CN111635420B

CN111635420B - Novel polyheterocyclic compound and application thereof

Info

Publication number: CN111635420B
Application number: CN202010662483.7A
Authority: CN
Inventors: 梁现丽; 李仲庆; 范洪涛; 段陆萌; 杭德余; 曹占广; 班全志; 陈婷
Original assignee: Beijing Yanhua Jilian Optoelectronic Technology Co ltd
Current assignee: Beijing Yanhua Jilian Optoelectronic Technology Co ltd
Priority date: 2020-07-10
Filing date: 2020-07-10
Publication date: 2022-05-13
Anticipated expiration: 2040-07-10
Also published as: CN111635420A

Abstract

The invention belongs to the technical field of organic electroluminescent display, and particularly relates to a novel polyheterocyclic compound and application thereof in an organic electroluminescent device. The structure of the novel polyheterocyclic compound provided by the invention is shown as a formula (I). The compound has good thermal stability, and can be applied to OLED devices as a green light main body material to effectively improve the photoelectric properties of the devices. The OLED device containing the polyheterocyclic compound can be applied to the fields of display or illumination.

Description

Novel polyheterocyclic compound and application thereof

Technical Field

The invention belongs to the technical field of organic electroluminescent display, and particularly relates to a novel organic material with a multi-heterocyclic structure and application thereof in an organic electroluminescent (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, low-voltage direct current driving, full curing, wide viewing angle, rich colors and the like, and compared with a liquid crystal display device, the OLED does not need a backlight source, has a wider viewing angle and low power consumption, has the response speed 1000 times that of the liquid crystal display device, and has a wider application prospect.

Since the first reports of OLEDs, many scholars have been working on how to improve device efficiency and stability. Forrest and Thompson research groups find that the transition metal complex can be applied to Ph OLEDs (phosphorescent OLEDs), the phosphorescent material has strong spin-orbit coupling effect, and singlet excitons and triplet excitons can be simultaneously utilized, so that the quantum efficiency in the phosphorescent electroluminescent device theoretically reaches 100%. However, phosphorescent materials have a longer excited state lifetime, and are prone to form triplet-triplet quenching and triplet-polaron- quenching when the triplet exciton concentration is higher. Therefore, the phosphorescent material is often incorporated as a guest into the host material to reduce the concentration quenching phenomenon itself. Therefore, it is also an important matter to select a suitable host material in Phosphorescent organic electroluminescent devices (Ph OLEDs). Essential characteristics of the host material: (1) possesses a triplet energy level higher than that of the guest dye; (2) the carrier mobility is better and can be matched with the energy level of the adjacent layer; (3) has high thermal stability and film forming stability.

At present, OLED display and illumination are widely commercialized and applied, the requirements of a client terminal on the photoelectricity and service life of an OLED screen body are continuously improved, in order to meet the requirements, in addition to the refinement and refinement on the OLED panel manufacturing process, the development of OLED materials capable of meeting higher device indexes is very important. Therefore, stable and efficient electroluminescent main materials are 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 electroluminescent main materials have important practical application values.

Disclosure of Invention

The invention aims to provide an OLED main body material which has higher triplet state energy level, better carrier mobility, higher thermal stability and film forming stability and can be matched with adjacent energy levels, and application of the organic material in an OLED device.

Specifically, the invention finds a novel heterocyclic structure compound which can be used for an organic electroluminescent device. The parent nucleus of the series of compounds has an electron withdrawing effect, is connected with five-membered heterocyclic groups such as carbazole, furan, thiophene and the like with electron donating capability, can be used as a bipolar green light main body material, has good thermal stability and can be well applied to OLED devices. The series of compounds can be represented by a formula (I), and can be applied to OLED devices to achieve the purpose.

In a first aspect, the present invention provides a compound of formula (I):

in the formula (I), R₁～R₁₂Each independently of the others, is selected from hydrogen atom, halogen atom, linear or branched alkyl, cycloalkyl, amino, alkylamino, substituted or unsubstituted aromatic group containing benzene ring and/or heteroaromatic ring, and R₁～R₁₂Wherein at least one group is an aromatic group containing a five-membered heterocyclic ring.

Preferably, said R is₁～R₁₂Wherein at least one group is a substituted or unsubstituted aromatic group containing a five-membered heterocycle, the substituted or unsubstituted aromatic group containing a five-membered heterocycle contains at least one five-membered heterocycle, preferably contains one, two or three five-membered heterocycles; the five-membered heterocyclic ring contains at least one heteroatom, preferably one, two or three heteroatoms; the heteroatom is optionally selected from the group consisting of N atoms, S atoms, and O atoms; when the substituted or unsubstituted aromatic group containing a five-membered heterocyclic ring contains a plurality of hetero atoms, the respective hetero atoms may be the same as each other, may be partially the same as each other, or may be different from each other.

As a preferred embodiment of the present invention, the substituted or unsubstituted aromatic group containing a five-membered heterocycle is selected from: substituted or unsubstituted carbazolyl, substituted or unsubstituted benzocarbazolyl, substituted or unsubstituted phenanthrocarbazolyl, substituted or unsubstituted indoloindolyl, substituted or unsubstituted thienyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted naphthofuranyl.

In a preferred embodiment of the present invention, in the substituted aromatic group containing a five-membered heterocycle, the substituent may be optionally selected from: phenyl, naphthyl, biphenyl, benzo, naphtho, phenanthro, indolo (e.g., N-benzaindolo), benzothieno, benzofuro. The number of the substituents is an integer of 1 to 5, preferably 1 to 3.

As a preferred embodiment of the present invention, the substituted or unsubstituted aromatic group containing a five-membered heterocycle is selected from:

preferably, the substituted or unsubstituted aromatic group containing a five-membered heterocycle is selected from:

more preferably, the substituted or unsubstituted aromatic group containing a five-membered heterocycle is selected from:

in each of the above-mentioned substituent groups, "- - -" represents a substitution position.

As a preferred embodiment of the present invention, the present invention provides a compound represented by the following structure:

the organic compound takes a multi-heterocyclic ring structure as a parent nucleus, the parent nucleus structure has good thermal stability, and simultaneously has proper HOMO and LUMO energy levels and Eg, and a group with strong electron donating capability is introduced into a proper position in the parent nucleus structure, namely a five-membered heterocyclic ring structure with strong electron donating capability, such as carbazole, furan, thiophene and the like, is introduced into the structure, so that a novel structure OLED material is obtained. The material is applied to OLED devices and used as a green light main body material, and the photoelectric property of the devices can be effectively improved. The device can be applied to the field of display or illumination.

In a second aspect, the present invention provides the use of an organic compound of formula (I) in the preparation of an organic electroluminescent device. Preferably, the present invention provides the use of the organic compound as a light emitting host material of an electroluminescent layer in an organic electroluminescent device; further preferably, the electroluminescent material is a green host material. The thickness of the electroluminescent layer can be 10-50 nm, and preferably 20-40 nm.

In a third aspect, the present invention provides an organic electroluminescent device comprising an electroluminescent layer comprising a compound according to the present invention.

As a preferable scheme of the invention, the organic electroluminescent device comprises a transparent substrate, an anode layer, a hole transport layer, an electroluminescent layer (containing the compound of the invention as a green light main body material), an electron transport layer, an electron injection layer and a cathode layer from bottom to top in sequence. Preferably, the thickness of the electroluminescent layer is 10-50 nm, preferably 20-40 nm.

In a fourth aspect, the present invention provides a display apparatus comprising the organic electroluminescent device.

In a fifth aspect, the present invention provides a lighting apparatus comprising the organic electroluminescent device.

The novel OLED material provided by the invention takes a multi-heterocyclic structure compound as a mother nucleus, and an electron-donating group is introduced into the structure of the mother nucleus, so that the novel OLED material which has a high triplet state energy level, a good carrier mobility, high thermal stability and high film forming stability and can be matched with an adjacent energy level is obtained. The material can be applied to the field of organic electroluminescence, can be used as a green light main body material, and can effectively improve the photoelectric property of a device.

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.

Example 1 Synthesis of intermediate M1

The synthetic route is as follows:

the method comprises the following specific steps:

(1) adding 4-chloro-1-fluoro-2-nitrobenzene (17.5g, 0.1mol) and 2-bromo-4-chloroaniline (30.8g, 0.15mol) into a 2L three-necked bottle with mechanical stirring, protecting with argon, heating to 180 ℃, keeping the temperature for reaction for more than 30 hours, wherein the color of the reaction solution gradually becomes red in the reaction process, and finally gradually becomes deep red. After the reaction is finished, an organic phase is separated, extracted, dried, subjected to column chromatography, and subjected to spin-drying to obtain 30g of orange-red solid M-01 with the yield of 83%.

(2) In a 1L three-necked flask equipped with a mechanical stirrer, M-01(36.0g, 0.1mol), sodium sulfide nonahydrate (96g, 0.4mol), ethanol (200mL), and water (100mL) were added, and the mixture was heated to reflux under nitrogen protection, and the reaction was terminated after refluxing for 3 hours. Separating organic phase, extracting, drying, column chromatography and spin-drying solvent to obtain 26.5g white solid M-02 with yield of 80%.

(3) Adding M-02(33.0g, 0.1mol) and 300mL of acetone into a 1L three-necked flask with mechanical stirring to completely dissolve the mixture, adding a solution of KOH (11.2g, 0.2mol) dissolved in water (50mL), slowly dropwise adding 2-bromo-4-chlorobenzoyl chloride (25.2g, 0.1mol) into the reaction flask, gradually precipitating solids in the reaction flask, reacting at normal temperature for 2 hours after the dropwise adding is finished, and finishing the reaction. Adjusting to neutrality, separating an organic phase, extracting, drying, performing column chromatography, and spin-drying the solvent to obtain 43.8g of white solid M-03 with the yield of 79%.

(4) Adding M-03(54.8g, 0.1mol) into a 1L three-necked bottle, adding 200mL of glycol ether under the protection of nitrogen, gradually heating to reflux, gradually dissolving the solid, magnetically stirring, keeping the temperature and reacting for 3 hours, and finishing the reaction. The organic phase was separated, extracted, dried, column chromatographed, and the solvent was spin-dried to give 40g of M-04 as a pale red solid in 76% yield.

(5) Under the protection of nitrogen, M-04(53.0g, 0.1mol) and THF (800 mL) are added into a 2L three-necked bottle, the mixture is cooled to-78 ℃, n-butyllithium (100mL, 0.25mol) is slowly added dropwise under stirring for about 30mins, 50mL of THF is used for flushing a dropping funnel after dropwise addition, and the temperature is kept for 1.5 hours to obtain a reaction solution of M-05. Slowly dropwise adding sulfur dichloride (16mL, 0.25mol) into a low-temperature system at-78 ℃, then flushing a dropping funnel with a small amount of THF, preserving the temperature for 1 hour after the addition is finished, slowly heating to room temperature, stirring at room temperature for reacting for 4 hours, and finishing the reaction. Adjusting to neutrality, separating an organic phase, extracting, drying, performing column chromatography, and spin-drying the solvent to obtain 26.6g of intermediate M1 as a white solid with the yield of 66%.

Product MS (m/e): 401.96, respectively; elemental analysis (C)₁₉H₉Cl₃N₂S): theoretical value C: 56.53%, H: 2.25%, N: 6.94 percent; found value C: 56.32%, H: 2.11%, N: 6.82 percent.

Example 2 Synthesis of intermediate M2

By using

Respectively replace

The intermediate M2 was obtained by selecting the appropriate material ratio and the other raw materials and procedures were the same as in example 1.

Product MS (m/e): 367.99, respectively; elemental analysis (C)₁₉H₁₀Cl₂N₂S): theoretical value C: 61.80%, H: 2.73%, N: 7.59 percent; found value C: 61.55%, H: 2.61%, N: 7.48 percent.

Example 3 Synthesis of intermediate M3

By using

Respectively replace

The intermediate M3 was obtained by selecting the appropriate material ratio and the other raw materials and procedures were the same as in example 1.

Product MS (m/e): 367.99, respectively; elemental analysis (C)₁₉H₁₀Cl₂N₂S): theoretical value C: 61.80%, H: 2.73%, N: 7.59 percent; found value C: 61.56%, H: 2.60%, N: 7.44 percent.

Example 4 Synthesis of intermediate M4

By using

Respectively replace

The intermediate M4 was obtained by selecting the appropriate material ratio and the other raw materials and procedures were the same as in example 1.

Product MS (m/e): 367.99, respectively; elemental analysis (C)₁₉H₁₀Cl₂N₂S): theoretical value C: 61.80%, H: 2.73%, N: 7.59 percent; found value C: 61.55%, H: 2.61%, N: 7.45 percent.

Example 5 Synthesis of intermediate M5

By using

Respectively replace

The intermediate M5 was obtained by selecting the appropriate material ratio and the other raw materials and procedures were the same as in example 1.

Product MS (m/e): 334.03, respectively; elemental analysis (C)₁₉H₁₁ClN₂S): theoretical value C: 68.16%, H: 3.31%, N: 8.37 percent; found value C: 68.01%, H: 3.16%, N: 8.25 percent.

Example 6 Synthesis of intermediate M6

By using

Respectively replace

The intermediate M6 was obtained by selecting the appropriate material ratio and the other raw materials and procedures were the same as in example 1.

Product MS (m/e): 334.03; elemental analysis (C)₁₉H₁₁ClN₂S): theoretical value C: 68.16%, H: 3.31%, N: 8.37 percent; found value C: 68.02%, H: 3.11%, N: 8.26 percent.

Example 7 Synthesis of intermediate M7

By using

Respectively replace

The intermediate M7 was obtained by selecting the appropriate material ratio and the other raw materials and procedures were the same as in example 1.

Product MS (m/e): 334.03, respectively; elemental analysis (C)₁₉H₁₁ClN₂S): theoretical value C: 68.16%, H: 3.31%, N: 8.37 percent; found value C: 68.02%, H: 3.11%, N: 8.26 percent.

Example 8 Synthesis of intermediate M8

By using

Instead of the former

The intermediate M8 was obtained by selecting the appropriate material ratio and the other raw materials and procedures were the same as in example 1.

Example 9 Synthesis of intermediate M9

The synthetic route is as follows:

the method comprises the following specific steps:

(1) synthesis of intermediate M9-04:

by using

Respectively replace

The M9-04 was obtained by selecting the appropriate material ratio and the other raw materials and procedures as in example 1.

(2) Synthesis of intermediate M9:

in N₂Under protection, M9-04(58.8g,0.1mol) and 500ml of anhydrous THF were added into a 2L three-necked flask, the reaction system was cooled to-78 ℃ with stirring by a liquid nitrogen ethanol bath, 70ml of a 1.6M hexane solution of n-butyllithium (0.11mol) was slowly added at this temperature, after completion of the dropwise addition, the temperature was maintained at this temperature for 15 minutes, sublimed sulfur powder (3.2g,0.1mol) was then added, after completion of the addition, the reaction system was stirred at-78 ℃ for 1 hour, and then the reaction system was slowly heated to-20 ℃ and kept at this temperature for 30 minutes. The reaction was then cooled further to-78 ℃ and CuCl (10g, 0.1mol) was added, the temperature was held at this temperature for 30 minutes, then the cold bath was removed, the reaction was allowed to warm to room temperature naturally, stirred for 2h, then the reaction was heated to reflux and reacted for 2 h. Cooling to room temperature, slowly adding saturated ammonium chloride solution, adding ethyl acetate 250ml, separating organic phase, extracting aqueous phase with ethyl acetate for 3 times, combining organic phases, drying anhydrous magnesium chloride, spin-drying solvent, and separating by column chromatography to obtain intermediate M9 19.4g altogether, white solid, yield about 47%.

Product MS (m/e): 411.94, respectively; elemental analysis (C)₁₉H₁₀BrClN₂S): theoretical value C: 55.16%, H: 2.44%, N: 6.77 percent; found value C: 55.02%, H: 2.21%, N: 6.59 percent.

Example 10 Synthesis of intermediate M10

By using

Respectively replace

The intermediate M10 was obtained by selecting the appropriate material ratio and the other raw materials and procedures were the same as in example 9.

EXAMPLE 11 Synthesis of Compounds I-16

The synthetic route is as follows:

A1L three-necked flask was equipped with magnetic stirring, and after nitrogen substitution, M1(40.2g, 0.1mol), (9-phenyl-9H-carbazol-3-yl) boronic acid (86.1g, 0.3mol), cesium carbonate (117g, 0.36mol) and dioxane 400ml were sequentially added, followed by stirring. After nitrogen replacement again, (2.2g, 11mmol) tri-tert-butylphosphine and (4.1g, 4.5mmol) 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 79.8g of pale yellow solid with the yield of about 78%.

Product MS (m/e): 1023.34, respectively; elemental analysis (C)₇₃H₄₅N₅S): theoretical value C: 85.60%, H: 4.43%, N: 6.84 percent; found value C: 85.39%, H: 4.26%, N: 6.73 percent.

EXAMPLE 12 Synthesis of Compound I-26

The synthetic route is as follows:

using M2 instead of M1, (9- (naphthalene-2-yl) -9H-carbazol-3-yl) boronic acid instead of (9-phenyl-9H-carbazol-3-yl) boronic acid, the appropriate material ratios were chosen and the other starting materials and procedures were the same as in example 11 to give 69.7g of a pale yellow solid with a yield of about 79%.

Product MS (m/e): 882.28, respectively; elemental analysis (C)₆₇H₄₂N₄S): theoretical value C: 85.69%, H: 4.34%, N: 6.34 percent; found value C: 85.45%, H: 4.26%, N: 6.22 percent.

EXAMPLE 13 Synthesis of Compound I-43

The synthetic route is as follows:

substituting M3 for M1, (4'- (9H-carbazol-9-yl) - [1,1' -biphenyl ] -4-yl) boronic acid for (9-phenyl-9H-carbazol-3-yl) boronic acid, selecting the appropriate material ratios, the other starting materials and procedures were the same as in example 11, yielding 74.7g of a pale yellow solid with a yield of about 80%.

Product MS (m/e): 934.31, respectively; elemental analysis (C)₆₇H₄₂N₄S): theoretical value C: 86.05%, H: 4.53%, N: 5.99 percent; found value C: 85.91%, H: 4.44%, N: 5.76 percent.

EXAMPLE 14 Synthesis of Compound I-60

The synthetic route is as follows:

m4 was used in place of M1, and (5-phenyl-5H-benzo [ b ] carbazol-2-yl) boronic acid was used in place of (9-phenyl-9H-carbazol-3-yl) boronic acid, and the other raw materials and procedures were the same as in example 11, except that the appropriate material ratio was selected, to give 63.5g of a pale yellow solid with a yield of about 72%.

Product MS (m/e): 882.28; elemental analysis (C)₆₃H₃₈N₄S): theoretical value C: 85.69%, H: 4.34%, N: 6.34 percent; found value C: 85.51%, H: 4.22%, N: 6.13 percent.

EXAMPLE 15 Synthesis of Compound I-77

The synthetic route is as follows:

the method comprises the following specific steps:

using M5 instead of M1 and (4- (7H-dibenzo [ c, g ] carbazol-7-yl) phenyl) boronic acid instead of (9-phenyl-9H-carbazol-3-yl) boronic acid, the appropriate material ratios were chosen and the other raw materials and procedures were the same as in example 11 to give 51.9g of a pale yellow solid with a yield of about 81%.

Product MS (m/e): 641.19, respectively; elemental analysis (C)₄₅H₂₇N₃S): theoretical value C: 84.22%, H: 4.24%, N: 6.54 percent; found value C: 84.01%, H: 4.14%, N: 6.40 percent.

EXAMPLE 16 Synthesis of Compound I-93

The synthetic route is as follows:

using M6 instead of M1, (4- (10-phenylindole [3,2-b ] indol-5 (10H) -yl) phenyl) boronic acid instead of (9-phenyl-9H-carbazol-3-yl) boronic acid, the appropriate material ratios were chosen and the other starting materials and procedures were the same as in example 11 to give 51.2g of a pale yellow solid with a yield of about 78%.

Product MS (m/e): 656.20, respectively; elemental analysis (C)₄₅H₂₈N₄S): theoretical value C: 82.29%, H: 4.30%, N: 8.53 percent; found value C: 82.03%, H: 4.21%, N: 8.43 percent.

EXAMPLE 17 Synthesis of Compound I-109

The synthetic route is as follows:

the procedure of example 11 was repeated except that M7 was used instead of M1 and (4- (11H-benzo [4,5] thieno [3,2-b ] carbazol-11-yl) phenyl) boronic acid was used instead of (9-phenyl-9H-carbazol-3-yl) boronic acid, and the appropriate material ratio was selected to obtain 54.3g of a pale yellow solid with a yield of about 84%.

Product MS (m/e): 647.15, respectively; elemental analysis (C)₄₃H₂₅N₃S₂): theoretical value C: 79.73%, H: 3.88%, N: 6.49 percent; found value C: 79.52%, H: 3.73%, N: 6.39 percent.

EXAMPLE 18 Synthesis of Compound I-125

The synthetic route is as follows:

m8 was used in place of M1, and (3-phenylbenzo [ b ] thiophen-2-yl) boronic acid was used in place of (9-phenyl-9H-carbazol-3-yl) boronic acid, and the other raw materials and procedures were the same as in example 11, except that the appropriate material ratio was selected, whereby 54.4g of a pale yellow solid was obtained with a yield of about 76%.

Product MS (m/e): 716.14, respectively; elemental analysis (C)₄₇H₂₈N₂S₃): theoretical value C: 78.74%, H: 3.93%, N: 3.91 percent; found value C: 78.54%, H: 3.81%, N: 3.83 percent.

EXAMPLE 19 Synthesis of Compound I-174

The synthetic route is as follows:

into a 1L three-necked flask, M9(41.2g, 0.1mol), (4'- (9H-carbazol-9-yl) - [1,1' -biphenyl) was charged]-4-yl) boronic acid (36.3g, 0.1mol), sodium carbonate (21.2g,0.2mol), toluene 150mL, ethanol 150mL, water 150mL, the reaction system was purged with nitrogen and Pd (PPh) was added₃)₄(11.5g, 0.01 mol). 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 53.4g of light yellow solid I-174-1 is obtained after filtration, and the yield is about 82%.

A1L three-necked flask is stirred by magnetic force, after nitrogen replacement, I-174-1(65.1g, 0.1mol), (5-phenyl-5H-benzo [ b ] carbazol-2-yl) boronic acid (33.7g, 0.1mol), cesium carbonate (39g, 0.12mol) and dioxane 400ml are added in sequence, and stirring is 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 organic phase, extracting, drying, column chromatography, and spin-drying solvent to obtain 69.0g pale yellow solid I-174 with yield of about 76%.

Product MS (m/e): 908.30, respectively; elemental analysis (C)₆₅H₄₀N₄S): theoretical value C: 85.88%, H: 4.44%, N: 6.15 percent; found value C: 85.63%, H: 4.29%, N: 6.02 percent.

EXAMPLE 20 Synthesis of Compound I-176

The synthetic route is as follows:

substituting M10 for M9, (4- (7H-dibenzo [ c, g ] carbazol-7-yl) phenyl) boronic acid and dibenzo [ b, d ] thiophen-2-ylboronic acid for (4'- (9H-carbazol-9-yl) - [1,1' -biphenyl ] -4-yl) boronic acid and (5-phenyl-5H-benzo [ b ] carbazol-2-yl) boronic acid, respectively, selecting appropriate material ratios and the other raw materials and procedures were the same as in example 9, yielding 61.7g of a pale yellow solid I-176 in about 75% yield.

Product MS (m/e): 823.21, respectively; elemental analysis (C)₅₇H₃₃N₃S₂): theoretical value C: 83.08%, H: 4.04%, N: 5.10 percent; found value C: 82.89%, H: 3.96%, N: 5.00 percent.

According to the technical schemes of the examples 1 to 20, other compounds of I-1 to I-180 can be synthesized only by simply replacing corresponding raw materials and not changing any substantial operation.

EXAMPLE 21 use of the Compound of the present invention as a Green host Material

The embodiment provides a group of OLED green light devices, and the structure of the device is as follows:

ITO/HATCN (1nm)/HT01(40nm)/NPB (20nm)/EML (30nm) (containing any of the compounds provided in examples 11-20)/Bphen (40nm)/LiF (1 nm)/Al.

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

the preparation process of the OLED green light device OLED-1 comprises the following steps:

(1) ultrasonically cleaning a glass substrate coated with an ITO transparent conductive film in cleaning solution, ultrasonically treating the glass substrate in deionized water, ultrasonically removing oil in a mixed solution of acetone and ethanol (the volume ratio is 1: 1), baking the glass substrate in a clean environment until the water is completely removed, carrying out etching and ozone treatment by using an ultraviolet lamp, and bombarding the surface by using low-energy cation beams;

(2) placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to 1 × 10^-5～9×10^-3Pa, performing vacuum evaporation on the anode layer film to form HATCN 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) vacuum evaporating EML (Electron cyclotron resonance) on the hole transport layer to serve as a light emitting layer of the device, wherein the EML comprises the green light host material (I-16) and the dye material, placing the host material serving as the light emitting layer in a chamber of vacuum vapor deposition equipment by using a multi-source co-evaporation method, and adding Ir (ppy) serving as a dopant₃Placing in another chamber of vacuum vapor deposition equipment, and adjusting evaporation rate of main material to 0.1nm/s, Ir (ppy)₃The concentration of (2) is 10%, and the total thickness of the evaporation coating is 30 nm;

(4) evaporating Bphen on the luminescent layer in vacuum to form an electron transport layer with the thickness of 40nm, wherein the evaporation rate is 0.1 nm/s;

(5) LiF with the thickness of 1nm is sequentially subjected to vacuum evaporation on the electron transport layer to serve as an electron injection layer, and an Al layer with the thickness of 150nm serves as a cathode of the device.

According to the same steps as the above, only replacing I-16 in the step (3) with I-26, I-43, I-60, I-77, I-93, I-109, I-125, I-174 and I-176 respectively, and using the materials as green host materials to obtain OLED-2-OLED-10 respectively provided by the invention.

Following the same procedure as above, only replacing I-16 in step (3) with CBP (comparative compound), comparative example OLED-11 provided by the present invention was obtained. The structure of the CBP 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

From the above, the devices OLED-1 to OLED-10 prepared by using the organic material shown in the formula (I) provided by the invention have higher current efficiency, and under the condition of the same brightness, the working voltage is obviously lower than that of the device OLED-11 using CBP as the main material, so that the organic material is a green light main material 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.

Claims

1. A compound of formula (I):

wherein,

R₁～R₁₂each independently is selected from hydrogen atom, and R₁～R₁₂Wherein at least one group is a substituted or unsubstituted aromatic group containing a five-membered heterocycle;

the substituted or unsubstituted aromatic group containing a five-membered heterocycle is selected from:

2. the compound of claim 1, selected from the compounds of the following specific structures:

3. use of a compound according to claim 1 or 2 in the preparation of an organic electroluminescent device.

4. Use according to claim 3, wherein the use is the use of a compound according to claim 1 or 2 as a light-emitting host material for an electroluminescent layer in an organic electroluminescent device.

5. An organic electroluminescent device comprising an electroluminescent layer containing the compound of claim 1 or 2.

6. The organic electroluminescent device according to claim 5, wherein the organic electroluminescent device comprises, in order from bottom to top, a transparent substrate, an anode layer, a hole transport layer, an electroluminescent layer comprising the compound of claim 1 or 2, an electron transport layer, an electron injection layer, and a cathode layer.

7. A display apparatus, wherein the display apparatus comprises the organic electroluminescent device according to claim 5 or 6.

8. A lighting apparatus, wherein the lighting apparatus comprises the organic electroluminescent device according to claim 5 or 6.