阅读说明：本技术 一种新型有机化合物及其在oled器件中的应用 (Novel organic compound and application thereof in OLED device ) 是由 梁现丽 刘阳 范洪涛 陈婷 杭德余 段陆萌 曹占广 班全志 于 2020-12-17 设计创作，主要内容包括：本发明属于有机电致发光显示技术领域,具体涉及一种新型有机化合物及其在OLED器件中的应用。所述新型有机材料的结构式如式(I)所示,可以作为电子传输材料使用,同时具有良好的热稳定性,能够很好地应用于OLED器件中,表现出低驱动电压和高发光效率。(The invention belongs to the technical field of organic electroluminescent display, and particularly relates to a novel organic compound and application thereof in an OLED device.The novel organic material has a structural formula shown in a formula (I), can be used as an electron transport material, has good thermal stability, can be well applied to OLED devices, and shows low driving voltage and high luminous efficiency.)

1. A novel organic compound having a structural formula as shown in formula (I):

in the formula:

L₁and L₂Each independently represents a single bond, a substituted or unsubstituted arylene group having C6-C30, a substituted or unsubstituted heteroarylene group having C3-C30;

R₁、R₂the aromatic groups are the same or different, each independently represent substituted or unsubstituted aromatic groups containing benzene rings and/or aromatic heterocycles, and at least one group is substituted or unsubstituted aromatic hydrocarbon or polycyclic aromatic hydrocarbon of C6-C40;

n is an integer of 1 to 8.

2. The novel organic compound according to claim 1, wherein in the formula (I), L represents₁And L₂Represents a single bond.

3. The novel organic compound according to claim 1 or 2, wherein n in formula (I) is 1 or 2.

4. A novel organic compound according to any one of claims 1 to 3, wherein in the substituted or unsubstituted aromatic or condensed aromatic hydrocarbon of C6 to C40 in formula (I), the aromatic or condensed aromatic hydrocarbon represents a benzene ring, biphenyl, terphenyl, naphthalene, fluorene, spirobifluorene, phenanthrene, anthracene, fluoranthene, pyrene, triphenylene, benzo (a) anthracene, benzo (b) fluoranthene, benzo (k) fluoranthene, or benzo (a) pyrene.

5. The novel organic compound according to any one of claims 1 to 4, wherein in the formula (I), the substituent used for the substitution in the substituted or unsubstituted C6-C40 aromatic hydrocarbon or condensed ring aromatic hydrocarbon is optionally selected from the group consisting of: halogen, C1-C5 straight chain or branched chain alkyl, C3-C6 naphthenic base, phenyl, benzophenanthryl and naphtho, wherein the number of the substituent groups is an integer selected from 1-3.

6. A novel organic compound according to any one of claims 1 to 3, wherein in formula (I), the substituted or unsubstituted aromatic or fused ring aromatic hydrocarbon of C6 to C40 is selected from:

7. the novel organic material according to claim 1, wherein the formula (I) is selected from the group consisting of compounds represented by the following general formulae I-1 to I-32:

8. use of the novel organic compound as claimed in any of claims 1 to 7 as an electron transport material in an organic electroluminescent device, a display device or a lighting device.

9. An organic electroluminescent device, wherein the novel organic compound according to any one of claims 1 to 7 is contained in an electron transport layer of the organic electroluminescent device, and preferably, the thickness of the electron transport layer is 10 to 50nm, and more preferably 20 to 40 nm.

10. A display device or a lighting device comprising the novel organic material according to any one of claims 1 to 7 or the organic electroluminescent element according to claim 9.

Technical Field

The invention belongs to the technical field of organic electroluminescent display, and particularly relates to a novel organic compound and application thereof in an OLED device.

Background

The application of the organic electroluminescent (OLED) material in the fields of information display materials, organic optoelectronic materials and the like has great research value and good application prospect. With the development of multimedia information technology, the requirements for the performance of flat panel display devices are higher and higher. The main display technologies at present are plasma display devices, field emission display devices, and organic electroluminescent display devices (OLEDs). The OLED has a series of advantages of self-luminescence, lightness, thinness, power saving, full curing, wide viewing angle, rich colors and the like, compared with a liquid crystal display device, the OLED does not need a backlight source, has wider viewing angle and low power consumption, and has the response speed 1000 times that of the liquid crystal display device, so the OLED has wider application prospect.

At present, the commonly used electron transport materials such as AlQ3 have low electron mobility, so that the working voltage of the device is higher, and the power consumption is serious; some electron transport materials such as LG201 are not high in triplet level, and when a phosphorescent light emitting material is used as a light emitting layer, an exciton blocking layer needs to be added, otherwise efficiency is reduced, and some materials such as Bephen are easily crystallized, resulting in a reduction in lifetime. Therefore, the stable and efficient electron transport material is developed, so that the driving voltage is reduced, the luminous efficiency of the device is improved, the service life of the device is prolonged, and the method has important practical application value.

Disclosure of Invention

The invention aims to provide a novel OLED electron transport material with low driving voltage and high luminous efficiency.

In order to develop materials with the properties, the inventor designs a novel benzindolone heterocyclic structure compound, the parent nucleus of the series of compounds has strong electron-withdrawing capability, is connected with a neutral group, can be used as an electron-transporting material, has good thermal stability, can be well applied to OLED devices, and can achieve the purpose. Namely, the present invention provides a novel organic compound having a structure represented by general formula (i):

in the general formula (I), L₁And L₂Each independently represents a single bond, a substituted or unsubstituted arylene group having C6-C30, a substituted or unsubstituted heteroarylene group having C3-C30;

R₁、R₂each independently represents a substituted or unsubstituted aromatic group containing a benzene ring and/or an aromatic heterocycle, and at least one group is a substituted or unsubstituted aromatic hydrocarbon or condensed aromatic hydrocarbon of C6-C40; r₁、R₂May be the same or different;

n is an integer of 1 to 8.

The term "substituted or unsubstituted" means that the substituent is substituted or unsubstituted with 1 or more substituents selected from the group consisting of hydrogen, deuterium, a halogen atom, a hydroxyl group, a nitrile group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxyl group or a carboxylate thereof, a sulfonic acid group or a sulfonate thereof, a phosphoric acid group or a phosphate thereof, a C1-C60 alkyl group, a C2-C60 alkenyl group, a C2-C60 alkynyl group, a C1-C60 alkoxy group, a C3-C60 cycloalkyl group, a C3-C60 cycloalkenyl group, a C6-C60 aryl group, a C6-C60 aryloxy group, a C6-C60 arylthioether group and a C2-C60 heteroaryl group, or is linked with 2 or more substituents among the above-exemplified substituents.

The substituted or unsubstituted aromatic hydrocarbon of C6-C40 can be monocyclic aromatic hydrocarbon or polycyclic aromatic hydrocarbon; the polycyclic aromatic hydrocarbon can be polyphenyl aliphatic hydrocarbon, biphenyl polycyclic aromatic hydrocarbon, spirobifluorene group and the like. When the above groups are substituted, the substituents are preferably: halogen, straight-chain or branched alkyl (more preferably C1-C5 straight-chain or branched alkyl), cycloalkyl, aryl, monocyclic aryl, benzo, phenanthro, naphtho, benzothieno and benzofuro, wherein the number of the substituents is an integer of 1-7.

As a preferred embodiment of the present invention, L is₁And L₂Represents a single bond.

In a preferred embodiment of the present invention, n is 1 or 2.

In a preferred embodiment of the present invention, the substituted or unsubstituted aromatic hydrocarbon or condensed aromatic hydrocarbon having C6 to C40 each independently represents a substituted or unsubstituted benzene ring, biphenyl, terphenyl, naphthalene, fluorene, spirobifluorene, phenanthrene, anthracene, fluoranthene, pyrene, triphenylene, benzo (a) anthracene, benzo (b) fluoranthene, benzo (k) fluoranthene, or benzo (a) pyrene. When the above groups are substituted, the substituents are preferably: halogen, C1-C5 straight chain or branched chain alkyl, C3-C6 naphthenic base, phenyl, benzophenanthryl and naphtho, wherein the number of the substituent groups is an integer selected from 1-3.

In a preferred embodiment of the present invention, the substituted or unsubstituted aromatic hydrocarbon or polycyclic aromatic hydrocarbon of C6 to C40 is selected from:

further preferred according to the invention are organic materials of formula I selected from the group consisting of compounds of formulae I-1 to I-32 as follows:

the novel organic compound takes a benzindolone heterocyclic structure as a parent nucleus, the parent nucleus structure has strong electron-withdrawing capability and good thermal stability, and the structure has proper HOMO and LUMO energy levels and Eg. We find that the electron transport performance of the material can be further improved by changing the intermolecular accumulation mode by further introducing a neutral group into the parent nucleus structure, and the material can be well applied to OLED devices, can be used as an electron transport material, and can effectively improve the photoelectric performance of the devices.

The present invention further provides the use of the above novel organic compounds in an organic electroluminescent device, a display device or a lighting device. The organic compound is preferably used as an electron transport material of an electron transport layer in an organic electroluminescent device. The thickness of the electron transport layer can be 10-50 nm, and preferably 20-40 nm.

In a preferred embodiment of the present invention, the organic electroluminescent device comprises, in order from bottom to top, a transparent substrate, an anode layer, a hole transport layer, an electroluminescent layer, an electron transport layer (containing the novel organic compound), an electron injection layer, and a cathode layer.

The novel OLED material provided by the invention takes a benzindolone heterocyclic structure compound as a parent nucleus, the parent nucleus structure has strong electron-withdrawing capability, and a neutral group is introduced into the parent nucleus structure to obtain the novel OLED material. The material has high electron transport performance, good film stability and proper molecular energy level, can be applied to the field of organic electroluminescence, can be used as an electron transport material, and can effectively improve the photoelectric performance of devices. The device can be applied in the fields of display and illumination.

Detailed Description

The following examples are intended to illustrate the present invention, but are not intended to limit the scope of the present invention, and other equivalent changes or modifications made without departing from the spirit of the present invention are intended to be included within the scope of the appended claims.

According to the preparation method provided by the present invention, a person skilled in the art can use known common means to implement, such as further selecting a suitable catalyst and a suitable solvent, and determining a suitable reaction temperature, a suitable reaction time, a suitable material ratio, and the like, which are not particularly limited in the present invention. If not specifically stated, the starting materials for the preparation of solvents, catalysts, bases, etc. may be obtained by published commercial routes or by methods known in the art.

The synthesis method of the present invention is briefly described below.

(1) When R1 is the same as R2, the synthetic route is as follows:

(2) when R1 is different from R2, the synthetic pathway is as follows (Cl and Br are adjusted as required):

EXAMPLE 1 Synthesis of Compound I-1

The synthetic route is as follows:

A1L three-necked flask was equipped with magnetic stirring, and after nitrogen substitution, M1(37.5g, 0.1mol), phenylboronic acid (24.4g, 0.2mol), cesium carbonate (78g, 0.24mol) and dioxane (400 ml) were added in this order, followed by stirring. After nitrogen replacement again, (1.5g, 8mmol) tri-tert-butylphosphine and (2.7g, 3mmol) tris (dibenzylideneacetone) dipalladium were added. After the addition, heating and raising the temperature, controlling the temperature to be 80-90 ℃ for reaction for 4 hours, and cooling after the reaction is finished. Adjusting to neutrality, separating organic phase, extracting, drying, column chromatography, and spin-drying solvent to obtain 40.4g pale yellow solid with yield about 88%.

Product MS (m/e): 459.16, respectively; elemental analysis (C)₃₄H₂₁NO): theoretical value C: 88.86%, H: 4.61%, N: 3.05 percent; found value C: 88.92%, H: 4.65%, N: 2.91 percent.

EXAMPLE 2 Synthesis of Compound I-4

The synthetic route is as follows:

into a 1L three-necked flask, M2(34.3g, 0.1mol), (4-cyclohexylphenyl) boronic acid (20.4g, 0.1mol), sodium carbonate (15.9g,0.15mol), toluene 150mL, ethanol 150mL, and water 150mL were charged, and Pd (PPh) was added after the reaction system was purged with nitrogen₃)₄(11.5g, 10 mmol). The reaction was heated under reflux (temperature in the system: about 78 ℃ C.) for 3 hours to stop the reaction. The solvent is evaporated, dichloromethane is extracted, anhydrous magnesium sulfate is dried, filtration is carried out, petroleum ether/ethyl acetate (2:1) column chromatography is carried out, the solvent is dried in a rotating mode, the ethyl acetate is pulped, and 35.1g of light yellow solid I-4-1 is obtained through filtration, and the yield is about 83%.

A1L three-necked flask was equipped with magnetic stirring, and after nitrogen substitution, I-4-1(42.3g, 0.1mol), dibenzo [ b, d ] furan-3-ylboronic acid (21.2g, 0.1mol), cesium carbonate (39g, 0.12mol) and dioxane (400 ml) were added in this order, followed by stirring. After nitrogen replacement again, (0.8g, 4mmol) tri-tert-butylphosphine and (1.4g, 1.5mmol) tris (dibenzylideneacetone) dipalladium were added. After the addition, heating and raising the temperature, controlling the temperature to be 80-90 ℃ for reaction for 4 hours, and cooling after the reaction is finished. Adjusting to neutrality, separating an organic phase, extracting, drying, performing column chromatography, and spin-drying the solvent to obtain 43.8g of light yellow solid with the yield of about 79%.

Product MS (m/e): 555.22, respectively; elemental analysis (C)₄₀H₂₉NO₂): theoretical value C: 86.46%, H: 5.26%, N: 2.52 percent; found value C: 86.52%, H: 5.33%, N: 2.35 percent.

EXAMPLE 3 Synthesis of Compound I-7

The synthetic route is as follows:

m3(46.9g, 0.1mol), dibenzo [ b, d ] was charged into a 1L three-necked flask]Thiophen-3-ylboronic acid (22.8g, 0.1mol), sodium carbonate (15.9g,0.15mol), toluene (150 mL), ethanol (150 mL), and water (150 mL), and Pd (PPh) was added after the reaction system was purged with nitrogen₃)₄(11.5g, 10 mmol). The reaction was heated under reflux (temperature in the system: about 78 ℃ C.) for 3 hours to stop the reaction. The solvent is evaporated off, dichloromethane is extracted, anhydrous magnesium sulfate is dried, filtration is carried out, petroleum ether/ethyl acetate (2:1) column chromatography is carried out, the solvent is dried in a rotating mode, ethyl acetate is pulped, and filtration is carried out to obtain 44.1g of light yellow solid I-7-1, wherein the yield is about 77%.

A1L three-necked flask was equipped with magnetic stirring, and after nitrogen substitution, I-7-1(57.3g, 0.1mol), phenylboronic acid (12.2g, 0.1mol), cesium carbonate (39g, 0.12mol) and 400ml dioxane were sequentially added, followed by stirring. After nitrogen replacement again, (0.8g, 4mmol) tri-tert-butylphosphine and (1.4g, 1.5mmol) tris (dibenzylideneacetone) dipalladium were added. After the addition, heating and raising the temperature, controlling the temperature to be 80-90 ℃ for reaction for 4 hours, and cooling after the reaction is finished. Adjusting to neutrality, separating an organic phase, extracting, drying, performing column chromatography, and spin-drying the solvent to obtain 51.7g of pale yellow solid with the yield of about 84%.

Product MS (m/e): 615.17, respectively; elemental analysis (C)₄₄H₂₅NOS): theoretical value C: 85.83%, H: 4.09%, N: 2.27 percent; found value C: 85.88 percent，H：4.14％，N：2.12％。

EXAMPLE 4 Synthesis of Compound I-11

The synthetic route is as follows:

A1L three-necked flask was equipped with magnetic stirring, and after nitrogen substitution, M4(37.5g, 0.1mol), phenanthren-9-ylboronic acid (44.4g, 0.2mol), cesium carbonate (78g, 0.24mol) and 400ml dioxane were sequentially added, followed by stirring. After nitrogen replacement again, (1.5g, 8mmol) tri-tert-butylphosphine and (2.7g, 3mmol) tris (dibenzylideneacetone) dipalladium were added. After the addition, heating and raising the temperature, controlling the temperature to be 80-90 ℃ for reaction for 4 hours, and cooling after the reaction is finished. Adjusting to neutrality, separating an organic phase, extracting, drying, performing column chromatography, and spin-drying the solvent to obtain 49.4g of pale yellow solid with the yield of about 75%.

Product MS (m/e): 659.22, respectively; elemental analysis (C)₅₀H₂₉NO): theoretical value C: 91.02%, H: 4.43%, N: 2.12 percent; found value C: 91.06%, H: 4.50%, N: 2.00 percent.

EXAMPLE 5 Synthesis of Compound I-16

The synthetic route is as follows:

into a 1L three-necked flask, M5(41.9g, 0.1mol), (3-phenylanthracen-9-yl) boronic acid (29.8g, 0.1mol), sodium carbonate (15.9g,0.15mol), toluene 150mL, ethanol 150mL, and water 150mL were charged, and Pd (PPh) was added after the reaction system was purged with nitrogen₃)₄(11.5g, 10 mmol). The reaction was heated under reflux (temperature in the system: about 78 ℃ C.) for 3 hours to stop the reaction. The solvent is evaporated off, dichloromethane is extracted, anhydrous magnesium sulfate is dried, filtration is carried out, petroleum ether/ethyl acetate (2:1) column chromatography is carried out, the solvent is dried in a rotating mode, ethyl acetate is pulped, and filtration is carried out to obtain 40.9g of light yellow solid I-16-1 with the yield being about 69%.

1L three-necked flask, stirring with magnetic force, replacing with nitrogen, sequentially adding I-16-1(59.3g, 0.1mol), [1, 1': 3', 1 "-terphenyl ] -5' -ylboronic acid (27.4g, 0.1mol), cesium carbonate (39g, 0.12mol) and dioxane 400ml were stirred with stirring. After nitrogen replacement again, (0.8g, 4mmol) tri-tert-butylphosphine and (1.4g, 1.5mmol) tris (dibenzylideneacetone) dipalladium were added. After the addition, heating and raising the temperature, controlling the temperature to be 80-90 ℃ for reaction for 4 hours, and cooling after the reaction is finished. Adjusting to neutrality, separating organic phase, extracting, drying, column chromatography, and spin-drying solvent to obtain 63.0g pale yellow solid with yield about 80%.

Product MS (m/e): 787.29, respectively; elemental analysis (C)₆₀H₃₇NO): theoretical value C: 91.46%, H: 4.73%, N: 1.78 percent; found value C: 91.52%, H: 4.79%, N: 1.63 percent.

EXAMPLE 6 Synthesis of Compound I-18

The synthetic route is as follows:

into a 1L three-necked flask, M6(34.3g, 0.1mol), triphenylen-2-ylboronic acid (27.2g, 0.1mol), sodium carbonate (15.9g,0.15mol), toluene 150mL, ethanol 150mL, and water 150mL were charged, and Pd (PPh) was added after the reaction system was purged with nitrogen₃)₄(11.5g, 10 mmol). The reaction was heated under reflux (temperature in the system: about 78 ℃ C.) for 3 hours to stop the reaction. Evaporating off solvent, extracting with dichloromethane, drying with anhydrous magnesium sulfate, filtering, and separating with petroleum ether/ethyl acetate (2:1) columnChromatography, spin-drying solvent, pulping with ethyl acetate, and filtering to obtain 34.9g pale yellow solid I-18-1 with yield of about 71%.

A1L three-necked flask was equipped with magnetic stirring, and after nitrogen substitution, I-18-1(49.1g, 0.1mol), (4 '- (methyl-d 3) - [1,1' -biphenyl ] -3-yl) boronic acid (21.5g, 0.1mol), cesium carbonate (39g, 0.12mol) and dioxane 400ml were added in this order, followed by stirring. After nitrogen replacement again, (0.8g, 4mmol) tri-tert-butylphosphine and (1.4g, 1.5mmol) tris (dibenzylideneacetone) dipalladium were added. After the addition, heating and raising the temperature, controlling the temperature to be 80-90 ℃ for reaction for 4 hours, and cooling after the reaction is finished. Adjusting to neutrality, separating organic phase, extracting, drying, column chromatography, and spin-drying solvent to obtain 40.7g pale yellow solid with yield about 65%.

Product MS (m/e): 626.24, respectively; elemental analysis (C)₄₇H₂₆D₃NO): theoretical value C: 90.07%, H: 5.15%, N: 2.23 percent; found value C: 90.13%, H: 5.19%, N: 2.09 percent.

EXAMPLE 7 Synthesis of Compound I-21

The synthetic route is as follows:

A1L three-necked flask was equipped with magnetic stirring, and after nitrogen substitution, M4(37.5g, 0.1mol), (9, 9-dimethyl-9H-fluoren-2-yl) boronic acid (47.6g, 0.2mol), cesium carbonate (78g, 0.24mol) and dioxane 400ml were sequentially added, and stirring was started. After nitrogen replacement again, (1.5g, 8mmol) tri-tert-butylphosphine and (2.7g, 3mmol) tris (dibenzylideneacetone) dipalladium were added. After the addition, heating and raising the temperature, controlling the temperature to be 80-90 ℃ for reaction for 4 hours, and cooling after the reaction is finished. Adjusting to neutrality, separating an organic phase, extracting, drying, performing column chromatography, and spin-drying the solvent to obtain 53.2g of pale yellow solid with the yield of about 77%.

Product MS (m/e): 691.29, respectively; elemental analysis (C)₅₂H₃₇NO): theoretical value C: 90.27%, H: 5.39%, N: 2.02 percent; found value C: 90.33%, H: 5.42%, N: 1.90 percent.

EXAMPLE 8 Synthesis of Compound I-24

The synthetic route is as follows:

m7(41.9g, 0.1mol), 9' -spirobis [ fluorene ] were added to a 1L three-necked flask]-4-yl boric acid (36.0g, 0.1mol), sodium carbonate (15.9g,0.15mol), toluene 150mL, ethanol 150mL, water 150mL, the reaction system was purged with nitrogen and Pd (PPh) was added₃)₄(11.5g, 10 mmol). The reaction was heated under reflux (temperature in the system: about 78 ℃ C.) for 3 hours to stop the reaction. The solvent was evaporated off, extracted with dichloromethane, dried over anhydrous magnesium sulfate, filtered, chromatographed on petroleum ether/ethyl acetate (2:1), the solvent was dried by spinning, slurried with ethyl acetate, filtered to obtain 43.9g of pale yellow solid I-24-1 with a yield of about 67%.

A1L three-necked flask was equipped with magnetic stirring, and after nitrogen substitution, I-24-1(65.5g, 0.1mol), 2-naphthylboronic acid (17.2g, 0.1mol), cesium carbonate (39g, 0.12mol) and 400ml dioxane were sequentially added, and stirring was started. After nitrogen replacement again, (0.8g, 4mmol) tri-tert-butylphosphine and (1.4g, 1.5mmol) tris (dibenzylideneacetone) dipalladium were added. After the addition, heating and raising the temperature, controlling the temperature to be 80-90 ℃ for reaction for 4 hours, and cooling after the reaction is finished. Adjusting to neutrality, separating an organic phase, extracting, drying, performing column chromatography, and spin-drying the solvent to obtain 58.3g of pale yellow solid with the yield of about 78%.

Product MS (m/e): 747.26, respectively; elemental analysis (C)₅₇H₃₃NO): theoretical value C: 91.54%, H: 4.45%, N: 1.87 percent; found value C: 91.59%, H: 4.50%, N: 1.73 percent.

EXAMPLE 9 Synthesis of Compound I-27

The synthetic route is as follows:

in a 1L three-necked bottle, M8(41.9g, 0.1mol) was charged,-6-ylboronic acid (27.2g, 0.1mol), sodium carbonate (15.9g,0.15mol), toluene 150mL, ethanol 150mL, and water 150mL, and Pd (PPh) was added after the reaction system was purged with nitrogen₃)₄(11.5g, 10 mmol). The reaction was heated under reflux (temperature in the system: about 78 ℃ C.) for 3 hours to stop the reaction. The solvent is evaporated off, dichloromethane is extracted, anhydrous magnesium sulfate is dried, filtration is carried out, petroleum ether/ethyl acetate (2:1) column chromatography is carried out, the solvent is dried in a rotating way, the ethyl acetate is pulped, and 36.9g of light yellow solid I-27-1 is obtained by filtration, and the yield is about 65 percent.

A1L three-necked flask was equipped with magnetic stirring, and after nitrogen substitution, I-27-1(56.7g, 0.1mol), 1-naphthylboronic acid (17.2g, 0.1mol), cesium carbonate (39g, 0.12mol) and 400ml dioxane were sequentially added, followed by stirring. After nitrogen replacement again, (0.8g, 4mmol) tri-tert-butylphosphine and (1.4g, 1.5mmol) tris (dibenzylideneacetone) dipalladium were added. After the addition, heating and raising the temperature, controlling the temperature to be 80-90 ℃ for reaction for 4 hours, and cooling after the reaction is finished. Adjusting to neutrality, separating organic phase, extracting, drying, column chromatography, and spin-drying solvent to obtain 50.7g pale yellow solid with yield of about 77%.

Product MS (m/e): 659.22, respectively; elemental analysis (C)₅₀H₂₉NO): theoretical value C: 91.02%, H: 4.43%, N: 2.12 percent; found value C: 91.8%, H: 4.50%, N: 1.94 percent.

EXAMPLE 10 Synthesis of Compound I-31

The synthetic route is as follows:

into a 1L three-necked flask, M9(41.9g, 0.1mol), perylene-3-ylboronic acid (29.6g, 0.1mol), sodium carbonate (15.9g,0.15mol), toluene 150mL, ethanol 150mL, and water 150mL were charged, and Pd (PPh) was added after the reaction system was purged with nitrogen₃)₄(11.5g, 10 mmol). The reaction was heated under reflux (temperature in the system: about 78 ℃ C.) for 3 hours to stop the reaction. The solvent is evaporated off, dichloromethane is extracted, anhydrous magnesium sulfate is dried, filtration is carried out, petroleum ether/ethyl acetate (2:1) column chromatography is carried out, the solvent is dried in a rotating way, the ethyl acetate is pulped, and filtration is carried out to obtain 35.5g of light yellow solid I-31-1 with the yield of about 60 percent.

A1L three-necked flask was equipped with magnetic stirring, and after nitrogen substitution, I-31-1(59.1g, 0.1mol), (4-phenylnaphthalen-1-yl) boronic acid (24.8g, 0.1mol), cesium carbonate (39g, 0.12mol) and dioxane 400ml were added in this order, followed by stirring. After nitrogen replacement again, (0.8g, 4mmol) tri-tert-butylphosphine and (1.4g, 1.5mmol) tris (dibenzylideneacetone) dipalladium were added. After the addition, heating and raising the temperature, controlling the temperature to be 80-90 ℃ for reaction for 4 hours, and cooling after the reaction is finished. Adjusting to neutrality, separating an organic phase, extracting, drying, performing column chromatography, and spin-drying the solvent to obtain 62.2g of pale yellow solid with the yield of about 82%.

Product MS (m/e): 759.26, respectively; elemental analysis (C)_5aH₃₃NO): theoretical value C: 91.67%, H: 4.38%, N: 1.84 percent; found value C: 91.74%, H: 4.43%, N: 1.69 percent.

According to the technical schemes of the examples 1 to 10, other compounds I-1 to I-32 can be synthesized only by simply replacing corresponding raw materials and not changing any substantial operation.

Device examples Using the Compounds of the invention as Electron transport materials

The embodiment provides a group of OLED blue light fluorescent devices OLED-1, and the structure of the device is as follows:

ITO/HATCN(1nm)/HT01(40nm)/NPB(20nm)/EML(30nm)/I-1(40nm)/LiF(1nm)/Al。

the molecular structure of each functional layer material is as follows:

the preparation method comprises the following steps:

(1) carrying out ultrasonic treatment on the glass plate coated with the ITO transparent conductive layer in a commercial cleaning agent, washing the glass plate in deionized water, ultrasonically removing oil in an acetone-ethanol mixed solvent (the volume ratio is 1: 1), baking the glass plate in a clean environment until the water is completely removed, cleaning the glass plate by using ultraviolet light and ozone, and bombarding the surface by using low-energy cationic beams;

(2) placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to 1 × 10^-5～9×10^-3pa, evaporating HATCN on the anode layer film in vacuum to serve as a first hole injection layer, wherein the evaporation rate is 0.1nm/s, and the total evaporation film thickness is 1 nm; then evaporating a second hole injection layer HT01 at the evaporation rate of 0.1nm/s and the thickness of 40 nm; then evaporating a hole transport layer NPB with the evaporation rate of 0.1nm/s and the evaporation film thickness of 20 nm;

(3) the method comprises the following steps of performing vacuum evaporation on an EML (electron emission layer) serving as a light emitting layer of a device on a hole transport layer, wherein the EML comprises a main material and a dye material, and adjusting the evaporation rate of the main material ADN to be 0.1nm/s, the evaporation rate of the dye material BD01 to be 5% and the total evaporation film thickness to be 30nm by using a multi-source co-evaporation method;

(4) vacuum evaporating an electron transport layer material I-1 of the device on the luminescent layer, wherein the evaporation rate is 0.1nm/s, and the total film thickness of the evaporation is 40 nm;

(5) LiF with the thickness of 1nm is sequentially vacuum-evaporated on the electron transport layer to be used as an electron injection layer, and an A1 layer with the thickness of 150nm is used as a cathode of the device.

According to the same steps as the above, only replacing I-1 in the step (4) with I-4, I-7, I-11, I-16, I-18, I-21, I-24, I-27 and I-31 respectively to obtain the OLED-2 to OLED-10 provided by the invention.

Following the same procedure as above, only replacing I-1 in step (4) with commercial Bphen (comparative compound) gave comparative example OLED-11 provided by the present invention. The structure of the Bphen is specifically as follows:

the performance of the obtained devices OLED-1 to OLED-11 is detected, and the detection results are shown in Table 1.

Table 1: performance test result of OLED device

The results show that the novel organic material is used for the organic electroluminescent device, and the device 1 has low current efficiency although the working voltage is low; device 10 has no advantage in both operating voltage and current efficiency; the devices 2-9 can effectively reduce the working voltage and improve the current efficiency, wherein the devices 2, 3, 7 and 8 have the best performance, the working voltage and the current efficiency are obviously superior to those of a comparison device, and the devices are electron transmission materials with good performance.

Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.