A phenanthrene-containing organic electroluminescent material, a preparation method, application and light-emitting device thereof

Abstract

The application relates to a phenanthrene-containing organic electroluminescent material and a preparation method, application and light-emitting device thereof. The phenanthrene-containing organic electroluminescent material provided by the application takes phenanthrenebenzofuran and anthracene as basic structural units, can be used as a host material of a blue fluorescent light-emitting layer, has a high glass transition temperature, high quantum efficiency, good electron transmission capacity, good film-forming property and stable property, shows high light-emitting efficiency and stability in a blue light-emitting device, and is an ideal blue fluorescent material.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic optoelectronic material application, and particularly relates to a phenanthrene-containing organic electroluminescent material, a preparation method and application thereof, and a light-emitting device. BACKGROUND

[0002] With the development of science and technology, the living standards of modern people have changed rapidly, and the requirements for display technology are also constantly improving. In the prior art, OLED technology has the advantages of high contrast, flexibility, wide viewing angle, fast response speed and the like. This makes OLED technology have the potential to replace traditional display technology.

[0003] The existing organic electroluminescent device generally comprises, from top to bottom, a cathode, an electron injection layer, an electron transport layer, an organic light-emitting layer, a hole transport layer, a hole injection layer, an anode and a substrate. In OLED materials, in order to realize full-color display of OLED, blue light material as one of the three primary colors can realize efficient and stable blue light emission, and as a host material, green light and red light can be obtained through energy transfer.

[0004] The device prepared from the existing material has a short service life and low efficiency, and cannot meet the needs of market development. Therefore, how to provide a host material for an organic electroluminescent device with high efficiency and long service life has become a problem to be solved. SUMMARY

[0005] Therefore, in view of the current technical deficiencies, the purpose of the present application is to provide a phenanthrene-containing organic electroluminescent material, a preparation method and application thereof, and a light-emitting device. The phenanthrene-containing organic electroluminescent material takes phenanthrene benzofuran and anthracene as basic structural units, can promote intermolecular charge transition, has high light-thermal stability, and can realize rapid electron flow, and is an ideal blue fluorescent material.

[0006] The phenanthrene-containing organic electroluminescent material provided by the present application has the structure shown in the following formula:

[0007]

[0008] wherein Ar is selected from aromatic groups with 6 to 18 ring carbons.

[0009] As a further improvement of the above-mentioned scheme of the present application, Ar is selected from deuterium-containing aromatic groups with 6 to 18 ring carbons.

[0010] As a further improvement of the above-mentioned scheme of the present application, Ar is selected from deuterium-free aromatic groups with 6 to 18 ring carbons.

[0011] As a further improvement of the above-mentioned scheme of the present application, Ar is selected from

[0012] As a further improvement of the above-mentioned scheme of the present application, it is one of the compounds represented by the following structural formula:

[0013]

[0014]

[0015]

[0016]

[0017] The present application provides a method for preparing the phenanthrene-containing organic electroluminescent material as described above, and the synthetic route is as follows:

[0018]

[0019] Wherein, Ar is selected from aromatic groups with 6 to 18 carbon atoms in the ring.

[0020] As a further improvement of the above-mentioned scheme of the present application, the preparation method of the compound A is as follows: 1-bromo-4-chloro-2-fluorobenzene is added with n-butyllithium to remove bromine, then reacted with tri-n-butyl borate to obtain product one; product one is added with 2-bromo-3-methoxyphenanthrene and acetic acid palladium to obtain product two; product two is dissolved in DCM and added with BBr3 to remove methyl to obtain product three; product three is dissolved in NMP and added with potassium carbonate to cyclize to obtain product four; product four is reacted with pinacol diboron to obtain compound A.

[0021] As a further improvement of the above-mentioned scheme of the present application, the preparation method of the compound B is as follows: o-fluoro nitrobenzene is reacted with p-bromoaniline to obtain product 1; product 1 is reduced with sodium hyposulfite to obtain product 2; aromatic ethanone is reacted with sodium sulfite to obtain product 3; product 2 is reacted with product 3 to obtain product 4; product 4 is reacted with pinacol diboron to obtain compound B.

[0022] The present application provides the use of the phenanthrene-containing organic electroluminescent material as described above in an organic electroluminescent device.

[0023] The present application provides an organic electroluminescent device, which comprises an organic light-emitting layer made of the phenanthrene-containing organic electroluminescent material as described above.

[0024] Compared with the prior art, the present application has the following beneficial effects:

[0025] The present invention provides a phenanthrene-containing organic electroluminescent material with phenanthrenebenzofuran and anthracene as basic structural units. It can promote charge transition between molecules, has high photothermal stability, and can achieve rapid electron flow. When used as the main material of a blue fluorescent light-emitting layer, it has a high glass transition temperature, high quantum efficiency, good electron transmission ability, good film-forming properties and stable properties. In blue light devices, it exhibits high luminous efficiency and stability, and is an ideal blue fluorescent material.

[0026] The present invention provides a method for preparing a phenanthrene-containing organic electroluminescent material, which has simple specific operations, a safe reaction process, and is convenient for scale-up production. The present invention applies the above-mentioned organic electroluminescent compound to prepare an organic electroluminescent device, which can increase the service life of the organic electroluminescent device, and exhibits a relatively low driving voltage, excellent luminous efficiency and high-purity color. DETAILED DESCRIPTION

[0027] To facilitate understanding of the present invention, the present invention will be described more fully below in conjunction with specific embodiments. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to provide a more thorough and comprehensive understanding of the disclosure of the present invention.

[0028] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used in the specification of the present invention herein are only for the purpose of describing specific embodiments and are not intended to limit the present invention.

[0029] Implementation Case 1

[0030] This embodiment proposes a phenanthrene-containing luminescent material, whose structural formula is

[0031]

[0032] The preparation method of compound 4 comprises the following steps:

[0033] (1) Preparation of Compound A:

[0034] Step 1: 1-Bromo-4-chloro-2-fluorobenzene (400 mmol, 1.0 eq) was dissolved in tetrahydrofuran (800 ml, 10 v / w) and bromine was removed by adding n-butyl lithium (520 mmol, 1.3 eq). The product was then reacted with tri-n-butyl borate (600 mmol, 1.5 eq) and acidified to obtain 59.3 g of product I in a yield of 85%.

[0035] Step 2: Reflux product I (330 mmol, 1.1 eq) with 2-bromo-3-methoxyphenanthrene (300 mmol, 1.0 eq), palladium acetate (0.005 eq), toluene (600 ml, 7 v / w), ethanol (85 ml, v / w), and water (260 ml, 3 v / w) to obtain 86.9 g of product II after purification, with a yield of 86%;

[0036] Step 3: Product II (86.9 g, 258 mmol) was dissolved in DCM (435 ml, 5 V / W), and boron tribromide (335 mmol, 1.3 eq) was added dropwise under ice bath for demethylation. The reaction was continued under ice bath for 1 h, and post-treatment was performed to obtain 83.3 g of product III, with a yield of 100%;

[0037] Step 4: Dissolve product III (83.3 g, 258 mmol) in NMP (417 ml, 5 V / W), add potassium carbonate (387 mmol, 1.5 eq) and react at 170-180°C for 1 h. Concentrate to remove most of the NMP, add water to precipitate the product, filter and dry to obtain 74.2 g of product IV, with a yield of 95%;

[0038] Step 5: Product IV (74.2 g, 245 mmol, 1.0 eq), pinacol diboron (319 mmol, 1.3 eq), potassium acetate (490 mmol, 2 eq), Pd2(dba)3 (0.005 eq), X-phos (0.01 eq) and 1,4-dioxane (600 ml, 8 v / w) were refluxed for 2 h, and post-processed and purified to obtain 86.9 g of compound A, with a yield of 90%;

[0039]

[0040] (2) Preparation of compound B:

[0041] Step 1: o-Fluoronitrobenzene (400 mmol) and p-bromoaniline (400 mmol) were dissolved in 400 ml of THF. Sodium tert-butoxide (600 mol) was added in batches. After the addition was complete, the mixture was refluxed for 3 h. After quenching with water, the mixture was recrystallized from toluene to obtain 59.8 g of the product with a yield of 51%.

[0042] Step 2: Add the product obtained in step 1 (59.8 g, 204 mmol), 300 ml of ethanol, 300 ml of water, and sodium dithionite (306 mmol) into a reaction flask, reflux for 2 h, filter, and wash with water to obtain 53.7 g of the product, with a yield of 100%;

[0043] Step 3: Add 400 mmol of acetophenone, 1.2 mol of sodium sulfite, 48 ml of ethanol, and 240 ml of water to a reaction flask, stir at room temperature for 2 h, filter and wash with water to obtain 77.3 g of solid, with a yield of 92%;

[0044] Step 4, Put the product from Step 2 (52.4g, 200mmol) and the product from Step 3 (58.9g, 280mmol) into 400ml DMF, react at 130°C for 1h, pour the reaction into water, filter, dry in oven, then dissolve in toluene, pass through column, concentrate, and crystallize to get 60.8g, yield 87%;

[0045] Step 5, Put the product from Step 4 (60.8g, 174mmol), bis(pinacolato)diboron (209mmol), potassium acetate (350mmol), Pd(dppf)Cl2(0.87mmol), 500ml 1,4-dioxane, reflux for 2h, remove most of 1,4-dioxane by concentration, dissolve in dichloromethane, pass through column, concentrate, add petroleum ether to crystallize, filter and dry to get 59.3g white solid, which is compound B, yield 86%;

[0046]

[0047] (3) Put 200mmol 9-bromanthracene, 210mmol compound A, 400mmol potassium carbonate, 2mmol palladium acetate, 400ml toluene, 50ml ethanol, 150ml water into a reaction bottle, replace with nitrogen, heat to reflux for 4-8h, stop the reaction when 9-bromanthracene is consumed. Cool to room temperature, filter, wash the filter cake with water until neutral, dry in air blast, dissolve in toluene, pass through silica gel column, concentrate the column liquid, crystallize, filter, and dry to get 72.0g yellow-green solid S1, yield 81% (calculated based on 9-bromanthracene);

[0048] (4) Put 150mmol yellow-green solid S1, 160mmol NBS, 670ml tetrahydrofuran into a reaction bottle, reflux for 2h, stop the reaction, cool to room temperature, quench with a small amount of sodium bisulfite aqueous solution, concentrate, crystallize, filter the obtained solid, slurry with ethanol, and dry to get 78.5g white-like solid S2, yield 100% (calculated based on yellow-green solid S1);

[0049] (5) Put 100mmol white-like solid S2, 110mmol compound B, 200mmol potassium carbonate, 0.5mmol palladium acetate into a reaction bottle, add 400ml toluene, 50ml ethanol, 150ml water, replace with nitrogen, reflux for 2-4h, stop the reaction, cool the reaction to room temperature, add water, filter, wash with water, slurry the obtained solid with ethanol, filter and dry, dissolve in toluene, pass through column, concentrate, crystallize, filter and dry to get 36.4g yellow-green compound 4, yield 51% (calculated based on white-like solid S2).

[0050] The reaction scheme is:

[0051]

[0052] Implementation Case 2

[0053] This embodiment proposes a phenanthrene-containing luminescent material, whose structural formula is

[0054]

[0055] The preparation method of compound 7 comprises the following steps:

[0056] (1) Preparation of Compound A:

[0057] Step 1: 1-Bromo-5-chloro-2-fluorobenzene (400 mmol, 1.0 eq) was dissolved in tetrahydrofuran (800 ml, 10 v / w) and bromine was removed by adding n-butyl lithium (520 mmol, 1.3 eq). The product was then reacted with tri-n-butyl borate (600 mmol, 1.5 eq) and acidified to obtain 60 g of product I in a yield of 86%.

[0058] Step 2: Reflux product I (330 mmol, 1.1 eq) with 2-bromo-3-methoxyphenanthrene (300 mmol, 1.0 eq), palladium acetate (0.005 eq), toluene (600 ml, 7 v / w), ethanol (85 ml, v / w), and water (260 ml, 3 v / w) to obtain 83.9 g of product II after purification, with a yield of 83%;

[0059] Step 3: Product II (83.9 g, 249 mmol) was dissolved in DCM (420 ml, 5 V / W), and boron tribromide (324 mmol, 1.3 eq) was added dropwise under ice bath for demethylation. The reaction was continued under ice bath for 1 h, and post-treatment was performed to obtain 80.4 g of product III, with a yield of 100%;

[0060] Step 4: Dissolve product III (80.4 g, 249 mmol) in NMP (400 ml, 5 V / W), add potassium carbonate (374 mmol, 1.5 eq) and react at 170-180°C for 1 h. Concentrate to remove most of the NMP, add water to precipitate the product, filter and dry to obtain 72.4 g of product IV, with a yield of 96%;

[0061] Step 5: Product IV (72.4 g, 239 mmol, 1.0 eq), pinacol diboron (311 mmol, 1.3 eq), potassium acetate (478 mmol, 2 eq), Pd2(dba)3 (0.005 eq), X-phos (0.01 eq) and 1,4-dioxane (580 ml, 8 v / w) were refluxed for 2 h, and post-processed and purified to obtain 83.8 g of compound A, with a yield of 89%;

[0062]

[0063] (2) Preparation of compound B:

[0064] Step 1, o-fluoronitrobenzene (400 mmol) and p-bromoaniline (400 mmol) were dissolved in THF 400 ml, after adding sodium tert-butoxide (600 mol) portionwise, the reaction was refluxed for 3 h, after quenching with water, the product was recrystallized from toluene to obtain 59.8 g of product with a yield of 51 %;

[0065] Step 2, the obtained product (59.8 g, 204 mmol), ethanol 300 ml, water 300 ml, and sodium hydrosulfite (306 mmol) were added to the reaction bottle, and the reaction was refluxed for 2 h, then the product was obtained by filtration and water washing with a yield of 100 %;

[0066] Step 3, phenylacetone 400 mmol, sodium sulfite 1.2 mol, ethanol 48 ml, and water 240 ml were added to the reaction bottle, and the mixture was stirred at room temperature for 2 h, then the product was obtained by filtration and water washing with a yield of 92 %;

[0067] Step 4, the product obtained in step 2 (52.4 g, 200 mmol) and the product obtained in step 3 (58.9 g, 280 mmol) were added to DMF 400 ml, and the mixture was reacted at 130 °C for 1 h, then the reaction liquid was poured into water, and the product was obtained by filtration, drying, dissolving in toluene, column chromatography, concentration, and crystallization to obtain 60.8 g of product with a yield of 87 %;

[0068] Step 5, the product obtained in step 4 (60.8 g, 174 mmol), pinacol diboronic acid (209 mmol), potassium acetate (350 mmol), Pd(dppf)Cl2(0.87 mmol), 1,4-dioxane 500 ml, refluxed for 2 h, most of the 1,4-dioxane was removed by concentration, the residue was dissolved in dichloromethane, column chromatography was performed, and the product was obtained by concentration, petroleum ether crystallization, filtration, and drying to obtain 59.3 g of white solid, which was compound B with a yield of 86 %.

[0069]

[0070] (3) 200 mmol of 9-bromoanthracene, 210 mmol of compound A, 400 mmol of potassium carbonate, 2 mmol of palladium acetate, 400 ml of toluene, 50 ml of ethanol, and 150 ml of water were added to a reaction bottle, nitrogen was replaced, the temperature was raised to reflux, the reaction was carried out for 4-8 h, the reaction was stopped when the 9-bromoanthracene raw material was consumed, the temperature was lowered to room temperature, the mixture was filtered, the filter cake was washed with water until neutral, and then dried by blowing air, the product was obtained by dissolving in toluene, column chromatography, concentration, crystallization, filtration, and drying to obtain 72.0 g of yellow-green solid S1 with a yield of 81 % (calculated based on 9-bromoanthracene);

[0071] (4) Add 150 mmol of yellow-green solid S1, 160 mmol of NBS, and 670 ml of tetrahydrofuran to the reaction flask, reflux for 2 h, stop the reaction, cool to room temperature, add a small amount of sodium bisulfite aqueous solution to quench, concentrate, crystallize, filter the obtained solid, beat with ethanol, and dry to obtain 78.5 g of off-white solid S2, with a yield of 100% (based on the yellow-green solid S1);

[0072] (5) Add 100 mmol of off-white solid S2, 110 mmol of compound B, 200 mmol of potassium carbonate, 0.5 mmol of palladium acetate, and add 400 ml of toluene, 50 ml of ethanol, and 150 ml of water to the reaction flask, replace with nitrogen, reflux for 2-4 hours, stop the reaction, cool the reactant to room temperature, add water, filter, and wash with water. The obtained solid is slurried with ethanol, filtered and dried, dissolved in toluene, passed through a column, concentrated, crystallized, filtered and dried to obtain 36.4 g of yellow-green compound 4, with a yield of 51% (based on the off-white solid S2).

[0073] The reaction process is:

[0074]

[0075] Implementation Case 3

[0076] This embodiment proposes a phenanthrene-containing luminescent material, whose structural formula is

[0077]

[0078] The preparation method of compound 10 comprises the following steps:

[0079] (1) Preparation of Compound A:

[0080] Step 1: 1-Bromo-6-chloro-2-fluorobenzene (400 mmol, 1.0 eq) was dissolved in tetrahydrofuran (800 ml, 10 v / w) and bromine was removed by adding n-butyl lithium (520 mmol, 1.3 eq). The product was then reacted with tri-n-butyl borate (600 mmol, 1.5 eq) and acidified to obtain 60.7 g of product I in a yield of 87%.

[0081] Step 2: Reflux product I (330 mmol, 1.1 eq) with 2-bromo-3-methoxyphenanthrene (300 mmol, 1.0 eq), palladium acetate (0.005 eq), toluene (600 ml, 7 v / w), ethanol (85 ml, v / w), and water (260 ml, 3 v / w) to obtain 75.8 g of product II after purification, with a yield of 75%;

[0082] Step 3: Product II (75.8 g, 225 mmol) was dissolved in DCM (435 ml, 5 V / W), and boron tribromide (335 mmol, 1.3 eq) was added dropwise under ice bath for demethylation. The reaction was continued under ice bath for 1 h, and post-treatment was performed to obtain 72.6 g of product III, with a yield of 100%;

[0083] Step 4: Dissolve product III (72.6 g, 225 mmol) in NMP (360 ml, 5 V / W), add potassium carbonate (338 mmol, 1.5 eq) and react at 170-180°C for 1 h. Concentrate to remove most of the NMP, add water to precipitate the product, filter and dry to obtain 65.4 g of product IV, with a yield of 96%;

[0084] Step 5: Product IV (65.4 g, 216 mmol, 1.0 eq), pinacol diboron (281 mmol, 1.3 eq), potassium acetate (432 mmol, 2 eq), Pd2(dba)3 (0.005 eq), X-phos (0.01 eq) and 1,4-dioxane (525 ml, 8 v / w) were refluxed for 2 h, and post-processed and purified to obtain 76.6 g of compound A in a yield of 90%;

[0085]

[0086] (2) Preparation of compound B:

[0087] Step 1: o-Fluoronitrobenzene (400 mmol) and p-bromoaniline (400 mmol) were dissolved in 400 ml of THF. Sodium tert-butoxide (600 mol) was added in batches. After the addition was completed, the mixture was refluxed for 3 h. After quenching with water, the mixture was recrystallized from toluene to obtain 59.8 g of the product with a yield of 51%.

[0088] Step 2: Add the product obtained in step 1 (59.8 g, 204 mmol), 300 ml of ethanol, 300 ml of water, and sodium dithionite (306 mmol) to a reaction flask, reflux for 2 h, filter, and wash with water to obtain 53.7 g of the product, with a yield of 100%;

[0089] Step 3: Add 400 mmol of acetophenone, 1.2 mol of sodium sulfite, 48 ml of ethanol, and 240 ml of water to a reaction flask, stir at room temperature for 2 h, filter, and wash with water to obtain 77.3 g of solid, with a yield of 92%;

[0090] Step 4: The product obtained in step 2 (52.4 g, 200 mmol) and the product obtained in step 3 (58.9 g, 280 mmol) were added to 400 ml of DMF and reacted at 130°C for 1 h. The reaction solution was poured into water, filtered, dried, dissolved in toluene, and concentrated by column to obtain 60.8 g, with a yield of 87%.

[0091] Step 5, add the product from Step 4 (60.8 g, 174 mmol), bis(pinacolato)diboron (209 mmol), potassium acetate (350 mmol), Pd(dppf)Cl2(0.87 mmol), 1,4-dioxane 500 ml, reflux for 2 h, concentrate to remove most of the 1,4-dioxane, dissolve in dichloromethane, concentrate to a large amount of solid, add petroleum ether to crystallize, filter and dry to obtain 59.3 g of white solid, which is compound B, yield 86%

[0092]

[0093] (3) In a reaction bottle, add 200 mmol of 9-bromoanthracene, 210 mmol of compound A, 400 mmol of potassium carbonate, 2 mmol of palladium acetate, 400 ml of toluene, 50 ml of ethanol, and 150 ml of water, replace with nitrogen, and heat to reflux for 4-8 h until the 9-bromoanthracene raw material is completely reacted. Stop the reaction. Cool to room temperature, filter, add water to the filter cake until it is neutral, and dry in a blast oven. Dissolve in toluene and pass through a silica gel column. Concentrate the column eluate, crystallize, filter, and dry to obtain 72.0 g of yellow-green solid S1, yield 81% (calculated based on 9-bromoanthracene);

[0094] (4) In a reaction bottle, add 150 mmol of yellow-green solid S1, 160 mmol of NBS, and 670 ml of tetrahydrofuran, and reflux for 2 h. Stop the reaction, cool to room temperature, add a small amount of sodium bisulfite aqueous solution to quench, concentrate, crystallize, and filter the obtained solid. Slurry the solid with ethanol and dry to obtain 78.5 g of white solid S2, yield 100% (calculated based on yellow-green solid S1).

[0095] (5) In a reaction bottle, add 100 mmol of white solid S2, 110 mmol of compound B, 200 mmol of potassium carbonate, 0.5 mmol of palladium acetate, and add 400 ml of toluene, 50 ml of ethanol, and 150 ml of water. Replace with nitrogen, reflux for 2-4 h, stop the reaction, cool the reaction to room temperature, add water, filter, wash with water, slurry the obtained solid with ethanol, filter and dry, dissolve in toluene, pass through a column, concentrate, crystallize, filter and dry to obtain 36.4 g of yellow-green compound 4, yield 51% (calculated based on white solid S2).

[0096] The reaction scheme is as follows:

[0097]

[0098] Embodiment 4

[0099] The embodiment provides a phenanthrene-containing luminescent material, and the structural formula is

[0100]

[0101] The preparation method of compound 14 comprises the following steps:

[0102] (1) Preparation of Compound A:

[0103] Step 1: 1-Bromo-4-chloro-2-fluorobenzene (400 mmol, 1.0 eq) was dissolved in tetrahydrofuran (800 ml, 10 v / w) and bromine was removed by adding n-butyl lithium (520 mmol, 1.3 eq). The product was then reacted with tri-n-butyl borate (600 mmol, 1.5 eq) and acidified to obtain 59.3 g of product I in a yield of 85%.

[0104] Step 2: Reflux product I (330 mmol, 1.1 eq) with 2-bromo-3-methoxyphenanthrene (300 mmol, 1.0 eq), palladium acetate (0.005 eq), toluene (600 ml, 7 v / w), ethanol (85 ml, v / w), and water (260 ml, 3 v / w) to obtain 86.9 g of the product after purification with a yield of 86%;

[0105] Step 3: Product II (86.9 g, 258 mmol) was dissolved in DCM (435 ml, 5 V / W), and boron tribromide (335 mmol, 1.3 eq) was added dropwise under ice bath for demethylation. The reaction was continued under ice bath for 1 h, and post-treatment was performed to obtain 83.3 g of product III, with a yield of 100%;

[0106] Step 4: Dissolve product III (83.3 g, 258 mmol) in NMP (417 ml, 5 V / W), add potassium carbonate (387 mmol, 1.5 eq) and react at 170-180°C for 1 h. Concentrate to remove most of the NMP, add water to precipitate the product, filter and dry to obtain 74.2 g of product IV, with a yield of 95%;

[0107] Step 5: Product IV (74.2 g, 245 mmol, 1.0 eq), pinacol diboronate (319 mmol, 1.3 eq), potassium acetate (490 mmol, 2 eq), Pd2(dba)3 (0.005 eq), X-phos (0.01 eq) and 1,4-dioxane (600 ml, 8 v / w) were refluxed for 2 h, and post-processed and purified to obtain 86.9 g of compound A with a yield of 90%;

[0108]

[0109] (2) Preparation of compound B:

[0110] Step 1: o-Fluoronitrobenzene (400 mmol) and p-bromoaniline (400 mmol) were dissolved in 400 ml of THF. Sodium tert-butoxide (600 mol) was added in batches. After the addition was complete, the mixture was refluxed for 3 h. After quenching with water, the mixture was recrystallized from toluene to obtain 59.8 g of the product with a yield of 51%.

[0111] Step 2: Add the product obtained in step 1 (59.8 g, 204 mmol), 300 ml of ethanol, 300 ml of water, and sodium dithionite (306 mmol) into a reaction flask, reflux for 2 h, filter and wash with water to obtain 53.7 g of the product, with a yield of 100%;

[0112] Step 3: Add 400 mmol of deuterated acetophenone, 1.2 mol of sodium sulfite, 50 ml of ethanol, and 250 ml of water to a reaction flask, stir at room temperature for 2 h, filter, and wash with water to obtain 80 g of solid, with a yield of 93%;

[0113] Step 4: The product obtained in step 2 (52.4 g, 200 mmol) and the product obtained in step 3 (60.3 g, 280 mmol) were added to 400 ml of DMF and reacted at 130°C for 1 h. The reaction solution was poured into water, filtered, dried, dissolved in toluene, and concentrated by column to obtain 60.2 g of the product, with a yield of 85%.

[0114] Step 5: The product obtained in step 4 (60.2 g, 170 mmol), bipyralidoborane (204 mmol), potassium acetate (340 mmol), Pd(dppf)Cl2 (0.85 mmol), and 480 ml of 1,4-dioxane were added to a reaction flask and refluxed for 2 h. The mixture was concentrated to remove most of the 1,4-dioxane, dissolved in dichloromethane, and concentrated through a column until a large amount of solid precipitated. Petroleum ether was added for crystallization, and the mixture was filtered and dried to obtain 59.4 g of a white solid, which was compound B, with a yield of 87%;

[0115]

[0116] (3) Add 200 mmol of 9-bromoanthracene, 210 mmol of compound A, 400 mmol of potassium carbonate, 2 mmol of palladium acetate, 400 ml of toluene, 50 ml of ethanol, and 150 ml of water to a reaction flask, replace the atmosphere with nitrogen, and heat to reflux for 4-8 hours. After the reaction of the 9-bromoanthracene raw material is complete, stop the reaction. Cool to room temperature, filter, wash the filter cake with water until neutral, air dry, dissolve the toluene, and pass it through a silica gel column. Concentrate the column liquid, filter, crystallize, and dry to obtain 72.0 g of yellow-green solid S1, with a yield of 81% (calculated based on 9-bromoanthracene).

[0117] (4) Add 150 mmol of yellow-green solid S1, 160 mmol of NBS, and 670 ml of tetrahydrofuran to the reaction flask, reflux for 2 h, stop the reaction, cool to room temperature, add a small amount of sodium bisulfite aqueous solution to quench, concentrate, crystallize, filter the obtained solid, beat with ethanol, and dry to obtain 78.5 g of off-white solid S2, with a yield of 100% (based on the yellow-green solid S1);

[0118] (5) Add 100 mmol of off-white solid S2, 110 mmol of compound B, 200 mmol of potassium carbonate, 0.5 mmol of palladium acetate, and add 400 ml of toluene, 50 ml of ethanol, and 150 ml of water to the reaction flask, replace with nitrogen, reflux for 2-4 hours, stop the reaction, cool the reactant to room temperature, add water, filter, and wash with water. The obtained solid is slurried with ethanol, filtered and dried, dissolved in toluene, passed through a column, concentrated, crystallized, filtered and dried to obtain 36.4 g of yellow-green compound 4, with a yield of 51% (based on the off-white solid S2).

[0119] The reaction process is:

[0120]

[0121] Compound 14 was tested by LCMS, and the data obtained were as follows: ESI-MS: C 53 H 27 D5N2O, standard molecular weight 717.86, test result 7172.35[M+].

[0122] Implementation Case 5

[0123] This embodiment proposes a phenanthrene-containing luminescent material, whose structural formula is

[0124]

[0125] The preparation method of compound 18 comprises the following steps:

[0126] (1) Preparation of Compound A:

[0127] Step 1: 1-Bromo-4-chloro-2-fluorobenzene (400 mmol, 1.0 eq) was dissolved in tetrahydrofuran (800 ml, 10 v / w) and bromine was removed by adding n-butyl lithium (520 mmol, 1.3 eq). The product was then reacted with tri-n-butyl borate (600 mmol, 1.5 eq) and acidified to obtain 59.3 g of product I in a yield of 85%.

[0128] Step 2, product I (330 mmol, 1.1 eq), 2-bromo-3-methoxyphenyl (300 mmol, 1.0 eq) and palladium acetate (0.005 eq), toluene (600 ml, 7 v / w), ethanol (85 ml, v / w), water (260 ml, 3 v / w) were refluxed, and 86.9 g of product II was obtained after purification, with a yield of 86%;

[0129] Step 3, product II (86.9 g, 258 mmol) was dissolved in DCM (435 ml, 5 V / W), and boron tribromide (335 mmol, 1.3 eq) was added dropwise under ice bath, and the reaction was carried out for 1 h under ice bath, and 83.3 g of product III was obtained after treatment, with a yield of 100%;

[0130] Step 4, product III (83.3 g, 258 mmol) was dissolved in NMP (417 ml, 5 V / W), potassium carbonate (387 mmol, 1.5 eq) was added, and the reaction was carried out at 170-180 ℃ for 1 h, most of the NMP was removed by concentration, water was added to precipitate the product, and the product was obtained by filtration and drying, with a yield of 74.2 g, and a yield of 95%;

[0131] Step 5, product IV (74.2 g, 245 mmol, 1.0 eq), pinacol diboron (319 mmol, 1.3 eq), potassium acetate (490 mmol, 2 eq), Pd2(dba)3(0.005 eq), X-phos (0.01 eq) and 1,4-dioxane (600 ml, 8 v / w) were refluxed for 2 h, and compound A was prepared by treatment and purification, with a yield of 86.9 g, and a yield of 90%;

[0132]

[0133] (2) Preparation of compound B:

[0134] Step 1, o-fluoronitrobenzene (400 mmol) and p-bromoaniline (400 mmol) were dissolved in THF 400 ml, sodium tert-butoxide (600 mol) was added portionwise, and after the addition was completed, the reaction was carried out under reflux for 3 h, water was added to quench the reaction, and toluene was recrystallized to obtain 59.8 g of product, with a yield of 51%;

[0135] Step 2, the obtained product (59.8 g, 204 mmol), ethanol 300 ml, water 300 ml, and sodium hydrosulfite (306 mmol) were added to the reaction bottle, and the reaction was carried out under reflux for 2 h, and the product was obtained by filtration and water washing, with a yield of 53.7 g, and a yield of 100%;

[0136] Step 3, 1-pyridine-3-ethanone 400 mmol, sodium sulfite 1.2 mol, ethanol 50 ml, water 250 ml were added to the reaction bottle, and stirred at room temperature for 2 h, and 75.2 g of solid was obtained by filtration and water washing, with a yield of 89%.

[0137] Step 4: The product obtained in step 2 (52.4 g, 200 mmol) and the product obtained in step 3 (59.1 g, 280 mmol) were added to 400 ml of DMF and reacted at 130°C for 1 h. The reaction solution was poured into water, filtered, dried, dissolved in toluene, and concentrated by column to obtain 52.5 g of the product, with a yield of 75%.

[0138] Step 5: The product obtained in step 4 (52.5 g, 150 mmol), bipyralidoborane (180 mmol), potassium acetate (300 mmol), Pd(dppf)Cl2 (0.75 mmol), and 420 ml of 1,4-dioxane were added to a reaction flask and refluxed for 2 h. The mixture was concentrated to remove most of the 1,4-dioxane, dissolved in dichloromethane, and concentrated through a column until a large amount of solid precipitated. Petroleum ether was added for crystallization, and the mixture was filtered and dried to obtain 51.8 g of a white solid, which was compound B, with a yield of 87%;

[0139]

[0140] (3) Add 200 mmol of 9-bromoanthracene, 210 mmol of compound A, 400 mmol of potassium carbonate, 2 mmol of palladium acetate, 400 ml of toluene, 50 ml of ethanol, and 150 ml of water to a reaction flask. Replace the atmosphere with nitrogen and heat to reflux for 4-8 hours. After the reaction of the 9-bromoanthracene raw material is complete, stop the reaction. Cool to room temperature, filter, wash the filter cake with water until neutral, air dry, dissolve the toluene, pass it through a silica gel column, concentrate the column liquid, filter, crystallize, and dry to obtain 72.0 g of yellow-green solid S1, with a yield of 81% (calculated based on 9-bromoanthracene).

[0141] (4) 150 mmol of yellow-green solid S1, 160 mmol of NBS, and 670 ml of tetrahydrofuran were added to a reaction flask and refluxed for 2 h. The reaction was stopped, cooled to room temperature, and quenched with a small amount of sodium bisulfite aqueous solution. The solution was concentrated, crystallized, filtered, and the resulting solid was slurried with ethanol and dried to obtain 78.5 g of off-white solid S2, with a yield of 100% (based on the yellow-green solid S1);

[0142] (5) 100 mmol of off-white solid S2, 110 mmol of compound B, 200 mmol of potassium carbonate, 0.5 mmol of palladium acetate were added to the reaction flask, and 400 ml of toluene, 50 ml of ethanol, and 150 ml of water were added. The atmosphere was replaced with nitrogen and refluxed for 2-4 h. The reaction was stopped. The reactant was cooled to room temperature, water was added, filtered, and washed with water. The obtained solid was slurried with ethanol, filtered and dried, dissolved in toluene, passed through a column, concentrated, crystallized, filtered, and dried to obtain 36.4 g of yellow-green compound 4, with a yield of 51% (based on the off-white solid S2).

[0143] The reaction process is:

[0144]

[0145] Compound 18 was tested by LCMS, and the data obtained were as follows: ESI-MS: C 52 H 31 N3O, standard molecular weight 713.82, test result 713.32[M+].

[0146] Implementation Case 6

[0147] This embodiment proposes a phenanthrene-containing luminescent material, whose structural formula is

[0148]

[0149] The preparation method of compound 22 comprises the following steps:

[0150] (1) Preparation of Compound A:

[0151] Step 1: 1-Bromo-4-chloro-2-fluorobenzene (400 mmol, 1.0 eq) was dissolved in tetrahydrofuran (800 ml, 10 v / w) and bromine was removed by adding n-butyl lithium (520 mmol, 1.3 eq). The product was then reacted with tri-n-butyl borate (600 mmol, 1.5 eq) and acidified to obtain 59.3 g of product I in a yield of 85%.

[0152] Step 2: Product I (330 mmol, 1.1 eq), 2-bromo-3-methoxyphenanthrene (300 mmol, 1.0 eq) and palladium acetate (0.005 eq), toluene (600 ml, 7 v / w), ethanol (85 ml, v / w), and water (260 ml, 3 v / w) were refluxed to obtain 86.9 g of product II after purification, with a yield of 86%;

[0153] Step 3: Product II (86.9 g, 258 mmol) was dissolved in DCM (435 ml, 5 V / W), and boron tribromide (335 mmol, 1.3 eq) was added dropwise under ice bath for demethylation. The reaction was continued under ice bath for 1 h, and post-treatment was performed to obtain 83.3 g of product III, with a yield of 100%;

[0154] Step 4: Dissolve product III (83.3 g, 258 mmol) in NMP (417 ml, 5 V / W), add potassium carbonate (387 mmol, 1.5 eq) and react at 170-180°C for 1 h. Concentrate to remove most of the NMP, add water to precipitate the product, filter and dry to obtain 74.2 g of product IV, with a yield of 95%;

[0155] Step 5: Product IV (74.2 g, 245 mmol, 1.0 eq), pinacol diboron (319 mmol, 1.3 eq), potassium acetate (490 mmol, 2 eq), Pd2(dba)3 (0.005 eq), X-phos (0.01 eq) and 1,4-dioxane (600 ml, 8 v / w) were refluxed for 2 h, and post-processed and purified to obtain 86.9 g of compound A in a yield of 90%;

[0156]

[0157] (2) Preparation of compound B:

[0158] Step 1: o-Fluoronitrobenzene (400 mmol) and p-bromoaniline (400 mmol) were dissolved in 400 ml of THF. Sodium tert-butoxide (600 mol) was added in batches. After the addition was complete, the mixture was refluxed for 3 h. After quenching with water, the mixture was recrystallized from toluene to obtain 59.8 g of the product with a yield of 51%.

[0159] Step 2: Add the obtained product (59.8 g, 204 mmol), 300 ml of ethanol, 300 ml of water, and sodium dithionite (306 mmol) into a reaction flask, reflux for 2 h, filter, and wash with water to obtain 53.7 g of the product, with a yield of 100%;

[0160] Step 3, 400 mmol of 1-naphthalene-2-ethanone, 1.2 mol of sodium sulfite, 70 ml of ethanol and 350 ml of water were added to a reaction flask, stirred at room temperature for 2 h, filtered and washed with water to obtain 96.8 g of solid, with a yield of 93%;

[0161] Step 4: The product obtained in step 2 (52.4 g, 200 mmol) and the product obtained in step 3 (72.9 g, 280 mmol) were added to 400 ml of DMF and reacted at 130°C for 1 h. The reaction solution was poured into water, filtered, dried, dissolved in toluene, and concentrated by column to obtain 67.1 g of the product, with a yield of 84%.

[0162] Step 5: The product obtained in step 4 (67.1 g, 172 mmol), bipyralidoborane (207 mmol), potassium acetate (344 mmol), Pd(dppf)Cl2 (0.86 mmol), and 540 ml of 1,4-dioxane were added to a reaction flask and refluxed for 2 h. The mixture was concentrated to remove most of the 1,4-dioxane, dissolved in dichloromethane, and concentrated through a column until a large amount of solid precipitated. Petroleum ether was added for crystallization, and the mixture was filtered and dried to obtain 68.3 g of a white solid, which was compound B, with a yield of 89%;

[0163]

[0164] (3) Add 200 mmol of 9-bromoanthracene, 210 mmol of compound A, 400 mmol of potassium carbonate, 2 mmol of palladium acetate, 400 ml of toluene, 50 ml of ethanol, and 150 ml of water to a reaction flask. Replace the atmosphere with nitrogen and heat to reflux for 4-8 hours. After the reaction of the 9-bromoanthracene raw material is complete, stop the reaction. Cool to room temperature, filter, wash the filter cake with water until neutral, air dry, dissolve the toluene, pass it through a silica gel column, concentrate the column liquid, filter, crystallize, and dry to obtain 72.0 g of yellow-green solid S1, with a yield of 81% (calculated based on 9-bromoanthracene).

[0165] (4) 150 mmol of yellow-green solid S1, 160 mmol of NBS, and 670 ml of tetrahydrofuran were added to a reaction flask and refluxed for 2 h. The reaction was stopped, cooled to room temperature, and quenched with a small amount of sodium bisulfite aqueous solution. The solution was concentrated, crystallized, filtered, and the resulting solid was slurried with ethanol and dried to obtain 78.5 g of off-white solid S2, with a yield of 100% (based on the yellow-green solid S1);

[0166] (5) 100 mmol of off-white solid S2, 110 mmol of compound B, 200 mmol of potassium carbonate, 0.5 mmol of palladium acetate were added to the reaction flask, and 400 ml of toluene, 50 ml of ethanol, and 150 ml of water were added. The atmosphere was replaced with nitrogen and refluxed for 2-4 h. The reaction was stopped. The reactant was cooled to room temperature, water was added, filtered, and washed with water. The obtained solid was slurried with ethanol, filtered and dried, dissolved in toluene, passed through a column, concentrated, crystallized, filtered, and dried to obtain 36.4 g of yellow-green compound 4, with a yield of 51% (based on the off-white solid S2).

[0167] The reaction process is:

[0168]

[0169] Compound 22 was tested by LCMS, and the data obtained were as follows: ESI-MS: C 57 H 34 N2O, standard molecular weight 762.89, test result 762.29 [M+].

[0170] Implementation Case 7

[0171] This embodiment proposes a phenanthrene-containing luminescent material, whose structural formula is

[0172]

[0173] The preparation method of compound 34 comprises the following steps:

[0174] (1) Preparation of Compound A:

[0175] Step 1: 1-Bromo-4-chloro-2-fluorobenzene (400 mmol, 1.0 eq) was dissolved in tetrahydrofuran (800 ml, 10 v / w) and bromine was removed by adding n-butyl lithium (520 mmol, 1.3 eq). The product was then reacted with tri-n-butyl borate (600 mmol, 1.5 eq) and acidified to obtain 59.3 g of product I in a yield of 85%.

[0176] Step 2: Product I (330 mmol, 1.1 eq), 2-bromo-3-methoxyphenanthrene (300 mmol, 1.0 eq) and palladium acetate (0.005 eq), toluene (600 ml, 7 v / w), ethanol (85 ml, v / w), and water (260 ml, 3 v / w) were refluxed to obtain 86.9 g of product II after purification, with a yield of 86%;

[0177] Step 3: Product II (86.9 g, 258 mmol) was dissolved in DCM (435 ml, 5 V / W), and boron tribromide (335 mmol, 1.3 eq) was added dropwise under ice bath for demethylation. The reaction was continued under ice bath for 1 h, and post-treatment was performed to obtain 83.3 g of product III, with a yield of 100%;

[0178] Step 4: Dissolve product III (83.3 g, 258 mmol) in NMP (417 ml, 5 V / W), add potassium carbonate (387 mmol, 1.5 eq) and react at 170-180°C for 1 h. Concentrate to remove most of the NMP, add water to precipitate the product, filter and dry to obtain 74.2 g of product IV, with a yield of 95%;

[0179] Step 5: Product IV (74.2 g, 245 mmol, 1.0 eq), pinacol diboron (319 mmol, 1.3 eq), potassium acetate (490 mmol, 2 eq), Pd2(dba)3 (0.005 eq), X-phos (0.01 eq) and 1,4-dioxane (600 ml, 8 v / w) were refluxed for 2 h, and post-processed and purified to obtain 86.9 g of compound A in a yield of 90%;

[0180]

[0181] (2) Preparation of compound B:

[0182] Step 1: o-Fluoronitrobenzene (400 mmol) and p-bromoaniline (400 mmol) were dissolved in 400 ml of THF. Sodium tert-butoxide (600 mol) was added in batches. After the addition was complete, the mixture was refluxed for 3 h. After quenching with water, the mixture was recrystallized from toluene to obtain 59.8 g of the product with a yield of 51%.

[0183] Step 2, Put the product from step 1 (59.8g, 204mmol), ethanol 300ml, water 300ml, sodium hydrosulfite (306mmol) into a flask, reflux for 2h, filter and wash with water to get product 53.7g, yield 100%;

[0184] Step 3, Put 1-biphenyl-4-ethanone 400mmol, sodium sulfite 1.2mol, ethanol 80ml, water 400ml into a flask, stir at room temperature for 2h, filter and wash with water to get 104.2g solid, yield 91%;

[0185] Step 4, Put the product from step 2 (52.4g, 200mmol) and the product from step 3 (80.2g, 280mmol) into DMF 400ml, react at 130℃ for 1h, pour the reaction solution into water, filter, dry, dissolve in toluene, pass through a column, concentrate, and crystallize to get 72.3g of product, yield 85%;

[0186] Step 5, Put the product from step 4 (72.3g, 170mmol), pinacol diborane (204mmol), potassium acetate (340mmol), Pd(dppf)Cl2(0.85mmol), 1,4-dioxane 580ml into a flask, reflux for 2h, concentrate to remove most of the 1,4-dioxane, dissolve in dichloromethane, pass through a column, concentrate to precipitate a large amount of solid, add petroleum ether to crystallize, filter and dry to get 70.7g of white solid, which is compound B, yield 88%;

[0187]

[0188] (3) Put 200mmol of 9-bromoanthracene, 210mmol of compound A, 400mmol of potassium carbonate, 2mmol of palladium acetate, 400ml of toluene, 50ml of ethanol, and 150ml of water into a flask, replace with nitrogen, heat to reflux for 4-8h, stop the reaction when the 9-bromoanthracene raw material is completely reacted. Cool to room temperature, filter, add water to the filter cake until it is neutral, and dry with a blast dryer. Dissolve in toluene and pass through a silica gel column. Concentrate the column eluate, crystallize, filter, and dry to get 72.0g of yellow-green solid S1, yield 81% (calculated based on 9-bromoanthracene);

[0189] (4) Put 150mmol of yellow-green solid S1, 160mmol of NBS, and 670ml of tetrahydrofuran into a flask, reflux for 2h, stop the reaction, cool to room temperature, quench with a small amount of sodium bisulfite aqueous solution, concentrate, crystallize, filter the obtained solid, and soak in ethanol, then dry to get 78.5g of white solid S2, yield 100% (calculated based on yellow-green solid S1);

[0190] (5) In a reaction bottle, 100 mmol of the white solid S2, 110 mmol of compound B, 200 mmol of potassium carbonate, 0.5 mmol of palladium acetate, 400 ml of toluene, 50 ml of ethanol, and 150 ml of water were added, and the reaction was carried out under reflux for 2-4 h. After the reaction was stopped, the reaction was cooled to room temperature, water was added, and the mixture was filtered, washed with water, and the obtained solid was slurried with ethanol, filtered, dried, dissolved in toluene, and column-purified to obtain 36.4 g of yellow-green compound 4 in a yield of 51% (based on the white solid S2).

[0191] The reaction scheme is as follows:

[0192]

[0193] Compound 34 was tested by LCMS, and the data are as follows: ESI-MS: C 59 H 36 N2O, standard molecular weight 788.93, test result 788.28 [M+].

[0194] Comparative Example 1

[0195] The present comparative example provides a light-emitting material, the structural formula of which is

[0196]

[0197] Comparative Example 2

[0198] The present comparative example provides a light-emitting material, the structural formula of which is

[0199]

[0200] Test Example

[0201] The light-emitting material prepared by the above Examples 1-8 and Comparative Examples 1-2 was used to prepare an OLED device, which comprises a first hole injection layer (HIL-1), a second hole injection layer (HIL-2), a first hole transport layer (HTL-1), a second hole transport layer (HTL-2), an organic light-emitting layer, an electron transport layer (ETL), an electron injection layer (EIL), and a cathode (Cthd) deposited on an ITO substrate in sequence.

[0202] The ITO substrate was prepared as follows: the glass substrate coated with an ITO transparent conductive layer (as an anode) was subjected to ultrasonic treatment in a cleaning agent, then washed in deionized water, then subjected to ultrasonic oil removal in a mixed solvent of acetone and ethanol, then baked in a clean environment until completely water-free, washed with an ultraviolet lamp and ozone, and the surface was bombarded with a low-energy cation beam to improve the surface properties and improve the binding ability with the hole transport layer. Then the vacuum degree of the vacuum evaporation machine was maintained at 1x10-6 torr to 3x10 -7 torr, and various organic materials and metal materials were sequentially deposited on the ITO substrate to obtain the OLED devices of the embodiment and the comparative example.

[0203] In the various layers of the above-mentioned OLED device, HAT is used to form HI-1 and HID; HI-2 is used to form HI-2; HT-1 and HT-2 are used to form HTL-1 and HTL-2; Liq is used to form ETD and EIL; ET is the main material for forming ETL; the novel compounds of the examples and the compounds of the comparative examples are used to form BEL; BD can serve as a dopant for BEL. The detailed structural formulas of the above-mentioned compounds are listed in Table 1 below.

[0204] Table 1

[0205]

[0206] The luminescent materials prepared in Examples 1-8 and Comparative Examples 1-2 are used to prepare BEL in OLED devices, as shown in Table 2.

[0207] Table 2

[0208]

[0209] Table 3 below shows the materials, thickness, doping ratio and coating sequence of each organic layer of the OLED device in this test case.

[0210] Table 3

[0211] organic layer HI-1 HI-2 HID HTL1 HTL2 BEL BD ET1 ETD EIL Cthd Material HAT HI-2 HAT HT1 HT2 BH BD ET1 Liq Liq A1 Thickness (nm) 10 50 / 10 10 20 / 20 / 20 150 Mixing ratio / / 5.00％ / / / 3.00％ / 30％ / / Coating order 1 2 2 3 4 5 5 6 6 7 8

[0212] Evaluation of the OLED Device: To evaluate the performance of the OLED device, the device was connected to a power supply (Keithley, Model 2400) and tested using a PR650 luminance meter. The OLED device was tested at a brightness of 1000 nits. The test results are shown in Table 4.

[0213] Table 4

[0214]

[0215] From the results in Table 4, it can be seen that compared with the comparative example, the material prepared in the implementation case of the present application can be used in organic electroluminescent devices, which can effectively reduce the driving voltage, improve the current efficiency, and increase the service life, and is a blue light material with good performance.

[0216] The technical features of the above-mentioned embodiments can be combined arbitrarily. In order to make the description concise, not all possible combinations of the technical features in the above-mentioned embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0217] The above-described embodiments merely illustrate several implementations of the present invention, and while their descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the patent. It should be noted that a person skilled in the art would be able to make numerous variations and improvements without departing from the spirit of the present invention, all of which fall within the scope of protection of the present invention. Therefore, the scope of protection of the patent for this invention shall be determined by the appended claims.

Claims

1. A phenanthrene-containing organic electroluminescent material, characterized in that: Its structure is shown below: wherein Ar is selected from an aromatic group having 6 to 18 carbon atoms, an unsubstituted or deuterium-substituted ring, or 2. The phenanthrene-containing organic electroluminescent material according to claim 1, characterized in that: Ar is selected from deuterated aromatic groups having 6 to 18 ring carbon atoms.

3. The phenanthrene-containing organic electroluminescent material according to claim 1, characterized in that: Ar is selected from aromatic groups having 6 to 18 ring carbon atoms and not containing deuterium.

4. The phenanthrene-containing organic electroluminescent material according to claim 1, characterized in that: Ar is selected from or 5. The phenanthrene-containing organic electroluminescent material according to claim 1, characterized in that: It is one of the compounds represented by the following structural formula:

6. A method for preparing a phenanthrene-containing organic electroluminescent material according to any one of claims 1 to 5, characterized in that: Its synthetic route is as follows: Wherein, Ar is the group as described in claim 1.

7. The method for preparing a phenanthrene-containing organic electroluminescent material according to claim 6, wherein: The preparation method of the compound A is as follows: 1-bromo-4-chloro-2-fluorobenzene is subjected to bromination removal with n-butyl lithium, and the product is reacted with tri-n-butyl borate to obtain product 1; product 1 is reacted with 2-bromo-3-methoxyphenanthrene and palladium acetate to obtain product 2; product 2 is dissolved in DCM, and BBr3 is added for demethylation to obtain product 3; product 3 is dissolved in NMP, potassium carbonate is added for reaction and cyclization to obtain product 4; product 4 is reacted with pinacol diboron to obtain compound A; The structure of product 1 is: The structure of product 2 is: The structure of product three is: The structure of product 4 is:

8. The method for preparing a phenanthrene-containing organic electroluminescent material according to claim 6, wherein: The preparation method of the compound B is as follows: o-fluoronitrobenzene is reacted with p-bromoaniline to obtain product 1; product 1 is reduced with sodium dithionite to obtain product 2; aromatic acetone is reacted with sodium sulfite to obtain product 3; product 2 is reacted with product 3 to obtain product 4; product 4 is reacted with bipyralidodiboric acid to obtain compound B; The structure of product 1 is: The structure of product 2 is: The structure of product 3 is: The structure of product 4 is:

9. Use of the phenanthrene-containing organic electroluminescent material according to any one of claims 1 to 5 in an organic electroluminescent device.

10. An organic electroluminescent device comprising an organic light-emitting layer, characterized in that: The organic light-emitting layer is made of the phenanthrene-containing organic electroluminescent material according to any one of claims 1 to 5.

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