Organic small-molecular luminescent material based on dibenzoxaheptacyclic derivative and preparation and application of organic small-molecular luminescent material

Abstract

The invention discloses an organic small-molecular luminescent material based on a dibenzoxaheptacyclic derivative as well as preparation and application of the organic small-molecular luminescent material. The dibenzoxahepta-ring is used as an acceptor core unit, and the molecular weight, charge transfer degree, light-emitting wavelength and other material 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, the 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, and the horizontal molecular orientation is improved, so that the device structure is simplified, and the device performance is improved. As a luminescent layer of an organic electroluminescent device, the material has the advantages of adjustable light color, high efficiency, high stability and the like.

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 dibenzoxetyl ring derivative as an acceptor core unit, and its preparation and application. 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 the thermally activated delayed fluorescence (TADF) mechanism have been widely used in OLED devices. Due to their small singlet-triplet energy gap, these materials effectively overcome the low exciton utilization rate of traditional fluorescent materials. By utilizing the 25% probability of generating singlet excitons and 75% probability of generating triplet excitons under electroinduced conditions, they significantly improve the luminous efficiency of OLEDs. Currently, the luminous efficiency of blue and green luminescent materials based on TAF 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 dibenzoxetyl derivatives as acceptor core units.

[0005] Using dibenzoxetyl ring as the acceptor core unit, by varying the conjugation length of the acceptor core unit and the type and size of the linker unit, material properties such as molecular weight, charge transfer degree, and emission wavelength 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 non-planarity of the structure and reducing the degree of material stacking, effectively suppressing the material's aggregation quenching and avoiding the carrier imbalance problem of unipolar organic optoelectronic materials. At the same time, it can effectively control the molecular conjugation length and improve horizontal molecular orientation, thereby simplifying the device structure and improving device performance.

[0006] The dibenzoxetyl aromatic amine derivative developed by this invention exhibits thermally activated delayed fluorescence. This small organic molecule has a simple structure, a defined molecular weight, and is easily purified. It can also be formed into organic thin films through vacuum evaporation or spin coating and applied to organic optoelectronic devices such as 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 aforementioned organic small molecule luminescent materials based on dibenzoxetyl derivatives as receptor core units. The preparation method for this type of material uses a novel dibenzoxetyl-diketone derivative as the initial reaction raw material, followed by a series of simple reactions to obtain the target compound.

[0008] Another object of the present invention is to provide the use of the above series of organic small molecule luminescent materials in the preparation of organic photoelectric 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 dibenzoxetyl 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 organic small molecule material based on a dibenzoxetyl derivative as a receptor core unit has at least one of the following structural formulas:

[0014]

[0015] Further preferably, the organic small molecule material based on the dibenzoxetyl derivative as the receptor core unit has at least one of the following structural formulas:

[0016]

[0017] More preferably, the R is the same or different At least one of , wherein * is a linking site.

[0018] Preferably, the organic small molecule material based on a dibenzoxetyl derivative as a receptor core unit has at least one of the structural formulas shown in 1 to 60:

[0019]

[0020]

[0021]

[0022]

[0023]

[0024] Further preferably, the organic small molecule material based on the dibenzoxetyl derivative as the receptor core unit has at least one of the structural formulas shown in 1 to 18:

[0025]

[0026]

[0027] Most preferably, the organic small molecule material based on a dibenzoxetyl derivative as a receptor core unit has at least one of the structural formulae shown in 7 to 18:

[0028]

[0029] The preparation method of the above-mentioned organic small molecule material based on a dibenzoxetyl derivative as a receptor core unit comprises the following steps:

[0030] (1) a dihalogenated dibenzoxepin-dione is subjected to a ring-forming reaction to obtain an electron-withdrawing intermediate;

[0031] (2) The dihalogenated dibenzoxetane-diones or the electron-withdrawing intermediate of step (1) are subjected to Suzuki coupling, Buchwald-Hartwig coupling or copper-catalyzed amination reaction of aryl halides to obtain an organic small molecule material based on a dibenzoxetane derivative as an acceptor core unit.

[0032] Preferably, the dihalogenated dibenzoxepin-dione in step (1) is obtained by reacting compound I with 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU) in the presence of a catalyst.

[0033] The structural formula of compound I is Wherein R1 is halogen, more preferably chlorine.

[0034] The molar ratio of the compound I to 1,8-diazabicyclo[5,4,0]undec-7-ene is 1:1-1.5, and more preferably 1:1.2.

[0035] The catalyst is 3-benzyl-5-(2-hydroxyethyl)-4-methylthiazole chloride; the amount of the catalyst used is 10-30% of the molar amount of compound I, more preferably 20%.

[0036] The reaction temperature is room temperature and the reaction time is 0.5 to 2 hours.

[0037] Preferably, the cyclization reaction in step (1) is specifically: dihalogenated dibenzoxepin-dione is subjected to a heating cyclization reaction with at least one of compounds m2 to m10 to obtain an electron-withdrawing intermediate;

[0038] The compound m2 is 3,4-diaminobenzophenone; the compound m3 is diaminomaleonitrile; the compound m4 is o-phenylenediamine; the compound m5 is diamino o-phenylenediamine; the compound m6 is [1,1':2',1"-terphenyl]-4',5'-diamine; and the compound m7 is Compound m8 is Compound m9 is Compound m10 is

[0039] The molar ratio of the dihalogenated dibenzoxepin-dione to the compounds m2 to m10 is 1:1 to 1.2, more preferably 1:1.

[0040] The heating cyclization reaction condition is heating under reflux for 8 to 24 hours.

[0041] Preferably, the dihalogenated dibenzoxadione or electron-withdrawing intermediate in step (2) is reacted with 4-(carbazol-9-yl)phenylboronic acid, triphenylamine-4-boronic acid, compound m11 Compound m12 Compound m13 and compound m14 At least one of the compounds is subjected to a Suzuki coupling reaction at a molar ratio of 1:1 to 1.5 to obtain an organic small molecule material based on a dibenzoxetyl ring derivative as a receptor core unit.

[0042] 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 dihalogenated dibenzoxepin-dione or the electron-withdrawing intermediate, and more preferably 5%.

[0043] The temperature of the Suzuki coupling reaction is 80-90° C., and the reaction time is 8-24 hours.

[0044] Preferably, the reactions in steps (1) and (2) are both carried out under an inert gas atmosphere, and the inert gas is more preferably at least one of nitrogen, argon and helium.

[0045] Preferably, the solvent medium of the reaction in step (1) is acetic acid; and the reaction medium in step (2) is at least one of toluene, dioxane and ethanol.

[0046] The application of the above-mentioned organic small molecule luminescent material based on the dibenzoxetyl ring derivative as the acceptor core unit in the preparation of organic optoelectronic devices.

[0047] Preferably, the organic photoelectric device is an organic light emitting diode.

[0048] 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;

[0049] 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;

[0050] The light-emitting layer includes the above-mentioned organic small molecule light-emitting material based on the dibenzoxetyl ring derivative as the acceptor core unit.

[0051] 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.

[0052] Preferably, the organic small molecule luminescent material based on the dibenzoxetyl derivative as the acceptor core unit accounts for 1 to 5 wt% of the mass of the luminescent layer; more preferably 3 wt%.

[0053] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0054] (1) The organic small molecule material of the present invention, which uses a dibenzoxetyl derivative as a 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.

[0055] (2) The organic small molecule material of the present invention with a dibenzoxetyl 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.

[0056] (3) The present invention uses dibenzoxetyl ring 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.

[0057] (4) The present invention uses a dibenzoxetyl 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.

[0058] (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 and improve the horizontal molecular orientation, thereby achieving the simplification of the device structure and the improvement of the device performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0059] Figure 1 is a current density-voltage-brightness relationship curve of compound 8 applied to an organic light-emitting diode device;

[0060] Figure 2 is a graph showing the relationship between current efficiency, brightness and external quantum efficiency of compound 8 when applied to an organic light-emitting diode device;

[0061] Figure 3 is the electroluminescence spectrum of compound 8. DETAILED DESCRIPTION

[0062] The present invention will be described in further detail below with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.

[0063] 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.

[0064] Example 1

[0065] In this example, intermediate M1 was prepared, and its structural formula and synthetic route are shown below:

[0066]

[0067] 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 the reaction mixture at room temperature for 30 minutes. Water is added to the reaction 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 H6Cl2O3; molecular weight m / z: 291.97.

[0068] Example 2

[0069] In this example, intermediate M2 was prepared, and its structural formula and synthetic route are shown below:

[0070]

[0071] The specific reaction steps are as follows: A mixture of M1 (8 mmol) and 3,4-diaminobenzophenone m2 (8 mmol) is dissolved in 80 mL of acetic acid under an argon atmosphere and then heated to reflux 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 M2 with a yield of 54.8%. Product molecular formula: C 27 H 14 Cl2N2O2; molecular weight m / z: 468.04.

[0072] Example 3

[0073] In this example, intermediate M3 was prepared, and its structural formula and synthetic route are shown below:

[0074]

[0075] The specific reaction steps are as follows: Compared with Example 2, the difference is that 3,4-diaminobenzophenone is replaced with an equivalent amount of diaminomaleonitrile m3. The other raw materials and steps are the same as Example 2. The intermediate M3 product is finally obtained with a yield of 73%. The product molecular formula is: C 18 H6Cl2N4O; molecular weight m / z: 365.17.

[0076] Example 4

[0077] In this example, intermediate M4 was prepared, and its structural formula and synthetic route are shown below:

[0078]

[0079] The specific reaction steps are as follows: Compared with Example 2, the difference is that 3,4-diaminobenzophenone is replaced with an equivalent amount of o-phenylenediamine m4. The other raw materials and steps are the same as Example 2. The intermediate M4 product is finally obtained with a yield of 72%. The product molecular formula is: C 20 H 10 Cl2N2O; molecular weight m / z: 364.02.

[0080] Example 5

[0081] In this example, intermediate M5 was prepared, and its structural formula and synthetic route are shown below:

[0082]

[0083] The specific reaction steps are as follows: Compared with Example 2, the difference is that 3,4-diaminobenzophenone is replaced with an equivalent amount of diamino-o-phenylenedicyanide M5. The other raw materials and steps are the same as Example 2, and the intermediate M5 product is finally obtained with a yield of 70%. Product molecular formula: C 22 H8Cl2N4O; molecular weight m / z: 414.01.

[0084] Example 6

[0085] In this example, intermediate M6 was prepared, and its structural formula and synthetic route are shown below:

[0086]

[0087] The specific reaction steps are as follows: Compared with Example 2, the difference is that 3,4-diaminobenzophenone is replaced with an equivalent amount of [1,1':2',1"-terphenyl]-4',5'-diamine m6. The other raw materials and steps are the same as Example 2, and the intermediate M6 product is finally obtained with a yield of 65%. The product molecular formula is: C 32 H 18 Cl2N2O; molecular weight m / z: 516.08.

[0088] Example 7

[0089] In this example, intermediate M7 was prepared, and its structural formula and synthetic route are shown below:

[0090]

[0091] The specific reaction steps are as follows: Compared with Example 2, the difference is that 3,4-diaminobenzophenone is replaced with an equivalent amount of m7. The other raw materials and steps are the same as Example 2. Finally, the intermediate M7 product is obtained with a yield of 65%. Product molecular formula: C 34 H 16 Cl2N4O; molecular weight m / z: 566.07.

[0092] Example 8

[0093] In this example, intermediate M8 was prepared, and its structural formula and synthetic route are shown below:

[0094]

[0095] The specific reaction steps are as follows: Compared with Example 2, the difference is that 3,4-diaminobenzophenone is replaced with an equivalent amount of m8. The other raw materials and steps are the same as Example 2. Finally, the intermediate M8 product is obtained with a yield of 46%. Product molecular formula: C28 H 14 Cl2N2O; molecular weight m / z: 464.05.

[0096] Example 9

[0097] In this example, intermediate M9 was prepared, and its structural formula and synthetic route are shown below:

[0098]

[0099] The specific reaction steps are as follows: Compared with Example 2, the difference is that 3,4-diaminobenzophenone is replaced with an equivalent amount of m9. The other raw materials and steps are the same as Example 2. The intermediate M9 product is finally obtained with a yield of 48%. The product molecular formula is: C 26 H12Cl2N4O; molecular weight m / z: 466.04.

[0100] Example 10

[0101] In this example, intermediate M10 was prepared, and its structural formula and synthetic route are shown below:

[0102]

[0103] The specific reaction steps are as follows: Compared with Example 2, the difference is that 3,4-diaminobenzophenone is replaced with an equivalent amount of m10. The other raw materials and steps are the same as Example 2, and the intermediate M10 product is finally obtained with a yield of 45%. Product molecular formula: C 32 H 16 Cl2N2O; molecular weight m / z: 514.06.

[0104] Example 11

[0105] In this example, compound 1 was prepared, and its structural formula and synthetic route are shown below:

[0106]

[0107] The specific reaction steps are as follows: The intermediate M1 (1.14 mmol) and 4-(carbazole-9-yl)phenylboronic acid (2.85 mmol) are dissolved in a 250 mL round-bottom flask containing 60 mL toluene, 25 mL ethanol and 20 mL K2CO3 aqueous solution (2 mol / L). After purging with argon for 15 minutes, the catalyst Pd(PPh3)4 (0.057 mmol, 66 mg) is quickly added, and then purged 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 three times with dichloromethane (DCM). The collected organic phase is further washed three 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 50 H 30 N2O3; molecular weight m / z: 706.23; elemental analysis results: C, 84.97; H, 4.28; N, 3.96; O, 6.79.

[0108] Example 12

[0109] In this example, compound 2 was prepared, and its structural formula and synthetic route are shown below:

[0110]

[0111] The specific reaction steps are as follows: Compared with Example 11, the difference is that 4-(carbazol-9-yl)phenylboronic acid is replaced with an equivalent amount of triphenylamine-4-boric acid. The other raw materials and steps are the same as Example 11, and the final product compound 2 is obtained with a yield of 83%. The product molecular formula is: C 50 H 34 N2O3; molecular weight m / z: 710.26; elemental analysis results are: C, 84.49; H, 4.82; N, 3.94; O, 6.75.

[0112] Example 13

[0113] In this example, compound 3 was prepared, and its structural formula and synthetic route are shown below:

[0114]

[0115] The specific reaction steps are as follows: Compared with Example 11, the difference is that 4-(carbazol-9-yl)phenylboronic acid is replaced with an equivalent amount of m11. The other raw materials and steps are the same as Example 11, and the final product compound 3 is obtained with a yield of 66%. The product molecular formula is: C 56 H 42N2O3; molecular weight m / z: 790.32; elemental analysis results are: C, 85.04; H, 5.35; N, 3.54; O, 6.07.

[0116] Example 14

[0117] In this example, compound 4 was prepared, and its structural formula and synthetic route are shown below:

[0118]

[0119] The specific reaction steps are as follows: Compared with Example 11, the difference is that 4-(carbazol-9-yl)phenylboronic acid is replaced with an equivalent amount of m12. The other raw materials and steps are the same as Example 11, and the final product compound 4 is obtained with a yield of 71%. The product molecular formula is: C 50 H 30 N2O5; molecular weight m / z: 738.22; elemental analysis results are: C, 81.29; H, 4.09; N, 3.79; O, 10.83.

[0120] Example 15

[0121] In this example, compound 5 was prepared, and its structural formula and synthetic route are shown below:

[0122]

[0123] The specific reaction steps are as follows: Compared with Example 11, the difference is that 4-(carbazol-9-yl)phenylboronic acid is replaced with an equivalent amount of m13. The other raw materials and steps are the same as Example 1. The final product compound 5 is obtained with a yield of 68%. The product molecular formula is: C 76 H 46 N2O3; molecular weight m / z: 1034.35; elemental analysis results: C, 88.18; H, 4.48; N, 2.71; O, 4.64.

[0124] Example 16

[0125] In this example, compound 6 was prepared, and its structural formula and synthetic route are shown below:

[0126]

[0127] The specific reaction steps are as follows: Compared with Example 11, the difference is that 4-(carbazol-9-yl)phenylboronic acid is replaced with an equivalent amount of m14. The other raw materials and steps are the same as Example 1. The final product compound 6 is obtained with a yield of 73%. The product molecular formula is: C 76 H 46N2O3S2; molecular weight m / z: 1098.29; elemental analysis results: C, 83.04; H, 4.22; N, 2.55; O, 4.37; S, 5.83.

[0128] Example 17

[0129] In this example, compound 7 was prepared, and its structural formula and synthetic route are shown below:

[0130]

[0131] The specific reaction steps are as follows: Compared with Example 11, the difference is that M1 is replaced with an equivalent amount of M2. The other raw materials and steps are the same as Example 11, and the product compound 7 is finally obtained with a yield of 73%. The product molecular formula is: C 63 H 38 N4O2; molecular weight m / z: 882.30; elemental analysis results are: C, 85.69; H, 4.34; N, 6.35; O, 3.62.

[0132] Example 18

[0133] In this example, compound 8 was prepared, and its structural formula and synthetic route are shown below:

[0134]

[0135] The specific reaction steps are as follows: Compared with Example 12, the difference is that M1 is replaced with an equivalent amount of M2. The other raw materials and steps are the same as Example 12, and the product compound 8 is finally obtained with a yield of 83%. The product molecular formula is: C 63 H 42 N4O2; molecular weight m / z: 886.33; elemental analysis results are: C, 85.30; H, 4.77; N, 6.32; O, 3.61.

[0136] Example 19

[0137] In this example, compound 9 was prepared, and its structural formula and synthetic route are shown below:

[0138]

[0139] The specific reaction steps are as follows: Compared with Example 13, the difference is that M1 is replaced with an equivalent amount of M2. The other raw materials and steps are the same as Example 13, and the product compound 9 is finally obtained with a yield of 66%. The product molecular formula is: C 69 H 50 N4O2; molecular weight m / z: 966.39; elemental analysis results are: C, 85.69; H, 5.21; N, 5.79; O, 3.31.

[0140] Example 20

[0141] In this example, compound 10 was prepared, and its structural formula and synthetic route are shown below:

[0142]

[0143] The specific reaction steps are as follows: Compared with Example 14, the difference is that M1 is replaced with an equivalent amount of M2. The other raw materials and steps are the same as Example 14. Finally, the product compound 10 is obtained with a yield of 71%. The product molecular formula is: C 63 H 38 N4O4; molecular weight m / z: 914.29; elemental analysis results: C, 82.70; H, 4.19; N, 6.12; O, 6.99.

[0144] Example 21

[0145] In this example, compound 11 was prepared, and its structural formula and synthetic route are shown below:

[0146]

[0147] The specific reaction steps are as follows: Compared with Example 15, the difference is that M1 is replaced with an equivalent amount of M2. The other raw materials and steps are the same as Example 15, and the product compound 11 is finally obtained with a yield of 73%. The product molecular formula is: C 89 H 54 N4O2; molecular weight m / z: 1210.42; elemental analysis results: C, 88.24; H, 4.49; N, 4.62; O, 2.64.

[0148] Example 22

[0149] In this example, compound 12 was prepared, and its structural formula and synthetic route are shown below:

[0150]

[0151] The specific reaction steps are as follows: Compared with Example 16, the difference is that M1 is replaced with an equivalent amount of M2. The other raw materials and steps are the same as Example 16. Finally, the product compound 12 is obtained with a yield of 73%. Product molecular formula: C 89 H 54 N4O2S2; molecular weight m / z: 274.37; elemental analysis results are: C, 83.80; H, 4.27; N, 4.39; O, 2.51; S, 5.03.

[0152] Example 23

[0153] In this example, compound 13 was prepared, and its structural formula and synthetic route are shown below:

[0154]

[0155] The specific reaction steps are as follows: Compared with Example 11, the difference is that M1 is replaced with an equivalent amount of M3. The other raw materials and steps are the same as Example 11, and the product compound 13 is finally obtained with a yield of 73%. Product molecular formula: C 56 H 32 N4O; molecular weight m / z: 776.26; elemental analysis results: C, 86.58; H, 4.15; N, 7.21; O, 2.06.

[0156] Example 24

[0157] In this example, compound 14 was prepared, and its structural formula and synthetic route are shown below:

[0158]

[0159] The specific reaction steps are as follows: Compared with Example 12, the difference is that M1 is replaced with an equivalent amount of M3. The other raw materials and steps are the same as Example 12, and the product compound 14 is finally obtained with a yield of 83%. The product molecular formula is: C 56 H 36 N4O; molecular weight m / z: 780.29; elemental analysis results: C, 86.13; H, 4.65; N, 7.17; O, 2.05.

[0160] Example 25

[0161] In this example, compound 15 was prepared, and its structural formula and synthetic route are shown below:

[0162]

[0163] The specific reaction steps are as follows: Compared with Example 13, the difference is that M1 is replaced with an equivalent amount of M3. The other raw materials and steps are the same as Example 13, and the product compound 15 is finally obtained with a yield of 66%. Product molecular formula: C 62 H 44 N4O; molecular weight m / z: 860.35; elemental analysis results: C, 86.48; H, 5.15; N, 6.51; O, 1.86.

[0164] Example 26

[0165] In this example, compound 16 was prepared, and its structural formula and synthetic route are shown below:

[0166]

[0167] The specific reaction steps are as follows: Compared with Example 14, the difference is that M1 is replaced with an equivalent amount of M3. The other raw materials and steps are the same as Example 14. The final product compound 16 is obtained with a yield of 71%. The product molecular formula is: C 56 H 32 N4O3; molecular weight m / z: 808.25; elemental analysis results are: C, 83.15; H, 3.99; N, 6.93; O, 5.93.

[0168] Example 27

[0169] In this example, compound 17 was prepared, and its structural formula and synthetic route are shown below:

[0170]

[0171] The specific reaction steps are as follows: Compared with Example 15, the difference is that M1 is replaced with an equivalent amount of M3. The other raw materials and steps are the same as Example 15. The final product compound 17 is obtained with a yield of 68%. The product molecular formula is: C 82 H 48 N4O; molecular weight m / z: 1104.38; elemental analysis results are: C, 89.11; H, 4.38; N, 5.07; O, 1.45.

[0172] Example 28

[0173] In this example, compound 18 was prepared, and its structural formula and synthetic route are shown below:

[0174]

[0175] The specific reaction steps are as follows: Compared with Example 16, the difference is that M1 is replaced with an equivalent amount of M3. The other raw materials and steps are the same as Example 16. Finally, the product compound 18 is obtained with a yield of 73%. Product molecular formula: C 82 H 48 N4OS2; molecular weight m / z: 1168.33; elemental analysis results: C, 84.22; H, 4.14; N, 4.79; O, 1.37; S, 5.48.

[0176] Example 29

[0177] In this example, compound 19 was prepared, and its structural formula and synthetic route are shown below:

[0178]

[0179] The specific reaction steps are as follows: Compared with Example 11, the difference is that M1 is replaced with an equivalent amount of M4. The other raw materials and steps are the same as Example 11, and the product compound 19 is finally obtained with a yield of 73%. The product molecular formula is: C 56 H 34 N4O; molecular weight m / z: 778.27; elemental analysis results: C, 86.35; H, 4.40; N, 7.19; O, 2.05.

[0180] Example 30

[0181] In this example, compound 20 was prepared, and its structural formula and synthetic route are shown below:

[0182]

[0183] The specific reaction steps are as follows: Compared with Example 12, the difference is that M1 is replaced with an equivalent amount of M4. The other raw materials and steps are the same as Example 12, and the product compound 20 is finally obtained with a yield of 83%. 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.

[0184] Example 31

[0185] In this example, compound 21 was prepared, and its structural formula and synthetic route are shown below:

[0186]

[0187] The specific reaction steps are as follows: Compared with Example 13, the difference is that M1 is replaced with an equivalent amount of M4. The other raw materials and steps are the same as Example 13, and the product compound 21 is finally obtained with a yield of 66%. The product molecular formula is: C 62 H 46 N4O; molecular weight m / z: 862.37; elemental analysis results: C, 86.28; H, 5.37; N, 6.49; O, 1.85.

[0188] Example 32

[0189] In this example, compound 22 was prepared, and its structural formula and synthetic route are shown below:

[0190]

[0191] The specific reaction steps are as follows: Compared with Example 14, the difference is that M1 is replaced with an equivalent amount of M4. The other raw materials and steps are the same as Example 14, and the product compound 22 is finally obtained with a yield of 71%. The product molecular formula is: C 56 H 34 N4O3; molecular weight m / z: 810.26; elemental analysis results are: C, 82.95; H, 4.23; N, 6.91; O, 5.92.

[0192] Example 33

[0193] In this example, compound 23 was prepared, and its structural formula and synthetic route are shown below:

[0194]

[0195] The specific reaction steps are as follows: Compared with Example 15, the difference is that M1 is replaced with an equivalent amount of M4. The other raw materials and steps are the same as Example 15, and the product compound 23 is finally obtained with a yield of 68%. The product molecular formula is: C 82 H 50 N4O; molecular weight m / z: 1106.40; elemental analysis results: C, 88.94; H, 4.55; N, 5.06; O, 1.44.

[0196] Example 34

[0197] In this example, compound 24 was prepared, and its structural formula and synthetic route are shown below:

[0198]

[0199] The specific reaction steps are as follows: Compared with Example 16, the difference is that M1 is replaced with an equivalent amount of M4. The other raw materials and steps are the same as Example 16. The final product compound 24 is obtained with a yield of 73%. The product molecular formula is: C 82 H 50 N4OS2; molecular weight m / z: 1170.34; elemental analysis results are: C, 84.08; H, 4.30; N, 4.78; O, 1.37; S, 5.47.

[0200] Example 35

[0201] In this example, compound 25 was prepared, and its structural formula and synthetic route are shown below:

[0202]

[0203] The specific reaction steps are as follows: Compared with Example 11, the difference is that M1 is replaced with an equivalent amount of M5. The other raw materials and steps are the same as Example 11, and the product compound 25 is finally obtained with a yield of 73%. Product molecular formula: C 58 H 32 N6O; molecular weight m / z: 828.26; elemental analysis results: C, 84.04; H, 3.89; N, 10.14; O, 1.93.

[0204] Example 36

[0205] In this example, compound 26 was prepared, and its structural formula and synthetic route are shown below:

[0206]

[0207] The specific reaction steps are as follows: Compared with Example 12, the difference is that M1 is replaced with an equivalent amount of M5. The other raw materials and steps are the same as Example 12, and the product compound 26 is finally obtained with a yield of 83%. 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.

[0208] Example 37

[0209] In this example, compound 27 was prepared, and its structural formula and synthetic route are shown below:

[0210]

[0211] The specific reaction steps are as follows: Compared with Example 13, the difference is that M1 is replaced with an equivalent amount of M5. The other raw materials and steps are the same as Example 13, and the product compound 27 is finally obtained with a yield of 66%. The product molecular formula is: 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.

[0212] Example 38

[0213] In this example, compound 28 was prepared, and its structural formula and synthetic route are shown below:

[0214]

[0215] The specific reaction steps are as follows: Compared with Example 14, the difference is that M1 is replaced with an equivalent amount of M5. The other raw materials and steps are the same as Example 14, and the product compound 28 is finally obtained with a yield of 71%. 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.

[0216] Example 39

[0217] In this example, compound 29 was prepared, and its structural formula and synthetic route are shown below:

[0218]

[0219] The specific reaction steps are as follows: Compared with Example 15, the difference is that M1 is replaced with an equivalent amount of M5. The other raw materials and steps are the same as Example 15, and the product compound 29 is finally obtained with a yield of 68%. The product molecular formula is: C 84 H 48 N6O; molecular weight m / z: 1156.39; elemental analysis results: C, 87.18; H, 4.18; N, 7.26; O, 1.38.

[0220] Example 40

[0221] In this example, compound 30 was prepared, and its structural formula and synthetic route are shown below:

[0222]

[0223] The specific reaction steps are as follows: Compared with Example 16, the difference is that M1 is replaced with an equivalent amount of M5. The other raw materials and steps are the same as Example 16, and the product compound 30 is finally obtained with a yield of 73%. The product molecular formula is: C 84 H 48 N6OS2; molecular weight m / z: 1220.33; elemental analysis results: C, 82.60; H, 3.96; N, 6.88; O, 1.31; S, 5.25.

[0224] Example 41

[0225] In this example, compound 31 was prepared, and its structural formula and synthetic route are shown below:

[0226]

[0227] The specific reaction steps are as follows: Compared with Example 11, the difference is that M1 is replaced with an equivalent amount of M6. The other raw materials and steps are the same as Example 11, and the product compound 31 is finally obtained with a yield of 73%. Product molecular formula: C 68 H 42 N4O; molecular weight m / z: 930.34; elemental analysis results: C, 87.72; H, 4.55; N, 6.02; O, 1.72.

[0228] Example 42

[0229] In this example, compound 32 was prepared, and its structural formula and synthetic route are shown below:

[0230]

[0231] The specific reaction steps are as follows: Compared with Example 12, the difference is that M1 is replaced with an equivalent amount of M6. The other raw materials and steps are the same as Example 12, and the product compound 32 is finally obtained with a yield of 83%. The product molecular formula is: C 68 H 46 N4O; molecular weight m / z: 934.37; elemental analysis results: C, 87.34; H, 4.96; N, 5.99; O, 1.71.

[0232] Example 43

[0233] In this example, compound 33 was prepared, and its structural formula and synthetic route are shown below:

[0234]

[0235] The specific reaction steps are as follows: Compared with Example 13, the difference is that M1 is replaced with an equivalent amount of M6. The other raw materials and steps are the same as Example 13, and the product compound 33 is finally obtained with a yield of 66%. The product molecular formula is: C 74 H 54 N4O; molecular weight m / z: 1014.43; elemental analysis results: C, 87.54; H, 5.36; N, 5.52; O, 1.58.

[0236] Example 44

[0237] In this example, compound 34 was prepared, and its structural formula and synthetic route are shown below:

[0238]

[0239] The specific reaction steps are as follows: Compared with Example 14, the difference is that M1 is replaced with an equivalent amount of M6. The other raw materials and steps are the same as Example 14, and the product compound 34 is finally obtained with a yield of 71%. The product molecular formula is: C 68 H 42 N4O3; molecular weight m / z: 962.33; elemental analysis results: C, 84.80; H, 4.40; N, 5.82; O, 4.98.

[0240] Example 45

[0241] In this example, compound 35 was prepared, and its structural formula and synthetic route are shown below:

[0242]

[0243] The specific reaction steps are as follows: Compared with Example 15, the difference is that M1 is replaced with an equivalent amount of M6. The other raw materials and steps are the same as Example 15, and the product compound 35 is finally obtained with a yield of 68%. The product molecular formula is: C 94 H 58 N4O; molecular weight m / z: 1258.46; elemental analysis results: C, 89.64; H, 4.64; N, 4.45; O, 1.27.

[0244] Example 46

[0245] In this example, compound 36 was prepared, and its structural formula and synthetic route are shown below:

[0246]

[0247] The specific reaction steps are as follows: Compared with Example 16, the difference is that M1 is replaced with an equivalent amount of M6. The other raw materials and steps are the same as Example 16, and the product compound 36 is finally obtained with a yield of 73%. The product molecular formula is: C 94 H 58 N4OS2; molecular weight m / z: 1322.41; elemental analysis results: C, 85.30; H, 4.42; N, 4.23; O, 1.21; S, 4.84.

[0248] Example 47

[0249] In this example, compound 37 was prepared, and its structural formula and synthetic route are shown below:

[0250]

[0251] The specific reaction steps are as follows: Compared with Example 11, the difference is that M1 is replaced with an equivalent amount of M7. The other raw materials and steps are the same as Example 11, and the product compound 37 is finally obtained with a yield of 73%. The product molecular formula is: C 70 H 40 N6O; molecular weight m / z: 980.33; elemental analysis results: C, 85.69; H, 4.11; N, 8.57; O, 1.63.

[0252] Example 48

[0253] In this example, compound 38 was prepared, and its structural formula and synthetic route are shown below:

[0254]

[0255] The specific reaction steps are as follows: Compared with Example 12, the difference is that M1 is replaced with an equivalent amount of M7. The other raw materials and steps are the same as Example 12, and the product compound 38 is finally obtained with a yield of 83%. The product molecular formula is: 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.

[0256] Example 49

[0257] In this example, compound 39 was prepared, and its structural formula and synthetic route are shown below:

[0258]

[0259] The specific reaction steps are as follows: Compared with Example 13, the difference is that M1 is replaced with an equivalent amount of M7. The other raw materials and steps are the same as Example 13, and the product compound 39 is finally obtained with a yield of 66%. The product molecular formula is: C 76 H 52 N6O; molecular weight m / z: 1064.42; elemental analysis results: C, 85.69; H, 4.92; N, 7.89; O, 1.50.

[0260] Example 50

[0261] In this example, compound 40 was prepared, and its structural formula and synthetic route are shown below:

[0262]

[0263] The specific reaction steps are as follows: Compared with Example 14, the difference is that M1 is replaced with an equivalent amount of M7. The other raw materials and steps are the same as Example 14. The final product compound 40 is obtained with a yield of 71%. The product molecular formula is: 70 H 40 N6O3; molecular weight m / z: 1012.32; elemental analysis results: C, 82.99; H, 3.98; N, 8.30; O, 4.74.

[0264] Example 51

[0265] In this example, compound 41 was prepared, and its structural formula and synthetic route are shown below:

[0266]

[0267] The specific reaction steps are as follows: Compared with Example 15, the difference is that M1 is replaced with an equivalent amount of M7. The other raw materials and steps are the same as Example 15, and the product compound 41 is finally obtained with a yield of 68%. The product molecular formula is: C 96 H 56 N6O; molecular weight m / z: 1308.45; elemental analysis results: C, 88.05; H, 4.31; N, 6.42; O, 1.22.

[0268] Example 52

[0269] In this example, compound 42 was prepared, and its structural formula and synthetic route are shown below:

[0270]

[0271] The specific reaction steps are as follows: Compared with Example 16, the difference is that M1 is replaced with an equivalent amount of M7. The other raw materials and steps are the same as Example 16. The final product compound 42 is obtained with a yield of 73%. The product molecular formula is: C 96 H 56 N6OS2; molecular weight m / z: 1372.40; elemental analysis results: C, 83.94; H, 4.11; N, 6.12; O, 1.16; S, 4.67.

[0272] Example 53

[0273] In this example, compound 43 was prepared, and its structural formula and synthetic route are shown below:

[0274]

[0275] The specific reaction steps are as follows: Compared with Example 11, the difference is that M1 is replaced with an equivalent amount of M8. The other raw materials and steps are the same as Example 11, and the product compound 43 is finally obtained with a yield of 73%. The product molecular formula is: C 64 H 38 N4O; molecular weight m / z: 878.30; elemental analysis results: C, 87.45; H, 4.36; N, 6.37; O, 1.82.

[0276] Example 54

[0277] In this example, compound 44 was prepared, and its structural formula and synthetic route are shown below:

[0278]

[0279] The specific reaction steps are as follows: Compared with Example 12, the difference is that M1 is replaced with an equivalent amount of M8. The other raw materials and steps are the same as Example 12, and the product compound 44 is finally obtained with a yield of 83%. The product molecular formula is: 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.

[0280] Example 55

[0281] In this example, compound 45 was prepared, and its structural formula and synthetic route are shown below:

[0282]

[0283] The specific reaction steps are as follows: Compared with Example 13, the difference is that M1 is replaced with an equivalent amount of M8. The other raw materials and steps are the same as Example 13, and the final product compound 45 is obtained with a yield of 66%. The product molecular formula is: 70 H 50 N4O; molecular weight m / z: 962.40; elemental analysis results: C, 87.29; H, 5.23; N, 5.82; O, 1.66.

[0284] Example 56

[0285] In this example, compound 46 was prepared, and its structural formula and synthetic route are shown below:

[0286]

[0287] The specific reaction steps are as follows: Compared with Example 14, the difference is that M1 is replaced with an equivalent amount of M8. The other raw materials and steps are the same as Example 14, and the product compound 46 is finally obtained with a yield of 71%. The product molecular formula is: C 64 H 38 N4O3; molecular weight m / z: 910.29; elemental analysis results are: C, 84.38; H, 4.20; N, 6.15; O, 5.27.

[0288] Example 57

[0289] In this example, compound 47 was prepared, and its structural formula and synthetic route are shown below:

[0290]

[0291] The specific reaction steps are as follows: Compared with Example 15, the difference is that M1 is replaced with an equivalent amount of M8. The other raw materials and steps are the same as Example 15, and the product compound 47 is finally obtained with a yield of 68%. The product molecular formula is: C 90 H 54 N4O; molecular weight m / z: 1206.43; elemental analysis results: C, 89.53; H, 4.51; N, 4.64; O, 1.33.

[0292] Example 58

[0293] In this example, compound 48 was prepared, and its structural formula and synthetic route are shown below:

[0294]

[0295] The specific reaction steps are as follows: Compared with Example 16, the difference is that M1 is replaced with an equivalent amount of M8. The other raw materials and steps are the same as Example 16. The final product compound 48 is obtained with a yield of 73%. The product molecular formula is: C 90 H 54 N4OS2; molecular weight m / z: 1270.37; elemental analysis results are: C, 85.01; H, 4.28; N, 4.41; O, 1.26; S, 5.04.

[0296] Example 59

[0297] In this example, compound 49 was prepared, and its structural formula and synthetic route are shown below:

[0298]

[0299] The specific reaction steps are as follows: Compared with Example 11, the difference is that M1 is replaced with an equivalent amount of M9. The other raw materials and steps are the same as Example 11, and the product compound 49 is finally obtained with a yield of 73%. The product molecular formula is: C 62 H 36 N6O; molecular weight m / z: 880.30; elemental analysis results: C, 84.53; H, 4.12; N, 9.54; O, 1.82.

[0300] Example 60

[0301] In this example, compound 50 was prepared, and its structural formula and synthetic route are shown below:

[0302]

[0303] The specific reaction steps are as follows: Compared with Example 12, the difference is that M1 is replaced with an equivalent amount of M9. The other raw materials and steps are the same as Example 12, and the product compound 50 is finally obtained with a yield of 83%. The product molecular formula is: C 62 H 40 N6O; molecular weight m / z: 884.33; elemental analysis results: C, 84.14; H, 4.56; N, 9.50; O, 1.81.

[0304] Example 61

[0305] In this example, compound 51 was prepared, and its structural formula and synthetic route are shown below:

[0306]

[0307] The specific reaction steps are as follows: Compared with Example 13, the difference is that M1 is replaced with an equivalent amount of M9. The other raw materials and steps are the same as Example 13, and the final product compound 51 is obtained with a yield of 66%. 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.

[0308] Example 62

[0309] In this example, compound 52 was prepared, and its structural formula and synthetic route are shown below:

[0310]

[0311] The specific reaction steps are as follows: Compared with Example 14, the difference is that M1 is replaced with an equivalent amount of M9. The other raw materials and steps are the same as Example 14, and the product compound 52 is finally obtained with a yield of 71%. The product molecular formula is: 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.

[0312] Example 63

[0313] In this example, compound 53 was prepared, and its structural formula and synthetic route are shown below:

[0314]

[0315] The specific reaction steps are as follows: Compared with Example 15, the difference is that M1 is replaced with an equivalent amount of M9. The other raw materials and steps are the same as Example 15, and the product compound 53 is finally obtained with a yield of 68%. The product molecular formula is: C 88 H 52 N6O; molecular weight m / z: 1208.42; elemental analysis results: C, 87.39; H, 4.33; N, 6.95; O, 1.32.

[0316] Example 64

[0317] In this example, compound 54 was prepared, and its structural formula and synthetic route are shown below:

[0318]

[0319] The specific reaction steps are as follows: Compared with Example 16, the difference is that M1 is replaced with an equivalent amount of M9. The other raw materials and steps are the same as Example 16, and the product compound 54 is finally obtained with a yield of 73%. The product molecular formula is: C 88 H 52 N6OS2; molecular weight m / z: 1272.36; elemental analysis results: C, 82.99; H, 4.12; N, 6.60; O, 1.26; S, 5.03.

[0320] Example 65

[0321] In this example, compound 55 was prepared, and its structural formula and synthetic route are shown below:

[0322]

[0323] The specific reaction steps are as follows: Compared with Example 11, the difference is that M1 is replaced with an equivalent amount of M10. The other raw materials and steps are the same as Example 11, and the product compound 55 is finally obtained with a yield of 73%. The product molecular formula is: C 68 H 40 N4O; molecular weight m / z: 928.32; elemental analysis results: C, 87.91; H, 4.34; N, 6.03; O, 1.72.

[0324] Example 66

[0325] In this example, compound 56 was prepared, and its structural formula and synthetic route are shown below:

[0326]

[0327] The specific reaction steps are as follows: Compared with Example 12, the difference is that M1 is replaced with an equivalent amount of M10. The other raw materials and steps are the same as Example 12, and the product compound 56 is finally obtained with a yield of 83%. The product molecular formula is: C 68 H 44 N4O; molecular weight m / z: 932.35; elemental analysis results are: C, 87.53; H, 4.75; N, 6.00; O, 1.71.

[0328] Example 67

[0329] In this example, compound 57 was prepared, and its structural formula and synthetic route are shown below:

[0330]

[0331] The specific reaction steps are as follows: Compared with Example 13, the difference is that M1 is replaced with an equivalent amount of M10. The other raw materials and steps are the same as Example 13, and the product compound 57 is finally obtained with a yield of 66%. The product molecular formula is: C 74 H 52 N4O; molecular weight m / z: 1012.41; elemental analysis results: C, 87.72; H, 5.17; N, 5.53; O, 1.58.

[0332] Example 68

[0333] In this example, compound 58 was prepared, and its structural formula and synthetic route are shown below:

[0334]

[0335] The specific reaction steps are as follows: Compared with Example 14, the difference is that M1 is replaced with an equivalent amount of M10. The other raw materials and steps are the same as Example 14, and the product compound 58 is finally obtained with a yield of 71%. The product molecular formula is: C 68 H 40 N4O3; molecular weight m / z: 960.31; elemental analysis results are: C, 84.98; H, 4.20; N, 5.83; O, 4.99.

[0336] Example 69

[0337] In this example, compound 59 was prepared, and its structural formula and synthetic route are shown below:

[0338]

[0339] The specific reaction steps are as follows: Compared with Example 15, the difference is that M1 is replaced with an equivalent amount of M10. The other raw materials and steps are the same as Example 15, and the product compound 59 is finally obtained with a yield of 68%. The product molecular formula is: C 94 H 56 N4O; molecular weight m / z: 1256.45; elemental analysis results: C, 89.78; H, 4.49; N, 4.46; O, 1.27.

[0340] Example 70

[0341] In this example, compound 60 was prepared, and its structural formula and synthetic route are shown below:

[0342]

[0343] The specific reaction steps are as follows: Compared with Example 16, the difference is that M1 is replaced with an equivalent amount of M10. The other raw materials and steps are the same as Example 16, and the product compound 60 is finally obtained with a yield of 73%. Product molecular formula: C 94 H 56 N4OS2; molecular weight m / z: 1320.39; elemental analysis results: C, 85.43; H, 4.27; N, 4.24; O, 1.21; S, 4.85.

[0344] Application Example 1

[0345] The preparation and performance evaluation of organic electroluminescent devices using dibenzoxadiazole-dione derivatives as acceptor units as organic small molecule materials are applied to the light-emitting layer.

[0346] The specific stacked structure of the general organic electroluminescent device in this embodiment is as follows:

[0347] 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.

[0348] The steps for preparing the light emitting device are as follows:

[0349] 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 under vacuum conditions of ~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.

[0350] The molecular structures of TAPC, mCP, CBP and TmPyPB described in Application Example 1 are shown below:

[0351]

[0352] In this embodiment, compound 3, compound 8 and compound 15 were compared with the reported materials E1, E2 and E3. The luminescence spectrum, current density-voltage-luminance relationship curve, and current efficiency-luminance-external quantum efficiency relationship curve of the organic electroluminescent device of compound 8 are shown in Figure 1. Figure 3 、 Figure 1 and Figure 2 The reported comparative materials E1, E2, and E3 have the following structures:

[0353]

[0354] Table 1 Device data comparison

[0355]

[0356] 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 dibenzoxetyl 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: Having at least one of the structural formulas shown in 1 to 60:

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

4. The organic small molecule material based on a dibenzoxepin derivative as a receptor core unit according to claim 1 or 3, characterized in that: The R is the same or different At least one of , wherein * is a linking site.

5. The organic small molecule material based on a dibenzoxepin derivative as a receptor core unit according to claim 2 or 3, characterized in that: It has at least one of the structural formulas 1 to 18:

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

7. The preparation method according to claim 6, characterized in that: The dihalogenated dibenzoxepin-dione in step (1) is obtained by reacting compound I with 1,8-diazabicyclo[5,4,0]undec-7-ene in the presence of a catalyst; The structural formula of compound I is wherein R1 is halogen; The molar ratio of the compound I to 1,8-diazabicyclo[5,4,0]undec-7-ene is 1:1 to 1.5; The reaction temperature is room temperature and the reaction time is 0.5 to 2 hours; The cyclization reaction in step (1) is specifically: dihalogenated dibenzoxepin-dione is subjected to a heating cyclization reaction with at least one of compounds m2 to m10 to obtain an electron-withdrawing intermediate; The compound m2 is 3,4-diaminobenzophenone; Compound m3 is diaminomaleonitrile; compound m4 is o-phenylenediamine; compound m5 is diamino o-phenylenediamine; compound m6 is [1,1':2',1"-terphenyl]-4',5'-diamine; compound m7 is Compound m8 is Compound m9 is Compound m10 is The molar ratio of the dihalogenated dibenzoxepin-dione to the compounds m2 to m10 is 1:1 to 1.2; The heating cyclization reaction condition is heating reflux reaction for 8 to 12 hours; Step (2) the dihalogenated dibenzoxadione-dione or electron-withdrawing intermediate and 4-(carbazole-9-yl)phenylboronic acid, triphenylamine-4-boronic acid, compound m11 Compound m12 Compound m13 and compound m14 At least one of the above compounds is subjected to a Suzuki coupling reaction at a molar ratio of 1:1 to 1.5 to obtain an organic small molecule material based on a dibenzoxetyl derivative as a receptor core unit; The temperature of the Suzuki coupling reaction is 80-90° C., and the reaction time is 8-24 hours.

8. The preparation method according to claim 7, characterized in that: The catalyst in the preparation process of the dihalogenated dibenzoxetane-dione is 3-benzyl-5-(2-hydroxyethyl)-4-methylthiazole chloride; the amount of the catalyst is 10 to 30% of the molar amount of compound I; 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 dihalogenated dibenzoxepin-dione or the electron-withdrawing intermediate; 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; The solvent medium of the reaction in step (1) is acetic acid; and the reaction medium in step (2) is at least one of toluene, dioxane and ethanol.

9. Use of the organic small molecule luminescent material comprising a dibenzoxepin derivative as an acceptor core unit according to any one of claims 1 to 5 in the preparation of an organic optoelectronic device.

10. An organic light emitting diode, characterized in that: Its 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 light-emitting material based on the dibenzoxetyl derivative as the acceptor core unit according to any one of claims 1 to 5.

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