CN111961019B - Organic photoelectric material containing butterfly structure and preparation method and application thereof - Google Patents

Organic photoelectric material containing butterfly structure and preparation method and application thereof Download PDF

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CN111961019B
CN111961019B CN202010986650.3A CN202010986650A CN111961019B CN 111961019 B CN111961019 B CN 111961019B CN 202010986650 A CN202010986650 A CN 202010986650A CN 111961019 B CN111961019 B CN 111961019B
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林存生
高斌
付少邦
慈振华
石宇
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Abstract

The invention relates to an organic photoelectric material containing a butterfly structure, a preparation method and application thereof, wherein the organic photoelectric material is shown as the following formula I:
Figure DDA0002689490850000011
wherein, ar is 1 、Ar 2 Same or different, said Ar 1 、Ar 2 Simultaneously or partially, said Ar 1 、Ar 2 Is selected from one of hydrogen and substituted or unsubstituted polycyclic conjugated aryl with 4 to 36 carbon atoms. The organic photoelectric material has the characteristics of difficult intermolecular crystallization, difficult aggregation and good film forming property, and the 3D rigid structure in the molecule can improve the thermal stability of the luminescent material and is applied to an organic electroluminescent device as the luminescent material, thereby improving the maximum current efficiency of the organic electroluminescent device, reducing the starting voltage of the organic electroluminescent device and greatly prolonging the service life of the organic electroluminescent device.

Description

Organic photoelectric material containing butterfly structure and preparation method and application thereof
Technical Field
The invention relates to an organic photoelectric material containing a butterfly structure, a preparation method and application thereof, belonging to the technical field of organic luminescent materials.
Background
The origin of organic light emitting diode (abbreviated as OLED) can be traced back to the sixties of the twentieth century, pope et al use anthracene single crystal to emit light by applying a dc voltage, but it does not attract much attention because of high driving voltage (100V) and low luminance and efficiency. With the continuous improvement of the technology, in 1987, 8-hydroxyquinoline aluminum (Alq 3) is used as a luminescent material by c.w.tang et al of Kodak company, and the OLED with a double-layer sandwich structure is manufactured by a vacuum evaporation method, the starting voltage is only a few volts, and the brightness can reach as high as 1000cd/m2, so that the marking OLED takes an important step towards the practicability, thereby becoming an important milestone in the field of organic electroluminescence.
Currently, research on the improvement of the performance of OLEDs includes: the driving voltage of the device is reduced, the luminous efficiency of the device is improved, the service life of the device is prolonged, and the like. In order to realize the continuous improvement of the performance of the OLED, not only the structure of the OLED and the innovation of the manufacturing process of the OLED are required, but also the photoelectric material used in the OLED needs to be continuously researched and innovated, so that a photoelectric functional material with higher performance and applied to the OLED is created.
The photoelectric functional materials can be divided into two broad categories from the aspect of application, namely charge injection transport materials and luminescent materials, further, the charge injection transport materials can be further divided into electron injection transport materials, electron blocking materials, hole injection transport materials and hole blocking materials, and the luminescent materials can be further divided into host luminescent materials and doping materials.
And for the butterfly-shaped material, because of having the plane configuration of intercrossing, can effectively avoid the molecule to gather to increase the film stability of material, through introducing different substituent groups at the appropriate position of the spiral-shaped material, can well adjust the spectral color of the material, improve the thermal stability and the film stability of the material.
In addition, the butterfly structure has strong modifiability, and the spiral structure with different types and structures is developed, and on the basis, the organic electroluminescent material with excellent performance is hopefully obtained through proper chemical modification.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the organic photoelectric material which has the characteristics of difficult crystallization and aggregation among molecules and good film forming property, and the rigid group in the molecule can improve the thermal stability of the material.
The technical scheme for solving the technical problems is as follows: an organic photoelectric material containing a butterfly structure, wherein the organic photoelectric material is represented by the following formula I:
Figure BDA0002689490830000021
/>
wherein, ar is 1 、Ar 2 Same or different, said Ar 1 、Ar 2 Simultaneously or partially present, said Ar 1 、Ar 2 Is selected from one of hydrogen and substituted or unsubstituted polycyclic conjugated aryl with 4 to 36 carbon atoms.
Further, the organic photoelectric material is represented by formula II or formula III:
Figure BDA0002689490830000022
wherein, ar is 1 、Ar 2 Same or different, said Ar 1 、Ar 2 Simultaneously or partially, said Ar 1 、Ar 2 Is selected from one of hydrogen and substituted or unsubstituted polycyclic conjugated aryl with 4 to 36 carbon atoms.
Further, ar is 1 、Ar 2 Any one selected from the following groups:
Figure BDA0002689490830000023
Figure BDA0002689490830000031
/>
Figure BDA0002689490830000032
* Indicates the bonding site.
Further, the organic photoelectric material is specifically any one of the following H01-H54 compounds:
Figure BDA0002689490830000033
/>
Figure BDA0002689490830000041
/>
Figure BDA0002689490830000051
/>
Figure BDA0002689490830000061
the invention has the beneficial effects that: the invention provides an organic photoelectric material containing a butterfly structure, the compound has the characteristics of difficult crystallization and aggregation among molecules and good film forming property as the organic photoelectric material, and the rigid group in the molecule can improve the thermal stability of the material.
The invention also discloses a preparation method of the organic photoelectric material containing the butterfly structure, which comprises the following steps:
(1) Under the protection of inert gas, adding parachlorophenol, titanium tetrachloride and an organic solvent into a reaction system, slowly adding ethoxyoxalyl chloride at the temperature of-20-50 ℃, keeping the temperature and stirring for 1-8.0 hrs, pouring into dilute hydrochloric acid to quench after the reaction is finished, thus obtaining the reaction system containing an intermediate 1, wherein the organic solvent is one or more selected from dichloromethane, chloroform and dichloroethane, the intermediate 1 is shown as the following formula 1, and X is selected from hydrogen, chlorine or bromine atoms;
Figure BDA0002689490830000071
/>
(2) Adding the intermediate 1 obtained in the step (1) and a basic substance into an organic solvent, and adding trifluoromethanesulfonyl chloride to react for 1-12.0 hrs at-10-60 ℃ under the protection of inert gas to obtain a reaction system containing an intermediate 3, wherein the basic substance is selected from one or more of triethylamine, diisopropylethylamine, pyridine and N, N-dimethylpyridine-4-amine, the organic solvent is selected from one or more of dichloromethane, trichloromethane, dichloroethane or toluene, the intermediate 2 is represented by the following formula 2, and X is selected from hydrogen, chlorine or bromine atoms;
Figure BDA0002689490830000072
(3) Adding the intermediate 2 obtained in the step (2), the raw material 2 and a basic substance into an organic solvent, adding a catalyst into the system under the protection of inert gas, and reacting at 60-150 ℃ for 3-12.0 hrs to obtain a reaction system containing the intermediate 3, wherein the basic substance is one or more of potassium carbonate, sodium carbonate, potassium phosphate and potassium hydroxide, the catalyst is a palladium-containing catalyst and an organic phosphine ligand, and the palladium-containing catalyst is Pd (OAc) 2 、Pd(PPh 3 ) 4 、Pd(PPh 3 ) 2 Cl 2 And Pd (dppf) Cl 2 One or more of triphenylphosphine and DPPP (CAS-RN: 6737-42-4), xantphos (CAS-RN: 161265-03-8), sphos (CAS-RN: 657408-07-6) and P (t-Bu) 3 ·HBF 4 (CAS-RN: 113978-91-9) by one or more of the following steps, wherein the raw material 2 is shown as the following formula 3, and the intermediate 3 is shown as the following formula 4, wherein Y is selected from hydrogen, chlorine or bromine atoms;
Figure BDA0002689490830000073
(4) Adding the intermediate 3 obtained in the step (3) and an alkaline substance into an organic solvent, and reacting for 1-12.0 hrs at 60-150 ℃ under the protection of inert gas to obtain a reaction system containing an intermediate 4, wherein the alkaline substance is one or more selected from potassium hydroxide, sodium hydroxide and sodium ethoxide, and the intermediate 4 is shown as the following formula 5;
Figure BDA0002689490830000081
(5) Adding the intermediate 4 obtained in the step (4) and N, N-carbonyl diimidazole into an organic solvent, and reacting for 1-24.0 hrs at-20-60 ℃ under the protection of inert gas; then at the temperature of minus 20 to 60 ℃, adding titanium tetrachloride, keeping the temperature for reaction for 1 to 12.0hrs, pouring into dilute hydrochloric acid for quenching to obtain a reaction system containing an intermediate 5, wherein the organic solvent is selected from one or more of dichloromethane, dichloroethane and chloroform, and the intermediate 5 is shown as the following formula 6;
Figure BDA0002689490830000082
(6) Adding the intermediate 5 obtained in the step (5) into an organic solvent, adding a 1-naphthyl magnesium bromide/4-methyl dihydropyran solution at the temperature of minus 20-60 ℃ under the protection of inert gas, and reacting for 1-24.0 hrs at the temperature of minus 20-60 ℃; then pouring into diluted hydrochloric acid for quenching to obtain a reaction system containing an intermediate 6, wherein the organic solvent is selected from one or more of THF and 4-methyl dihydropyran, and the intermediate 6 is shown as the following formula 7;
Figure BDA0002689490830000083
(7) Adding the intermediate 6 obtained in the step (6) into an organic solvent, adding trifluoromethanesulfonic acid under the protection of inert gas, and reacting at 30-150 ℃ for 1-24.0 hrs to obtain a reaction system containing an intermediate 7, wherein the organic solvent is selected from one or more of toluene and xylene, and the intermediate 7 is represented by the following formula 8;
Figure BDA0002689490830000091
(8) Under the protection of inert gas, adding the intermediate 7 obtained in the step (7), polycyclic conjugated aromatic boric acid, an alkaline substance and a reaction solvent into a reaction system, adding a catalyst into the system, reacting at 60-150 ℃ for 3-12.0 hrs to obtain a reaction system containing the organic photoelectric material with the butterfly structure, wherein the alkaline substance is selected from potassium carbonate,One or more of sodium carbonate, potassium phosphate and potassium hydroxide, wherein the catalyst is a palladium-containing catalyst and an organic phosphine ligand, and the palladium-containing catalyst is Pd (OAc) 2 、Pd(PPh 3 ) 4 、Pd(PPh 3 ) 2 Cl 2 And Pd (dppf) Cl 2 One or more of triphenylphosphine, DPPP (CAS-RN: 6737-42-4), xantphos (CAS-RN: 161265-03-8), sphos (CAS-RN: 657408-07-6), P (t-Bu) 3 ·HBF 4 (CAS-RN: 113978-91-9) in a single or a mixture of several.
Preferably, in step (1), the organic solvent is selected from dichloromethane, chloroform or dichloroethane, and the molar ratio of the p-chlorophenol to the titanium tetrachloride is p-chlorophenol: titanium tetrachloride =1: 1.0-1.5, the molar ratio of the dosage of p-chlorophenol to the dosage of ethoxy oxalyl chloride is p-chlorophenol: ethoxy oxalyl chloride =1:1.0 to 1.5;
in the step (2), the organic solvent is selected from dichloromethane, chloroform, dichloroethane or toluene, the basic substance is selected from triethylamine, diisopropylethylamine, pyridine and N, N-dimethylpyridine-4-amine, and the molar ratio of the amount of the intermediate 1 to the amount of the basic substance is that the intermediate 1: basic substance =1.0: 1.0-1.5, wherein the molar ratio of the dosage of the intermediate 1 to the dosage of the trifluoromethanesulfonyl chloride is that the intermediate 1: trifluoromethanesulfonyl chloride =1:1.0 to 1.5;
in the step (3), the organic solvent is selected from tetrahydrofuran, dioxane, toluene, xylene or trimethylbenzene, and the molar ratio of the amount of the intermediate 2 to the amount of the raw material 2 is that the intermediate 2: raw material 2=1: 1.0-1.2, wherein the molar ratio of the using amount of the intermediate 2 to the using amount of the alkaline substance is that the intermediate 2: basic substance =1: 1.0-3.0, wherein the molar ratio of the using amount of the intermediate 3 to the using amount of the catalyst is that the intermediate 2: catalyst =1: 0.001-0.1, wherein the molar ratio of the palladium catalyst dosage to the phosphine ligand dosage is that the palladium catalyst: phosphine ligand =1:0.5 to 4;
in the step (4), the organic solvent is selected from methanol, ethanol or isopropanol, and the molar ratio of the amount of the intermediate 3 to the amount of the alkaline substance is that the intermediate 3: basic substance =1:1.0 to 2.0;
in step (5), the organic solvent is selected from dichloromethane, dichloroethane or chloroform, and the molar ratio of the amount of the intermediate 4 to the amount of the N, N-carbonyldiimidazole is intermediate 4: n, N-carbonyldiimidazole =1: 1.5-3.0, wherein the molar ratio of the using amount of the intermediate 4 to the using amount of the titanium tetrachloride is that the intermediate 4: titanium tetrachloride =1:3.0 to 5.0;
in step (6), the organic solvent is selected from THF or 4-methyl dihydropyran, and the molar ratio of the amount of the intermediate 5 to the amount of the 1-naphthyl magnesium bromide is intermediate 5: 1-naphthyl magnesium bromide =1:2.0 to 2.2;
in step (7), the organic solvent is selected from toluene or xylene, and the molar ratio of the amount of the intermediate 6 to the amount of the trifluoromethanesulfonic acid is intermediate 6: trifluoromethanesulfonic acid =1:2.0 to 3.0;
in the step (8), the organic solvent is selected from tetrahydrofuran, dioxane, toluene, xylene or trimethylbenzene, and the molar ratio of the amount of the intermediate 7 to the amount of the polycyclic conjugated aromatic hydrocarbon boric acid is that the intermediate 7: polycyclic conjugated arene boronic acid =1: 1.0-1.2, wherein the molar ratio of the using amount of the intermediate 7 to the using amount of the alkaline substance is that the intermediate 7: basic substance =1: 1.0-3.0, wherein the molar ratio of the using amount of the intermediate 7 to the using amount of the catalyst is that the intermediate 7: catalyst =1: 0.001-0.1, wherein the molar ratio of the dosage of the palladium catalyst to the dosage of the phosphine ligand is that the palladium catalyst: phosphine ligand =1:0.5 to 4.
The invention also provides application of the organic photoelectric material containing the butterfly structure, which is characterized in that the organic photoelectric material is applied to an OLED (organic light-emitting device), and the organic light-emitting device comprises an anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer and a cathode; wherein the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer, the electron injection layer and the cathode are sequentially stacked on the anode; the organic photoelectric material is applied as at least one functional layer in an organic electroluminescent device.
Preferably, the organic photoelectric material is applied to a light emitting layer of the OLED.
The invention provides an organic photoelectric material containing a butterfly structure, and provides a synthesis method of the organic photoelectric material, an OLED device manufactured by taking the organic photoelectric material as a luminescent material shows better efficiency, and the specific beneficial effects comprise:
1. the preparation method of the organic photoelectric material is a new method for preparing the organic photoelectric material containing the butterfly structure;
2. the organic photoelectric material has better film stability and proper molecular energy level, can be used as a blue light-emitting material and applied to the field of organic electroluminescence;
3. the organic photoelectric material has good thermal stability, high glass transition temperature and decomposition temperature, is easy to form a good amorphous film, and can obtain more stable effect and longer service life when being applied to an electroluminescent device;
4. in the organic electroluminescent device provided by the invention, the organic photoelectric material provided by the invention is contained, so that the power efficiency of the organic electroluminescent device can be greatly improved, the maximum current efficiency of an organic electroluminescent device is improved, and meanwhile, the driving voltage is also reduced, so that the service life of the organic electroluminescent device is obviously prolonged.
Drawings
FIG. 1 is a schematic structural diagram of an organic electroluminescent device in a second embodiment;
in the figure, 1 a transparent substrate layer, 2 an anode layer, 3 a hole injection layer, 4 a hole transport layer, 5 an electron blocking layer, 6 a light emitting layer, 7 an electron transport layer, 8 an electron injection layer, 9 a cathode layer, and 10 a light extraction layer.
Detailed Description
The present invention will be described in detail with reference to the following embodiments in order to make the above objects, features and advantages of the present invention more comprehensible. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Example one
This example shows the preparation of some of the compounds H01 to H54.
Preparation of Compound H03 of embodiment 1
(1) Preparation of intermediate 1
Figure BDA0002689490830000111
Preparation of intermediate 1: into a 1L three-necked flask, under a nitrogen atmosphere, p-hydroxychlorobenzene (12.9g, 0.1mol), titanium tetrachloride (20.9g, 0.11mol), and 200mL of dry methylene chloride were charged, ethoxyoxalyl chloride (15.0g, 0.11mol) was gradually dropped at an internal temperature of-5 to 0 ℃ for about 2.0hrs, the reaction was maintained at an internal temperature of-5 to 0 ℃ for 2.0hrs, the progress of the reaction was followed by TLC, and after completion of the reaction, 300mL of methylene chloride was charged, and the mixture was slowly poured into 1.0L of 12% dilute hydrochloric acid in ice water. Stirring for 30min, separating, collecting organic phase, removing solvent under reduced pressure, and recrystallizing with ethanol petroleum ether to obtain 20.1g of brown yellow solid intermediate 1, which can be used in the next step without purification, with a yield of 88.16%.
(2) Preparation of intermediate 2
Figure BDA0002689490830000121
Preparation of intermediate 2: adding the intermediate 1 (13.7g, 0.06mol) and 400mL of dry dichloroethane in a 1L three-necked flask under the protection of nitrogen, controlling the internal temperature to be-5-0 ℃, slowly adding triethylamine (7.3g, 0.072mol), further controlling the internal temperature to be-5-0 ℃, slowly adding trifluoromethanesulfonyl chloride (12.1g, 0.072mol), and keeping the temperature for reaction for 2.0hrs. After the reaction was completed, the reaction system was slowly poured into 200g of ice water, stirred for 30min, separated, washed once with 5% aqueous sodium bicarbonate, the organic phase was collected, dried, and the solvent was removed under reduced pressure to give 22.0g of a brownish black solid intermediate 2, which was used in the next step without purification, with a yield of 100%.
(3) Preparation of intermediate 3
Figure BDA0002689490830000122
Preparation of intermediate 3: adding intermediate 2 (18.0g, 0.05mol), dibenzofuran-4-boric acid (12.7g, 0.06mol), potassium carbonate (10.4g, 0.075 mol), 60g of water, 120mL of toluene and 60mL of ethanol into a 500L three-necked flask under the protection of nitrogen, after the nitrogen replacement is finished, adding palladium acetate (450mg, 0.002mol) and tricyclohexylphosphine (1.12g, 0.004mol), heating to reflux, keeping the internal temperature at 75-78 ℃, carrying out reflux heat preservation for 6.0hrs, after TLC tracking reaction, cooling to room temperature, layering, drying organic phase anhydrous sodium sulfate, passing through a silica gel column, and carrying out reduced pressure desolventization until no fraction is obtained, thus obtaining 19.0g of light yellow solid intermediate 3, wherein the yield is 100% without purification.
(4) Preparation of intermediate 4
Figure BDA0002689490830000123
Preparation of intermediate 4: crude intermediate 3 (19.0g, 0.05mol), sodium hydroxide (2.4g, 0.06mol) and 150mL of isopropanol are added into a 1L three-necked flask under the protection of nitrogen, after the nitrogen replacement is finished, the mixture is heated to reflux, the reflux temperature is kept for 3.0hrs, after the TLC tracing reaction is finished, the mixture is cooled to room temperature, and the mixture is slowly poured into and poured into 100mL of 6% dilute hydrochloric acid in ice water. Stirring for 30min, suction filtering, pulping with ethanol petroleum ether to obtain 14.2g of brown yellow solid intermediate 4, which can be used in the next step without purification, with a yield of 81.00%.
(5) Preparation of intermediate 5
Figure BDA0002689490830000131
Preparation of intermediate 5: adding the crude intermediate 4 (14.2g, 0.040mol), N, N-carbonyl diimidazole (13.0 g, 0.080mol) and 150mL of dichloromethane into a 500mL three-mouth bottle under the protection of nitrogen, after nitrogen replacement, keeping the temperature at 15-20 ℃ for 12.0hrs, then slowly cooling to-12-5 ℃, and dropwise adding TiCl 4 (30.3 g, 0.160mol)/50 mL of dichloromethane solution, after the completion of the dropwise addition, the reaction was incubated at room temperature for 6.0hrs, and quenched by slowly pouring into 300g,6mol/L of dilute hydrochloric acid. Stirring for 30min, suction filtration gave 8.8g of tan solid intermediate 5 in 66.16% yield.
(6) Preparation of intermediate 6
Figure BDA0002689490830000132
Preparation of intermediate 6: adding the intermediate 5 (8.3 g, 0.025mol) and 100mL 4-methyl dihydropyran into a 500mL three-mouth bottle under the protection of nitrogen, after nitrogen replacement, slowly cooling to 0-10 ℃, dropwise adding 103mL, 0.5mol/L1-naphthyl magnesium bromide/4-methyl dihydropyran solution, after dropwise adding, keeping the temperature at the temperature for reacting for 1.0hr, then slowly heating to 20-25 ℃, stirring for reacting for 3.0hr, slowly pouring into 200g,1mol/L diluted hydrochloric acid for quenching. Stirring for 30min, layering, washing with water, and removing solvent by organic phase under reduced pressure to obtain 15.0g brown viscous solid intermediate 6 without purification, with yield of 100%.
(7) Preparation of intermediate 7
Figure BDA0002689490830000133
Preparation of intermediate 7: adding the crude intermediate 6 (15.0 g, 0.025mol) and 120mL toluene into a 250mL three-neck flask under the protection of nitrogen, slowly dropwise adding trifluoromethanesulfonic acid (8.0 g, 0.053mol) under stirring, then slowly heating to 120-130 ℃, keeping the temperature at the temperature for reaction for 5.0hrs, then slowly heating to 20-25 ℃, and adding 50g water to quench and react. Stirring for 30min, layering, washing with water, removing solvent by organic phase vacuum pressure until no fraction is produced, and recrystallizing with THF ethanol to obtain 6.5g of off-white solid intermediate 7 without purification, wherein the yield is 47.10%.
(8) Preparation of Compound H03
Figure BDA0002689490830000141
Preparation of compound H03: adding the intermediate 7 (5.5g, 0.01mol), 9-phenanthreneboronic acid (2.5g, 0.011mol), potassium carbonate (2.1g, 0.015mol), 30g of water, 60mL of toluene and 20mL of ethanol into a 250mL three-neck flask under the protection of nitrogen, after the nitrogen replacement is finished, adding palladium acetate (450mg, 0.002mol) and tricyclohexylphosphine (1.12g, 0.004mol), heating to reflux, keeping the internal temperature at 75-78 ℃, carrying out reflux heat preservation for 6.0hrs, after TLC tracking reaction, cooling to room temperature, layering, drying organic phase anhydrous sodium sulfate, passing through a silica gel column, reducing the pressure to remove the solvent to no fraction, and recrystallizing THF ethanol to obtain 4.8g of H03 with the yield of 69.59 percent.
The crude product was further purified by sublimation at 360 ℃ in a chemical vapor deposition system to obtain 3.6g of off-white solid powder. HR-MS was used to identify this compound, formula C 54 H 30 O, detection value [ M ]]+ =694.2299, calculated 694.2297.
1 H NMR(400MHz，CDCl3)δ(ppm)：9.044～9.062ppm(dd,1H)，8.803～8.821ppm(dd,1H)，8.211～8.229ppm(dd,1H)，8.019ppm(s,1H)，7.891～7.987ppm(m,5H)，7.665～7.730(m,5H)，7.173～7.453(m,16H)。
Preparation of Compound H13 of embodiment 2
(1) Preparation of intermediate 1
Figure BDA0002689490830000142
Preparation of intermediate 1: into a 1L three-necked flask, under a nitrogen atmosphere, p-hydroxychlorobenzene (12.9g, 0.1mol), titanium tetrachloride (20.9g, 0.11mol), and 200mL of dry methylene chloride were charged, ethoxyoxalyl chloride (15.0g, 0.11mol) was gradually dropped at an internal temperature of-5 to 0 ℃ for about 2.0hrs, the reaction was maintained at an internal temperature of-5 to 0 ℃ for 2.0hrs, the progress of the reaction was followed by TLC, and after completion of the reaction, 300mL of methylene chloride was charged, and the mixture was slowly poured into 1.0L of 12% dilute hydrochloric acid in ice water. Stirring for 30min, separating, collecting organic phase, removing solvent under reduced pressure, and recrystallizing with ethanol petroleum ether to obtain 20.1g of brown yellow solid intermediate 1, which can be used in the next step without purification, with a yield of 88.16%.
(2) Preparation of intermediate 2
Figure BDA0002689490830000151
Preparation of intermediate 2: adding the intermediate 1 (13.7 g, 0.06mol) and 400mL of dry dichloroethane in a 1L three-necked bottle under the protection of nitrogen, controlling the internal temperature to be-5-0 ℃, slowly adding triethylamine (7.3 g, 0.072mol), further controlling the internal temperature to be-5-0 ℃, slowly adding trifluoromethanesulfonyl chloride (12.1g, 0.072mol), and reacting for 2.0hrs under heat preservation. After the reaction was completed, the reaction system was slowly poured into 200g of ice water, stirred for 30min, separated, washed once with 5% aqueous sodium bicarbonate, the organic phase was collected, dried, and the solvent was removed under reduced pressure to give 22.0g of a brownish black solid intermediate 2, which was used in the next step without purification, with a yield of 100%.
(3) Preparation of intermediate 3
Figure BDA0002689490830000152
Preparation of intermediate 3: adding intermediate 2 (18.0g, 0.05mol), dibenzofuran-4-boric acid (12.7g, 0.06mol), potassium carbonate (10.4g, 0.075 mol), 60g of water, 120mL of toluene and 60mL of ethanol into a 500L three-necked flask under the protection of nitrogen, after the nitrogen replacement is finished, adding palladium acetate (450mg, 0.002mol) and tricyclohexylphosphine (1.12g, 0.004mol), heating to reflux, keeping the internal temperature at 75-78 ℃, carrying out reflux heat preservation for 6.0hrs, after TLC tracking reaction, cooling to room temperature, layering, drying organic phase anhydrous sodium sulfate, passing through a silica gel column, and carrying out reduced pressure desolventization until no fraction is obtained, thus obtaining 19.0g of light yellow solid intermediate 3, wherein the yield is 100% without purification.
(4) Preparation of intermediate 4
Figure BDA0002689490830000161
Preparation of intermediate 4: crude intermediate 3 (19.0 g, 0.05mol), sodium hydroxide (2.4 g, 0.06mol) and 150mL of isopropanol were added in a 1L three-necked flask under nitrogen, after nitrogen substitution, heated to reflux, kept at reflux for 3.0hrs, and after TLC tracing, cooled to room temperature, poured slowly into 100mL of 6% dilute hydrochloric acid in ice water. Stirring for 30min, suction filtration, beating with ethanol petroleum ether to obtain 14.4g of a brown yellow solid intermediate 4, which is used in the next step without purification, with a yield of 82.09%.
(5) Preparation of intermediate 5
Figure BDA0002689490830000162
Preparation of intermediate 5: adding the crude intermediate 4 (14.2g, 0.040mol), N, N-carbonyl diimidazole (13.0 g, 0.080mol) and 150mL of dichloromethane into a 500mL three-mouth bottle under the protection of nitrogen, after nitrogen replacement, keeping the temperature at 15-20 ℃ for 12.0hrs, then slowly cooling to-12-5 ℃, and dropwise adding TiCl 4 (30.3 g, 0.160mol)/50 mL of dichloromethane solution, after the completion of the dropwise addition, the reaction was incubated at room temperature for 6.0hrs, and quenched by slowly pouring into 300g,6mol/L of dilute hydrochloric acid. Stirring for 30min, suction filtering, and pulping with acetonitrile to obtain 8.4g of brown yellow solid intermediate 5 with a yield of 63.16%.
(6) Preparation of intermediate 6
Figure BDA0002689490830000163
Preparation of intermediate 6: adding the intermediate 5 (8.3 g, 0.025mol) and 100mL 4-methyl dihydropyran into a 500mL three-mouth bottle under the protection of nitrogen, after nitrogen replacement, slowly cooling to 0-10 ℃, dropwise adding 103mL, 0.5mol/L1-naphthyl magnesium bromide/4-methyl dihydropyran solution, after dropwise adding, keeping the temperature at the temperature for reacting for 1.0hr, then slowly heating to 20-25 ℃, stirring for reacting for 3.0hr, slowly pouring into 200g,1mol/L diluted hydrochloric acid for quenching. Stirring for 30min, layering, washing with water, and vacuum desolventizing to no fraction to obtain 15.0g brown viscous solid intermediate 6 without purification in 100% yield.
(7) Preparation of intermediate 7
Figure BDA0002689490830000171
Preparation of intermediate 7: adding the crude intermediate 6 (15.0g, 0.025mol) and 120mL of toluene into a 250mL three-neck flask under the protection of nitrogen, slowly dropwise adding trifluoromethanesulfonic acid (8.0g, 0.053mol) under the stirring state, slowly heating to 120-130 ℃, keeping the temperature at the temperature for reaction for 5.0hrs, slowly heating to 20-25 ℃, and adding 50g of water to quench the reaction. Stirring for 30min, layering, washing with water, removing solvent by organic phase vacuum pressure until no fraction is produced, and recrystallizing with THF ethanol to obtain 6.0g of off-white solid intermediate 7 without purification, wherein the yield is 43.48%.
(8) Preparation of Compound H13
Figure BDA0002689490830000172
Preparation of compound H13: in a 250mL three-necked flask, under the protection of nitrogen, the intermediate 7 (5.5g, 0.01mol), (10-phenylanthracen-9-yl) boronic acid (3.3g, 0.011mol), potassium carbonate (2.1g, 0.015mol), 30g of water, 60mL of toluene and 20mL of ethanol were added, after nitrogen substitution was completed, palladium acetate (450mg, 0.002mol) and tricyclohexylphosphine (1.12g, 0.004mol) were added, heating was carried out until reflux, the internal temperature was 75 to 78 ℃, reflux heat preservation was carried out for 6.0hrs, TLC tracking reaction was completed, cooling was carried out to room temperature, layering was carried out, organic phase anhydrous sodium sulfate was dried, silica gel column was passed, desolvation was carried out under reduced pressure until no fraction, THF ethanol was recrystallized to obtain 5.6g of H13, and the yield was 72.73%.
Further depositing the crude product in chemical vaporSublimation purification was carried out at 360 ℃ in the system to obtain 4.9g of off-white solid powder. HR-MS was used to identify this compound, formula C 60 H 34 O, detection value [ M ]], + =770.2612, calculated 770.2610.
1 H NMR(400MHz，CDCl3)δ(ppm)：8.229～8.231ppm(dd,1H)，8.183～8.202ppm(d,1H)，8.145～8.140ppm(d,1H)，7.799～7.847ppm(m,4H)，7.562～7.697ppm(m,6H)，7.391～7.427ppm(m,4H)，7.172～7.448(m,16H),7.147～7.165(dd,1H)。
Preparation of Compound H21 of embodiment 3
(1) Preparation of intermediate 1
Figure BDA0002689490830000181
Preparation of intermediate 1: phenol (9.4 g, 0.1mol), titanium tetrachloride (20.9g, 0.11mol), and 200mL of dry methylene chloride were charged into a 1L three-necked flask under nitrogen atmosphere, ethoxyoxalyl chloride (15.0g, 0.11mol) was slowly dropped thereto at an internal temperature of-5 to 0 ℃ for about 2.0hrs, the reaction was kept at an internal temperature of-5 to 0 ℃ for 2.0hrs after completion of the dropping, the progress of the reaction was followed by TLC, and after completion of the reaction was confirmed, 300mL of methylene chloride was charged and slowly poured into 1.0L of 12% dilute hydrochloric acid in ice water. Stirring for 30min, separating, collecting organic phase, removing solvent under reduced pressure, and recrystallizing with ethanol petroleum ether to obtain 16.1g of brown yellow solid intermediate 1, which can be directly used in the next step without purification, with a yield of 82.99%.
(2) Preparation of intermediate 2
Figure BDA0002689490830000182
Preparation of intermediate 2: adding the intermediate 1 (11.7g, 0.06mol) and 400mL of dry dichloroethane in a 1L three-necked flask under the protection of nitrogen, controlling the internal temperature to be-5-0 ℃, slowly adding triethylamine (7.3g, 0.072mol), further controlling the internal temperature to be-5-0 ℃, slowly adding trifluoromethanesulfonyl chloride (12.1g, 0.072mol), and keeping the temperature for reaction for 2.0hrs. After the reaction, the reaction system was slowly poured into 200g of ice water, stirred for 30min, separated, washed once with 5% aqueous sodium bicarbonate, the organic phase was collected, dried, and the solvent was removed under reduced pressure to give 20.0g of a brownish black solid intermediate 2, which was used in the next step without purification, with a yield of 100%.
(3) Preparation of intermediate 3
Figure BDA0002689490830000191
Preparation of intermediate 3: in a 500L three-necked flask, under nitrogen protection, intermediate 2 (16.3 g, 0.05mol), (4-chlorodibenzo [ b, d ] furan-1-yl) boronic acid (14.8g, 0.06mol), potassium carbonate (10.4 g, 0.075mol), 60g of water, 120mL of toluene and 60mL of ethanol were charged, after nitrogen substitution was completed, palladium acetate (450mg, 0.002mol) and tricyclohexylphosphine (1.12g, 0.004mol) were charged, and the mixture was heated to reflux with an internal temperature of 75 to 78 ℃ and under reflux for 6.0hrs, after TLC-follow-up reaction was completed, cooled to room temperature, separated into layers, dried over anhydrous sodium sulfate for organic phase, passed through a silica gel column, and desolvated under reduced pressure to no fraction, to obtain 18.8g of pale yellow solid intermediate 3 without purification, with a yield of 100%.
(4) Preparation of intermediate 4
Figure BDA0002689490830000192
Preparation of intermediate 4: crude intermediate 3 (18.8g, 0.05mol) above, sodium hydroxide (2.4g, 0.06mol) and 150mL of isopropyl alcohol were charged in a 1L three-necked flask under nitrogen, after nitrogen substitution, heated to reflux, maintained at reflux for 3.0hrs, followed by TLC, cooled to room temperature, and slowly poured into 100mL of 6% dilute hydrochloric acid in ice water. Stirring for 30min, suction filtration, beating with ethanol petroleum ether to obtain 11.3g of tan solid intermediate 4, which is used in the next step without purification, with a yield of 59.79%.
(5) Preparation of intermediate 5
Figure BDA0002689490830000193
Preparation of intermediate 5: adding the crude intermediate 4 (10.5g, 0.030mol), N, N-carbonyldiimidazole (9.8g, 0.060mol) and 120mL of dichloromethane into a 500mL three-neck flask under the protection of nitrogen, keeping the temperature at 15-20 ℃ for 12.0hrs after the replacement of nitrogen, then slowly cooling to-12-5 ℃, and dropwise adding TiCl 4 (22.8 g, 0.120mol)/50 mL dichloromethane solution, after dropping, the reaction was incubated at this temperature for 6.0hrs, and quenched by slowly pouring into 300g,6mol/L dilute hydrochloric acid. Stirring for 30min, suction filtering, and pulping with acetonitrile to obtain 3.7g of brown yellow solid intermediate 5 with a yield of 37.00%.
(6) Preparation of intermediate 6
Figure BDA0002689490830000201
Preparation of intermediate 6: adding the intermediate 5 (3.3 g, 0.010mol) and 100mL 4-methyl dihydropyran into a 500mL three-necked flask under the protection of nitrogen, replacing the nitrogen, slowly cooling to 0-10 ℃, dropwise adding a 20mL, 0.5mol/L1-naphthyl magnesium bromide/4-methyl dihydropyran solution, preserving the temperature at the temperature for reacting for 1.0hr after dropwise adding, slowly heating to 20-25 ℃, stirring for reacting for 3.0hr, and slowly pouring into 200g,1mol/L diluted hydrochloric acid for quenching. Stirring for 30min, layering, washing with water, and removing the solvent by organic phase vacuum until no fraction is obtained to obtain 6.0g of brown viscous solid intermediate 6 without purification, wherein the yield is 100%.
(7) Preparation of intermediate 7
Figure BDA0002689490830000202
Preparation of intermediate 7: adding the crude intermediate 6 (6.0 g, 0.01mol) and 120mL of toluene into a 250mL three-neck flask under the protection of nitrogen, slowly dropwise adding trifluoromethanesulfonic acid (3.3 g, 0.022mol) while stirring, slowly heating to 120-130 ℃, keeping the temperature at the temperature for reaction for 5.0hrs, slowly heating to 20-25 ℃, and adding 50g of water to quench and react. Stirring for 30min, layering, washing with water, removing solvent by organic phase vacuum pressure until no fraction is produced, and recrystallizing with THF ethanol to obtain 2.3g of off-white solid intermediate 7 without purification, wherein the yield is 41.82%.
(8) Preparation of Compound H21
Figure BDA0002689490830000203
Preparation of compound H21: in a 100mL three-necked flask, under nitrogen protection, the intermediate 7 (2.3 g,4.3 mmol), (4- (phenanthren-9-yl) phenyl) boronic acid (1.5g, 5.0mmol), potassium carbonate (1.1g, 8mmol), 10g of water, 30mL of toluene and 10mL of ethanol were added, after nitrogen substitution was completed, palladium acetate (450mg, 0.002mol) and tricyclohexylphosphine (1.12g, 0.004mol) were added, heating was carried out at reflux, the internal temperature was 75 to 78 ℃, reflux incubation was carried out for 6.0hrs, after TLC tracking reaction was completed, the temperature was reduced to room temperature, layering was carried out, organic phase anhydrous sodium sulfate was dried, silica gel column was passed, desolvation was carried out under reduced pressure until no fraction, THF ethanol was recrystallized to obtain 2.2g of H21, and the yield was 66.67%.
The crude product was further purified by sublimation at 360 ℃ in a chemical vapor deposition system to obtain 1.8g of an off-white solid powder. HR-MS was used to identify this compound, formula C 60 H 34 O, detection value [ M ]], + =770.2608, calculated 770.2610.
1 H NMR(400MHz，CDCl 3 )δ(ppm)：9.063～9.079ppm(dd,1H)，8.841～8.858ppm(dd,1H)，8.281～8.299ppm(dd,1H)，8.119ppm(s,1H)，7.941～7.982ppm(m,2H)，7.545～7.730(m,6H)，7.193～7.453(m,22H)。
Preparation of Compound H37 of embodiment 4
(1) Preparation of intermediate 1
Figure BDA0002689490830000211
Preparation of intermediate 1: phenol (9.4 g, 0.1mol), titanium tetrachloride (20.9g, 0.11mol) and 200mL of dried methylene chloride were charged into a 1L three-necked flask under nitrogen atmosphere, the internal temperature was controlled to-5 to 0 ℃, ethoxyoxalyl chloride (15.0 g, 0.11mol) was slowly added dropwise over about 2.0hrs, the reaction was carried out at-5 to 0 ℃ for 2.0hrs by TLC, and after completion of the addition, 300mL of methylene chloride was added and the mixture was slowly poured into 1.0L of 12% dilute hydrochloric acid in ice water. Stirring for 30min, separating, collecting organic phase, removing solvent under reduced pressure, and recrystallizing with ethanol petroleum ether to obtain 16.1g of brown yellow solid intermediate 1, which can be directly used in the next step without purification, with a yield of 82.99%.
(2) Preparation of intermediate 2
Figure BDA0002689490830000212
Preparation of intermediate 3: adding the intermediate 1 (11.7g, 0.06mol) and 400mL of dry dichloroethane in a 1L three-necked flask under the protection of nitrogen, controlling the internal temperature to be-5-0 ℃, slowly adding triethylamine (7.3g, 0.072mol), further controlling the internal temperature to be-5-0 ℃, slowly adding trifluoromethanesulfonyl chloride (12.1g, 0.072mol), and keeping the temperature for reaction for 2.0hrs. After the reaction, the reaction system was slowly poured into 200g of ice water, stirred for 30min, separated, washed once with 5% aqueous sodium bicarbonate, the organic phase was collected, dried, and the solvent was removed under reduced pressure to give 20.0g of a brownish black solid intermediate 2, which was used in the next step without purification, with a yield of 100%.
(3) Preparation of intermediate 3
Figure BDA0002689490830000221
Preparation of intermediate 3: in a 500L three-necked flask, under the protection of nitrogen, adding intermediate 2 (16.3 g, 0.05mol), (4-chlorodibenzo [ b, d ] furan-1-yl) boronic acid (14.8g, 0.06mol), potassium carbonate (10.4g, 0.075mol), 60g of water, 120mL of toluene and 60mL of ethanol, after the nitrogen replacement is completed, adding palladium acetate (450mg, 0.002mol) and tricyclohexylphosphine (1.12g, 0.004mol), heating to reflux, keeping the internal temperature at 75-78 ℃, keeping the reflux for 6.0hrs, after the TLC tracing reaction is completed, cooling to room temperature, carrying out layering, drying with anhydrous sodium sulfate as an organic phase, passing through a silica gel column, and removing the solvent under reduced pressure until no fraction to obtain 18.9g of pale yellow solid intermediate 3 without purification, wherein the yield is 100%.
(4) Preparation of intermediate 4
Figure BDA0002689490830000222
Preparation of intermediate 4: crude intermediate 3 (18.9g, 0.05mol), sodium hydroxide (2.4g, 0.06mol) and 150mL of isopropanol are added into a 1L three-necked flask under the protection of nitrogen, after the nitrogen replacement is finished, the mixture is heated to reflux, the reflux temperature is kept for 3.0hrs, after the TLC tracing reaction is finished, the mixture is cooled to room temperature, and the mixture is slowly poured into and poured into 100mL of 6% dilute hydrochloric acid in ice water. Stirring for 30min, suction filtration, beating with ethanol petroleum ether to obtain 10.7g of a tan solid intermediate 4, which is used in the next step without purification, with a yield of 61.02%.
(5) Preparation of intermediate 5
Figure BDA0002689490830000231
Preparation of intermediate 5: adding the crude intermediate 4 (10.5g, 0.030mol), N, N-carbonyldiimidazole (9.8g, 0.060mol) and 120mL of dichloromethane into a 500mL three-neck flask under the protection of nitrogen, keeping the temperature at 15-20 ℃ for 12.0hrs after the replacement of nitrogen is finished, then slowly cooling to-12 to-5 ℃, dropwise adding TiCl4 (22.8g, 0.120mol)/50 mL of dichloromethane solution, keeping the temperature at the temperature for reaction for 6.0hrs after the dropwise addition is finished, and slowly pouring into 300g,6mol/L of dilute hydrochloric acid for quenching. Stirring for 30min, suction filtering, and pulping with acetonitrile to obtain 4.1g of brown yellow solid intermediate 5 with a yield of 41.02%.
(6) Preparation of intermediate 6
Figure BDA0002689490830000232
Preparation of intermediate 6: adding the intermediate 5 (3.3 g, 0.010mol) and 100mL 4-methyl dihydropyran into a 500mL three-necked flask under the protection of nitrogen, replacing the nitrogen, slowly cooling to 0-10 ℃, dropwise adding a 20mL, 0.5mol/L1-naphthyl magnesium bromide/4-methyl dihydropyran solution, preserving the temperature at the temperature for reacting for 1.0hr after dropwise adding, slowly heating to 20-25 ℃, stirring for reacting for 3.0hr, and slowly pouring into 200g,1mol/L diluted hydrochloric acid for quenching. Stirring for 30min, layering, washing with water, and removing solvent by organic phase under reduced pressure to obtain 6.0g brown viscous solid intermediate 6 without purification, with yield of 100%.
(7) Preparation of intermediate 7
Figure BDA0002689490830000241
Preparation of intermediate 7: adding the crude intermediate 6 (6.0 g, 0.01mol) and 120mL of toluene into a 250mL three-neck flask under the protection of nitrogen, slowly dropwise adding trifluoromethanesulfonic acid (3.3 g, 0.022mol) while stirring, slowly heating to 120-130 ℃, keeping the temperature at the temperature for reaction for 5.0hrs, slowly heating to 20-25 ℃, and adding 50g of water to quench and react. Stirring for 30min, layering, washing with water, removing solvent by organic phase vacuum pressure until no fraction is produced, and recrystallizing with THF ethanol to obtain 2.4g of off-white solid intermediate 7 without purification, wherein the yield is 43.39%.
(8) Preparation of Compound H37
Figure BDA0002689490830000242
Preparation of compound H37: in a 100mL three-necked flask, under the protection of nitrogen, the intermediate 7 (2.4g, 4.3mmol), (4- (10-phenylanthen-9-yl) phenyl) boronic acid (1.9g, 5.0mmol), potassium carbonate (1.1g, 8mmol), 10g of water, 30mL of toluene and 10mL of ethanol were added, after nitrogen substitution was completed, palladium acetate (450mg, 0.002mol) and tricyclohexylphosphine (1.12g, 0.004mol) were added, heating was carried out to reflux, the internal temperature was 75-78 ℃, reflux incubation was carried out for 6.0hrs, TLC tracing reaction was completed, cooling was carried out to room temperature, delamination, drying over anhydrous sodium sulfate as an organic phase, passing through a silica gel column, removing the solvent under reduced pressure to no fraction, and recrystallizing with THF ethanol to obtain 2.6g of H37, with a yield of 70.84%.
Further carrying out sublimation purification on the crude product at 360 ℃ in a chemical vapor deposition system to obtain 2.0g of the crude productWhite solid powder. HR-MS was used to identify this compound, formula C 66 H 38 O, detection value [ M]+ =846.2920, calculated 846.2923.
1 H NMR(400MHz，CDCl3)δ(ppm)：8.218～8.235ppm(dd,1H)，8.173～8.191ppm(dd,1H)，8.051～8.253ppm(m,4H)，7.543～7.782ppm(m,6H)，7.221～7.429(m,26H)。
Organic photoelectric materials (compounds H01 to H54) were prepared according to the methods described in embodiments 1 to 4 of compound sample preparation.
The compound of the invention is used as a material of a luminescent layer in a luminescent device. The compounds of the invention H03, H13, H21, H28, H37 and the prior art BH1 were tested for thermal properties and the results are shown in Table 1.
TABLE 1 thermal stability test
Figure BDA0002689490830000251
Note: the glass transition temperature Tg is determined by differential scanning calorimetry (DSC, DSC204F1 differential scanning calorimeter of Germany Chi-resistant company), and the heating rate is 10 ℃/min; the thermogravimetric loss temperature Td is a temperature at which the weight loss is 5% in a nitrogen atmosphere, and is measured on a TGA-50H thermogravimetric analyzer of Shimadzu corporation, japan, and the nitrogen flow rate is 20mL/min; the highest occupied molecular orbital HOMO level and the lowest occupied molecular orbital LUMO level were calculated from photoelectron emission spectroscopy (AC-2 type PESA) and ultraviolet spectrophotometer (UV) tests, which were conducted in an atmospheric environment.
From the data in the table, the compound provided by the invention has suitable HOMO and LUMO energy levels and is suitable to be used as a blue light host material in an OLED device; in the table above, the compound provided by the invention has higher thermal stability, so that the service life of the manufactured OLED device containing the compound provided by the invention is prolonged.
The embodiment provides the preparation method of part of the compounds of the organic electroluminescent material provided in the first embodiment, the compound obtained by the preparation method provided in the first embodiment has a rigid 3D spatial structure, and has the characteristics of difficult crystallization, difficult aggregation and good film forming property among molecules, and the rigid group in the molecule can improve the thermal stability of the material; the compound can be used as a main material of a luminescent layer of an OLED luminescent device, so that the distribution of electrons and holes in the luminescent layer is more balanced, the exciton utilization rate and the high fluorescence radiation efficiency can be effectively improved, the efficiency roll-off under high current density is reduced, the voltage of the device is reduced, the current efficiency of the device is improved, and the service life of the device is prolonged.
EXAMPLE two preparation of organic electroluminescent device (hereinafter referred to as device)
Device example 1
The preparation process comprises the following steps:
as shown in fig. 1, the transparent substrate layer 1 is a transparent PI film, and the ITO (15 nm)/Ag (150 nm)/ITO (15 nm) anode layer 2 is washed, i.e., sequentially washed with alkali, washed with pure water, dried, and then washed with ultraviolet-ozone to remove organic residues on the surface of the anode layer. On the anode layer 2 after the above washing, HT-1 and P-1 were deposited by a vacuum deposition apparatus to a film thickness of 10nm as the hole injection layer 3, and the mass ratio of HT-1 to P-1 was 97. HT-1 was then evaporated to a thickness of 55nm as the hole transport layer 4. EB-1 was then evaporated to a thickness of 10nm as an electron blocking layer 5. After the evaporation of the electron blocking material is finished, the light emitting layer 6 of the OLED light emitting device is manufactured, and the structure of the OLED light emitting device comprises that the OLED light emitting layer 6 uses a compound H03 as a main material, BD-1 as a doping material, the doping proportion of the doping material is 3% by weight, and the thickness of the light emitting layer is 20nm. After the light-emitting layer 6, ET-1 and Liq were continuously vacuum-evaporated, the mass ratio of ET-1 to Liq was 1, the film thickness was 35nm, and this layer was a hole-blocking/electron-transporting layer 7. On the hole-blocking/electron-transporting layer 7, a Yb layer having a film thickness of 1nm, which is an electron-injecting layer 8, was formed by a vacuum evaporation apparatus. On the electron injection layer 8, a vacuum deposition apparatus was used to produce a 15 nm-thick Mg: the Ag electrode layer has the mass ratio of Mg to Ag of 1; then, CPL-1 of 80nm was deposited as a light extraction layer 10.
After the electroluminescent device was fabricated according to the above procedure, I-V-L data of the device was measured using FS-1000GA4 test equipment, foster science instruments, suzhou, and the lifetime of the device was measured using EAS-62C test equipment, japan SYSTEM research, inc., and the results are shown in Table 2. The molecular structural formula of the related material is shown as follows:
Figure BDA0002689490830000261
device example 2
This embodiment differs from device embodiment 1 in that: the compound H13 provided by the invention is used for preparing a main material of a light-emitting layer of an organic electroluminescent device.
Device example 3
This embodiment differs from device embodiment 1 in that: the compound H21 provided by the invention is used as the main material of the light-emitting layer of the prepared organic electroluminescent device.
Device example 4
This embodiment differs from device embodiment 1 in that: the compound H28 provided by the invention is used as the main material of the light-emitting layer of the prepared organic electroluminescent device.
Device example 5
This embodiment differs from device embodiment 1 in that: the compound H37 provided by the invention is used as the main material of the light-emitting layer of the prepared organic electroluminescent device.
Device comparative example 1
Device comparative example 1 differs from device example 1 in that: the main material of the light-emitting layer of the organic electroluminescent device is BH1.
The results of the tests on device examples 1 to 5 and device comparative example 1 are shown in table 2 below:
TABLE 2
Figure BDA0002689490830000271
From the analysis in the above table 2, it can be seen that, in the device prepared by applying the organic photoelectric material provided by the present invention, the driving voltage, the current efficiency and the lifetime are greatly improved compared with those of the known OLED material, and particularly, the driving lifetime of the device is greatly improved.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present patent should be subject to the appended claims.

Claims (4)

1. The organic photoelectric material containing the butterfly structure is characterized by being specifically any one of the following H01-H54 compounds:
Figure FDA0004034709910000011
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Figure FDA0004034709910000021
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Figure FDA0004034709910000031
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Figure FDA0004034709910000041
2. the preparation method of the organic photoelectric material containing the butterfly structure according to claim 1, characterized by comprising the following steps:
(1) Under the protection of inert gas, adding p-chlorophenol, titanium tetrachloride and an organic solvent into a reaction system, slowly adding ethoxy oxalyl chloride at the temperature of-20-50 ℃, keeping the temperature and stirring for 1-8.0 hrs, pouring into dilute hydrochloric acid after the reaction is finished, and quenching to obtain a reaction system containing an intermediate 1, wherein the organic solvent is selected from one or more of dichloromethane, chloroform and dichloroethane, the intermediate 1 is shown as the following formula 1, and X is selected from chlorine atoms;
Figure FDA0004034709910000042
(2) Adding the intermediate 1 obtained in the step (1) and a basic substance into an organic solvent, and adding trifluoromethanesulfonyl chloride to react for 1-12.0 hrs at-10-60 ℃ under the protection of inert gas to obtain a reaction system containing the intermediate 2, wherein the basic substance is selected from one or more of triethylamine, diisopropylethylamine, pyridine and N, N-dimethylpyridine-4-amine, the organic solvent is selected from one or more of dichloromethane, trichloromethane, dichloroethane or toluene, the intermediate 2 is represented by the following formula 2, and X is selected from chlorine atoms;
Figure FDA0004034709910000043
(3) Adding the intermediate 2 obtained in the step (2), the raw material 2 and a basic substance into an organic solvent, adding a catalyst into the system under the protection of inert gas, and reacting at 60-150 ℃ for 3-12.0 hrs to obtain a reaction system containing the intermediate 3, wherein the basic substance is one or more of potassium carbonate, sodium carbonate, potassium phosphate and potassium hydroxide, the catalyst is a palladium-containing catalyst and an organic phosphine ligand, and the palladium-containing catalyst is Pd (OAc) 2 、Pd(PPh 3 ) 4 、Pd(PPh 3 ) 2 Cl 2 And Pd (dppf) Cl 2 The organic phosphine ligand is one or more of triphenylphosphine, DPPP, xantphos, sphos and P (t-Bu) 3 ·HBF 4 The raw material 2 is shown as the following formula 3, the intermediate 3 is shown as the following formula 4, wherein Y is selected from hydrogen, chlorine or bromine atoms;
Figure FDA0004034709910000051
(4) Adding the intermediate 3 obtained in the step (3) and an alkaline substance into an organic solvent, and reacting for 1-12.0 hrs at 60-150 ℃ under the protection of inert gas to obtain a reaction system containing an intermediate 4, wherein the alkaline substance is one or more selected from potassium hydroxide, sodium hydroxide and sodium ethoxide, and the intermediate 4 is shown as the following formula 5;
Figure FDA0004034709910000052
(5) Adding the intermediate 4 obtained in the step (4) and N, N-carbonyl diimidazole into an organic solvent, and reacting for 1-24.0 hrs at-20-60 ℃ under the protection of inert gas; then at the temperature of minus 20 to 60 ℃, adding titanium tetrachloride, keeping the temperature for reaction for 1 to 12.0hrs, pouring into dilute hydrochloric acid for quenching to obtain a reaction system containing an intermediate 5, wherein the organic solvent is selected from one or more of dichloromethane, dichloroethane and chloroform, and the intermediate 5 is shown as the following formula 6;
Figure FDA0004034709910000053
Figure FDA0004034709910000061
(6) Adding the intermediate 5 obtained in the step (5) into an organic solvent, adding 1-naphthyl magnesium bromide/4-methyl dihydropyran solution at the temperature of-20-60 ℃ under the protection of inert gas, and reacting for 1-24.0 hrs at the temperature of-20-60 ℃; then pouring into diluted hydrochloric acid for quenching to obtain a reaction system containing an intermediate 6, wherein the organic solvent is selected from one or more of THF and 4-methyl dihydropyran, and the intermediate 6 is shown as the following formula 7;
Figure FDA0004034709910000062
(7) Adding the intermediate 6 obtained in the step (6) into an organic solvent, adding trifluoromethanesulfonic acid under the protection of inert gas, and reacting at 30-150 ℃ for 1-24.0 hrs to obtain a reaction system containing an intermediate 7, wherein the organic solvent is selected from one or more of toluene and xylene, and the intermediate 7 is represented by the following formula 8;
Figure FDA0004034709910000063
(8) Adding the intermediate 7 obtained in the step (7), polycyclic conjugated aromatic boric acid, a basic substance and a reaction solvent into a reaction system under the protection of inert gas, adding a catalyst into the system, and reacting at 60-150 ℃ for 3-12.0 hrs to obtain the reaction system containing the organic photoelectric material with the butterfly structure, wherein the basic substance is one or more of potassium carbonate, sodium carbonate, potassium phosphate and potassium hydroxide, the catalyst is a palladium-containing catalyst and an organic phosphine ligand, and the palladium-containing catalyst is Pd (OAc) 2 、Pd(PPh 3 ) 4 、Pd(PPh 3 ) 2 Cl 2 And Pd (dppf) Cl 2 The organic phosphine ligand is one or more of triphenylphosphine, DPPP, xantphos, sphos, P (t-Bu) 3 ·HBF 4 One or more of them are mixed.
3. The method for preparing an organic photoelectric material containing a butterfly structure according to claim 2, wherein:
in the step (1), the organic solvent is selected from dichloromethane, chloroform or dichloroethane, and the molar ratio of the dosage of the p-chlorophenol to the dosage of the titanium tetrachloride is p-chlorophenol: titanium tetrachloride =1: 1.0-1.5, the molar ratio of the dosage of the p-chlorophenol to the dosage of the ethoxy oxalyl chloride is that the p-chlorophenol: ethoxy oxalyl chloride =1:1.0 to 1.5;
in the step (2), the organic solvent is selected from dichloromethane, chloroform, dichloroethane or toluene, the basic substance is selected from triethylamine, diisopropylethylamine, pyridine and N, N-dimethylpyridine-4-amine, and the molar ratio of the amount of the intermediate 1 to the amount of the basic substance is that the intermediate 1: basic substance =1.0: 1.0-1.5, wherein the molar ratio of the dosage of the intermediate 1 to the dosage of the trifluoromethanesulfonyl chloride is that the intermediate 1: trifluoromethanesulfonyl chloride =1:1.0 to 1.5;
in the step (3), the organic solvent is selected from tetrahydrofuran, dioxane, toluene, xylene or trimethylbenzene, and the molar ratio of the amount of the intermediate 2 to the amount of the raw material 2 is that the intermediate 2: raw material 2=1: 1.0-1.2, wherein the molar ratio of the using amount of the intermediate 2 to the using amount of the alkaline substance is that the intermediate 2: basic substance =1: 1.0-3.0, wherein the molar ratio of the using amount of the intermediate 2 to the using amount of the catalyst is that the intermediate 2: catalyst =1: 0.001-0.1, wherein the molar ratio of the dosage of the palladium catalyst to the dosage of the phosphine ligand is that the palladium catalyst: phosphine ligand =1:0.5 to 4;
in the step (4), the organic solvent is selected from methanol, ethanol or isopropanol, and the molar ratio of the amount of the intermediate 3 to the amount of the alkaline substance is that the intermediate 3: basic substance =1:1.0 to 2.0;
in step (5), the organic solvent is selected from dichloromethane, dichloroethane or chloroform, and the molar ratio of the amount of the intermediate 4 to the amount of the N, N-carbonyldiimidazole is intermediate 4: n, N-carbonyldiimidazole =1: 1.5-3.0, wherein the molar ratio of the using amount of the intermediate 4 to the using amount of the titanium tetrachloride is that the intermediate 4: titanium tetrachloride =1:3.0 to 5.0;
in step (6), the organic solvent is selected from THF or 4-methyl dihydropyran, and the molar ratio of the amount of the intermediate 5 to the amount of the 1-naphthyl magnesium bromide is intermediate 5: 1-naphthyl magnesium bromide =1:2.0 to 2.2;
in step (7), the organic solvent is selected from toluene or xylene, and the molar ratio of the amount of the intermediate 6 to the amount of the trifluoromethanesulfonic acid is intermediate 6: trifluoromethanesulfonic acid =1:2.0 to 3.0;
in the step (8), the organic solvent is selected from tetrahydrofuran, dioxane, toluene, xylene or trimethylbenzene, and the molar ratio of the amount of the intermediate 7 to the amount of the polycyclic conjugated aromatic hydrocarbon boric acid is that the intermediate 7: polycyclic conjugated arene boronic acid =1: 1.0-1.2, wherein the molar ratio of the using amount of the intermediate 7 to the using amount of the alkaline substance is that the intermediate 7: basic substance =1: 1.0-3.0, wherein the molar ratio of the using amount of the intermediate 7 to the using amount of the catalyst is that the intermediate 7: catalyst =1: 0.001-0.1, wherein the molar ratio of the dosage of the palladium catalyst to the dosage of the phosphine ligand is that the palladium catalyst: phosphine ligand =1:0.5 to 4.
4. Use of the organic photoelectric material comprising a butterfly structure according to claim 1, wherein the organic photoelectric material is used in an OLED, and the organic photoelectric material according to claim 1 is used in a light emitting layer of the OLED.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009133917A1 (en) * 2008-04-30 2009-11-05 出光興産株式会社 Anthracene derivative and organic electroluminescent element using the same
CN109020979A (en) * 2018-10-11 2018-12-18 中节能万润股份有限公司 A kind of electroluminescent organic material and preparation method and application with heterocycle structure

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009133917A1 (en) * 2008-04-30 2009-11-05 出光興産株式会社 Anthracene derivative and organic electroluminescent element using the same
CN109020979A (en) * 2018-10-11 2018-12-18 中节能万润股份有限公司 A kind of electroluminescent organic material and preparation method and application with heterocycle structure

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