor core unit according to claim 5, characterized in that: The cyclization reaction in step (1) is specifically: heating and cyclizing at least one of the dibenzoxadione derivatives M1 to M5 with at least one of the compounds m3 to m7 to obtain an electron-withdrawing intermediate; The compound M1 is M2 is M3 is M4 is M5 is m3 is 3,6-dibromophenanthrene-9,10-diamine; compound m4 is Compound m5 is 4,5-dibromo-o-phenylenediamine; Compound m6 is Compound m7 is The molar ratio of at least one of the dibenzoxepin-dione derivatives M1 to M5 to at least one of the compounds m3 to m7 is 1:1 to 1.2; The heating cyclization reaction condition is heating under reflux for 8 to 24 hours.

7. The method for preparing an organic small molecule material based on a dibenzoxepin derivative as a receptor core unit according to claim 5 or 6, characterized in that: Step (2) the halogen atom in the electron-withdrawing intermediate reacts with triphenylamine-4-boric acid in a molar ratio of 1:1 to 1.5 through a Suzuki coupling reaction to obtain an organic small molecule material based on a dibenzoxepin derivative as an acceptor core unit; The Suzuki coupling reaction is carried out in the presence of a palladium catalyst and a base, wherein the amount of the palladium catalyst is 1 to 10% of the molar amount of the electron-withdrawing intermediate; The temperature of the Suzuki coupling reaction is 80-90° C., and the reaction time is 8-24 hours.

8. The method for preparing an organic small molecule material based on a dibenzoxepin derivative as a receptor core unit according to claim 5 or 6, characterized in that: Step (2) the halogen atom in the electron-withdrawing intermediate reacts with at least one of 9,9-dimethyl-9,10-dihydroacridine and phenoxazine in a molar ratio of 1:1 to 1.5 through a Buchwald-Hartwig coupling reaction to obtain an organic small molecule material based on a dibenzoxepin derivative as an acceptor core unit; The Buchwald-Hartwig coupling reaction is carried out in the presence of a palladium catalyst and a base, wherein the amount of the palladium catalyst is 1 to 10% of the molar amount of the electron-withdrawing intermediate; The Buchwald-Hartwig coupling reaction temperature is 80-90° C. and the reaction time is 8-24 hours.

9. Use of the organic small molecule material based on a dibenzoxepin derivative as an acceptor core unit according to any one of claims 1 to 4 in the preparation of an organic optoelectronic device.

10. An organic light emitting diode, characterized in that: The structure includes, from bottom to top, a transparent substrate, a transparent anode layer, one or more organic light-emitting layer units, and a cathode layer; The organic light-emitting layer unit includes a hole injection layer, a hole transport layer, one or more light-emitting layers, and an electron transport layer; The light-emitting layer comprises the organic small molecule material based on the dibenzoxepin derivative as the acceptor core unit according to any one of claims 1 to 4; The organic small molecule material based on the dibenzoxepin derivative as the acceptor core unit accounts for 1 to 5 wt % of the mass of the light-emitting layer.

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