Triazine fused ring electron transport material containing aryl

Abstract

The invention provides a triazine aromatic group-containing fused ring electron transport material. The structural formula of the triazine aromatic group-containing fused ring electron transport material is # imgabs0 #, wherein Ar1 and Ar2 are deuterium-containing or deuterium-free aromatic groups with the carbon number on the ring being 6-18. Phenanthrene and carbazole are introduced to a substituent group of triazine, so that a conjugated system of the material is enhanced, the electron transport performance and the thermal stability of the compound are improved, and the compound has a wide application prospect.

Description

Technical Field

[0001] The invention relates to the technical field of organic synthesis, and in particular to a triazine-based aromatic-containing condensed ring electron transport material. Background Art

[0002] OLED was first invented and proposed by Eastman Kodak Company. Tang and Van Slyke reported a double-layer organic electroluminescent device, which includes an arylamine hole transport layer and a tri-8-hydroxyquinoline-aluminum layer as an electron transport layer and a light-emitting layer. OLED has attracted much attention due to its advantages of fast reaction rate, light weight, thinness, wide viewing angle, high brightness, high contrast, no need for backlight source and low energy consumption.

[0003] Existing organic electroluminescent devices generally include 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 arranged from top to bottom. The efficiency of organic electroluminescent devices is improved mainly by increasing the probability of exciton formation in the organic light-emitting layer as much as possible. The material of the electron transport layer adjacent to the organic light-emitting layer plays a vital role in the luminous efficiency of organic electroluminescence.

[0004] In OLED materials, the mobility of electrons is generally 2-3 orders of magnitude lower than that of holes, so the number of holes in OLEDs is much greater than the number of electrons. Therefore, developing efficient electron transport materials is very important to improve the efficiency of OLEDs. Summary of the invention

[0005] In order to solve the above problems, the present invention provides a triazine-based aromatic fused ring electron transport material. The electron transport material provided by the present invention has better electron transport properties and stability.

[0006] The present invention provides a triazine-based aromatic-containing condensed ring electron transport material, the structural formula of which is:

[0007]

[0008] Furthermore, Ar1 and Ar2 are deuterium-containing and non-deuterium-containing aromatic groups with 6 to 18 carbon atoms on the ring. The present invention introduces groups such as carbazole and triazine to enhance the electronegativity of the material, improve the electron transport performance of the compound, and utilize phenanthrene to connect the conjugated system of the enhanced material to improve the thermal stability of the compound. The present invention provides an organic electroluminescent compound with high thermal stability and film-forming properties and strong electron mobility.

[0009] Further, the structural formula of Ar1 and Ar2 is

[0010] One or more of .

[0011] Furthermore, the structural formula of the triazine-based aromatic-containing fused ring electron transport material can be:

[0012]

[0013]

[0014] Furthermore, the main structure of the triazine-based aromatic-containing fused ring electron transport material is compound 1.

[0015] Furthermore, the structural formula of the compound 1 is:

[0016] Furthermore, the preparation method of compound 1 is:

[0017] S1: Carbazole (1.5 eq), sodium tert-butoxide (2 eq), a metal catalyst (0.005 eq), a metal catalyst ligand (0.01 eq) and toluene (12 v / w) were refluxed and reacted after nitrogen was introduced to replace the air. After the reaction was completed, toluene was added for crystallization and purification to obtain S1;

[0018] S2: The S1 is placed in a reactor, and p-chlorophenylboric acid (1.2 eq), potassium carbonate (2.0 eq), palladium acetate (0.005 eq), toluene (7 v / w), ethanol (1 v / w) and deionized water (3 v / w) are added, and nitrogen is introduced to replace the air and then reflux reaction is carried out. After the reaction is completed, toluene is crystallized and purified to obtain S2;

[0019] S3: The S2 is placed in a reactor, and diboric acid pinacol ester (1.2 eq), potassium acetate (1.5 eq), a metal catalyst (0.005 eq), a metal catalyst ligand (0.01 eq) and 1,4-dioxane (8 v / w) are added. Nitrogen is introduced to replace the air and a reflux reaction is performed. After the reaction is completed, the compound 1 is purified to obtain the compound 1.

[0020] Furthermore, the metal catalyst is Pd2(dba)3.

[0021] Furthermore, the step catalyst ligand is X-phos.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] 1. Introduce phenanthrene and carbazole into the substituent of triazine to strengthen the conjugated system of the material, improve the electron transport performance and thermal stability of the compound. DETAILED DESCRIPTION

[0024] In order to make the purpose, technical solution and advantages of the present invention clearer, the technical solution of the present invention will be clearly and completely described below in combination with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0025] Reagent Description:

[0026] Carbazole (CAS: 86-74-8), 98%, Anage (Shanghai) Pharmaceutical Chemistry Co., Ltd.; 2,7-Dibromophenanthrene (CAS: 62325-30-8), 98%, p-Chlorophenylboric acid (CAS: 1679-18-1), 98%, Cyanuric chloride (CAS: 108-77-0), 99%, Shanghai MacLean Biochemical Technology Co., Ltd.

[0027] Example 1

[0028] Preparation of ET9:

[0029] S1: 300 mmol of 2,7-dibromophenanthrene, 450 mmol of carbazole, 600 mmol of sodium tert-butoxide, 1.5 mmol of Pd2(dba)3, and 3 mmol of X-phos were added to a reaction flask, and 1200 ml of toluene was replaced with nitrogen. The reaction was refluxed for 2 h. The carbazole part remained, and the reaction was stopped. 500 ml of water was added, and diluted acid was added to neutralize to neutrality. The liquid was separated, and 500 ml of toluene was added to extract the aqueous phase, washed with water, dried over anhydrous sodium sulfate, filled with silica gel and passed through a column. The column liquid was concentrated to about 200 ml, 300 ml of ethanol was added for crystallization for 1 h, filtered and dried, and the obtained solid was recrystallized from toluene and dried to obtain 77.2 g of off-white solid S1;

[0030] S2: Add 150mmol of S1, 160mmol of p-chlorophenylboronic acid, 300mmol of potassium carbonate, 1.5mmol of palladium acetate to a reaction flask, add 450ml of toluene, 65ml of ethanol, and 190ml of water, replace with nitrogen, reflux for 2h, stop the reaction after the reaction of the raw materials, add 200ml of water each time, wash with water 3 times, add anhydrous sodium sulfate to dry, fill with silica gel column, concentrate to 130ml, add 130ml of ethanol to crystallize for 0.5h, filter and dry, the obtained solid is recrystallized from toluene, and dried to obtain 57.9g of off-white solid S2;

[0031] S3: Add 100mmol of S2, 120mmol of biboric acid pinacol ester, 200mmol of potassium acetate, 0.5mmol of Pd2(dba)3, 1mmol of X-phos, 450mL of 1,4-dioxane to the reaction bottle, replace with nitrogen, reflux for 4h, stop the reaction after the reaction of the raw materials is completed. Concentrate to almost dryness, add 900mL of dichloromethane, dissolve in 0.5L of water, separate the liquid, wash the organic phase with water until neutral, add anhydrous sodium sulfate to dry, fill with silica gel to pass through a column, concentrate until a large amount of solid precipitates, add 200ml of petroleum ether to crystallize for 0.5h, filter, and dry 43.6g of off-white solid compound 1;

[0032] S4: 400mmol of bromobenzene, 405mmol of magnesium chips, and 640mL of tetrahydrofuran were used to prepare phenylmagnesium bromide, and the temperature was controlled to 5°C in an ice bath. 400mmol of cyanuric chloride and 300ml of tetrahydrofuran were added to the reaction bottle, and the temperature was lowered to 5°C. The prepared deuterated benzene magnesium bromide solution was slowly added dropwise to the reaction system at a temperature of about 30°C. After the addition was completed, the temperature was raised to 30°C and the reaction was continued for 2h. The reaction was stopped, and the reaction solution was slowly poured into dilute hydrochloric acid to quench. The reaction solution was extracted with tetrahydrofuran, washed with saturated brine, concentrated to dryness, and 1.3L of toluene was added to dissolve the solution and passed through a column. The solution was concentrated to 130ml for crystallization for 1h, filtered and dried, and the obtained solid toluene was recrystallized to obtain 63.2g of off-white solid S4;

[0033] S5: 200mmol of 4-bromopyridine, 205mmol of magnesium chips, and 320mL of tetrahydrofuran were prepared into a Grignard solution, and the solution was stored in an ice bath at 5°C. 280mmol of S4 and 160ml of tetrahydrofuran were added to the reaction bottle, and the temperature was lowered to 5°C. The prepared Grignard solution was slowly added dropwise to the reaction system at a temperature of about 30°C. After the addition was completed, the temperature was raised to 30°C and the reaction was continued for 2h. The reaction was stopped, and the reaction solution was slowly poured into dilute hydrochloric acid to quench, and tetrahydrofuran was added for extraction, and the solution was washed with saturated brine, concentrated to dryness, and 1.2L of toluene was added to dissolve the solution and passed through the column. The solution was concentrated to 120ml for crystallization for 1h, filtered and dried, and the obtained solid was recrystallized from toluene to obtain 25.6g of off-white solid S5;

[0034] S6: Add 70 mmol of S5, 80 mmol of compound 1, 140 mmol of potassium carbonate, 0.35 mmol of palladium acetate, 140 ml of toluene, 20 ml of ethanol, and 60 ml of water into a reaction flask, replace with nitrogen, reflux for 16 hours, a small amount of S5 remains, stop the reaction, cool the reactants to room temperature, add water, filter, and wash with water. Slurry the obtained solid with 100 ml of ethanol, filter and dry. Heat and dissolve 1 L of toluene, fill with silica gel and pass through a column. Concentrate the column liquid to 80 ml, crystallize for 1 hour, filter and dry to obtain 14.1 g of off-white solid ET9.

[0035] ET9 was tested by LCMS and the data obtained were as follows:

[0036] ESI-MS: C46H29N5, standard molecular weight 651.76, test result 652.25 [M+H].

[0037] Embodiment 2:

[0038] Preparation of ET10:

[0039] S1: 300 mmol of 2,7-dibromophenanthrene, 450 mmol of carbazole, 600 mmol of sodium tert-butoxide, 1.5 mmol of Pd2(dba)3, and 3 mmol of X-phos were added to a reaction flask, and 1200 ml of toluene was replaced with nitrogen. The reaction was refluxed for 2 h. The carbazole part remained, and the reaction was stopped. 500 ml of water was added, and diluted acid was added to neutralize to neutrality. The liquid was separated, and 500 ml of toluene was added to extract the aqueous phase, washed with water, dried over anhydrous sodium sulfate, filled with silica gel and passed through a column. The column liquid was concentrated to about 200 ml, 300 ml of ethanol was added for crystallization for 1 h, filtered and dried, and the obtained solid was recrystallized from toluene and dried to obtain 77.2 g of off-white solid S1;

[0040] S2: Add 150mmol of S1, 160mmol of p-chlorophenylboronic acid, 300mmol of potassium carbonate, 1.5mmol of palladium acetate to a reaction flask, add 450ml of toluene, 65ml of ethanol, and 190ml of water, replace with nitrogen, reflux for 2h, stop the reaction after the reaction of the raw materials, add 200ml of water each time, wash with water 3 times, add anhydrous sodium sulfate to dry, fill with silica gel column, concentrate to 130ml, add 130ml of ethanol to crystallize for 0.5h, filter and dry, the obtained solid is recrystallized from toluene, and dried to obtain 57.9g of off-white solid S2;

[0041] S3: Add 100mmol of S2, 120mmol of biboric acid pinacol ester, 200mmol of potassium acetate, 0.5mmol of Pd2(dba)3, 1mmol of X-phos, 450mL of 1,4-dioxane to the reaction bottle, replace with nitrogen, reflux for 4h, stop the reaction after the reaction of the raw materials is completed. Concentrate to almost dryness, add 900mL of dichloromethane, dissolve in 0.5L of water, separate the liquid, wash the organic phase with water until neutral, add anhydrous sodium sulfate to dry, fill with silica gel to pass through a column, concentrate until a large amount of solid precipitates, add 200ml of petroleum ether to crystallize for 0.5h, filter, and dry 43.6g of off-white solid compound 1;

[0042] S4: 400mmol of 4-bromopyridine, 405mmol of magnesium chips, and 320mL of tetrahydrofuran were prepared into a Grignard solution, and the temperature was controlled to 5°C in an ice bath. 200mmol of cyanuric chloride and 300ml of tetrahydrofuran were added to the reaction bottle, and the temperature was lowered to 5°C. The prepared Grignard solution was slowly added dropwise to the reaction system at a temperature of about 30°C. After the addition was completed, the temperature was raised to 30°C and the reaction was carried out for 2h. The reaction was stopped, and the reaction solution was slowly poured into dilute hydrochloric acid to quench, and tetrahydrofuran was added for extraction, and saturated brine was washed, and tetrahydrofuran was added for extraction, and saturated brine was washed, and the solution was concentrated to dryness, and 1.5L of toluene was added to dissolve the solution and passed through the column, and 150ml was concentrated for crystallization for 1h, and the solid toluene obtained was recrystallized to obtain 24.3g of off-white solid S4;

[0043] S5: Add 70 mmol of S4, 80 mmol of compound 1, 140 mmol of potassium carbonate, 0.35 mmol of palladium acetate, 140 ml of toluene, 20 ml of ethanol, and 60 ml of water into a reaction flask, replace with nitrogen, reflux for 16 hours, a small amount of S4 remains, stop the reaction, cool the reactants to room temperature, add water, filter, and wash with water. Slurry the obtained solid with 100 ml of ethanol, filter and dry. Heat and dissolve 1 L of toluene, fill with silica gel and pass through a column. Concentrate the column liquid to 80 ml, crystallize for 1 hour, filter and dry to obtain 12.8 g of off-white solid ET10.

[0044] ET10 was tested by LCMS and the data obtained are as follows:

[0045] ESI-MS: C45H28N6, standard molecular weight 652.74, test result 653.25 [M+H].

[0046] Embodiment 3:

[0047] Preparation of ET16:

[0048] S1: 300 mmol of 2,7-dibromophenanthrene, 450 mmol of carbazole, 600 mmol of sodium tert-butoxide, 1.5 mmol of Pd2(dba)3, and 3 mmol of X-phos were added to a reaction flask, and 1200 ml of toluene was replaced with nitrogen. The reaction was refluxed for 2 h. The carbazole part remained, and the reaction was stopped. 500 ml of water was added, and diluted acid was added to neutralize to neutrality. The liquid was separated, and 500 ml of toluene was added to extract the aqueous phase, washed with water, dried over anhydrous sodium sulfate, filled with silica gel and passed through a column. The column liquid was concentrated to about 200 ml, 300 ml of ethanol was added for crystallization for 1 h, filtered and dried, and the obtained solid was recrystallized from toluene and dried to obtain 77.2 g of off-white solid S1;

[0049] S2: Add 150mmol of S1, 160mmol of p-chlorophenylboronic acid, 300mmol of potassium carbonate, 1.5mmol of palladium acetate to a reaction flask, add 450ml of toluene, 65ml of ethanol, and 190ml of water, replace with nitrogen, reflux for 2h, stop the reaction after the reaction of the raw materials, add 200ml of water each time, wash with water 3 times, add anhydrous sodium sulfate to dry, fill with silica gel column, concentrate to 130ml, add 130ml of ethanol to crystallize for 0.5h, filter and dry, the obtained solid is recrystallized from toluene, and dried to obtain 57.9g of off-white solid S2;

[0050] S3: Add 100mmol of S2, 120mmol of biboric acid pinacol ester, 200mmol of potassium acetate, 0.5mmol of Pd2(dba)3, 1mmol of X-phos, 450mL of 1,4-dioxane to the reaction bottle, replace with nitrogen, reflux for 4h, stop the reaction after the reaction of the raw materials is completed. Concentrate to almost dryness, add 900mL of dichloromethane, dissolve in 0.5L of water, separate the liquid, wash the organic phase with water until neutral, add anhydrous sodium sulfate to dry, fill with silica gel to pass through a column, concentrate until a large amount of solid precipitates, add 200ml of petroleum ether to crystallize for 0.5h, filter, and dry 43.6g of off-white solid compound 1;

[0051] S4: 400mmol of bromobenzene, 405mmol of magnesium chips, and 640mL of tetrahydrofuran were used to prepare phenylmagnesium bromide, and the mixture was stored in an ice bath at 5°C. 400mmol of cyanuric chloride (CAS: 108-77-0) and 300ml of tetrahydrofuran were added to the reaction bottle, and the temperature was lowered to 5°C. The prepared deuterated benzene magnesium bromide solution was slowly added dropwise to the reaction system at a temperature of about 30°C. After the addition was completed, the temperature was raised to 30°C and the reaction was continued for 2h. The reaction was stopped, and the reaction solution was slowly poured into dilute hydrochloric acid to quench. The mixture was extracted with tetrahydrofuran, washed with saturated brine, concentrated to dryness, dissolved in 1.5L of toluene, and passed through a column. The mixture was concentrated to 150ml for crystallization for 1h, filtered and dried, and the obtained solid toluene was recrystallized to obtain 63.2g of off-white solid S4;

[0052] S5: 200mmol of 4-(4-bromophenyl)pyridine, 205mmol of magnesium chips, and 450mL of tetrahydrofuran were used to prepare a Grignard solution, which was stored in an ice bath at 5°C. 280mmol of S4 and 160ml of tetrahydrofuran were added to the reaction bottle, and the temperature was lowered to 5°C. The prepared Grignard solution was slowly added dropwise to the reaction system at a temperature of about 30°C. After the addition was completed, the temperature was raised to 30°C and the reaction was continued for 2h. The reaction was stopped, and the reaction solution was slowly poured into dilute hydrochloric acid to quench. The reaction solution was extracted with tetrahydrofuran, washed with saturated brine, concentrated to dryness, dissolved in 3.2L of toluene, and passed through a column. The solution was concentrated to 160ml for crystallization for 1h, filtered and dried, and the obtained solid toluene was recrystallized to obtain 34.7g of off-white solid S5;

[0053] S6: Add 70 mmol of S5, 80 mmol of compound 1, 140 mmol of potassium carbonate, 0.35 mmol of palladium acetate, 140 ml of toluene, 20 ml of ethanol, and 60 ml of water into a reaction flask, replace with nitrogen, reflux for 16 hours, a small amount of S5 remains, stop the reaction, cool the reactants to room temperature, add water, filter, and wash with water. Slurry the obtained solid with 100 ml of ethanol, filter and dry. Heat and dissolve 1 L of toluene, fill with silica gel and pass through a column. Concentrate the column liquid to 80 ml, crystallize for 1 hour, filter and dry to obtain 14.8 g of off-white solid ET16.

[0054] ET16 was tested by LCMS and the data obtained are as follows:

[0055] ESI-MS: C52H33N5, standard molecular weight 727.85, test result 728.30 [M+H].

[0056] Results and Testing

[0057] The blue light OLED device was connected to a power supply (brand: Keithley; model: 2400) and tested with a PR650 luminance meter, wherein the OLED device was tested at a brightness of 1000 nits.

[0058]

[0059] Implementation Example 2 has lower driving voltage, higher current efficiency, and higher external quantum efficiency by introducing pyridine groups, triazine groups, and carbazole groups. Due to its symmetrical structure and higher stability, its service life is longer.

[0060] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A triazine-based aromatic fused ring electron transport material, characterized in that: The structural formula is:

2. A triazine-based aromatic fused ring electron transport material according to claim 1, characterized in that: Ar1 and Ar2 are deuterated or non-deuterated aromatic groups having 6 to 18 carbon atoms in the ring.

3. A triazine-based aromatic fused ring electron transport material according to claim 1, characterized in that: The structural formula of Ar1 and Ar2 is One or more of .

4. A triazine-based aromatic fused ring electron transport material according to claim 1, characterized in that: The main structure of the triazine-based aromatic fused ring electron transport material is compound 1.

5. A triazine-based aromatic fused ring electron transport material according to claim 1, characterized in that: The structural formula of the compound 1 is:

6. A triazine-based aromatic fused ring electron transport material according to claim 5, characterized in that: The preparation method of compound 1 is: S1: 2,7-dibromophenanthrene, potassium carbonate, a metal catalyst, a metal catalyst ligand and toluene are refluxed after nitrogen is introduced to replace air, and S1 is obtained after purification after the reaction is completed; S2: placing the S1 in a reactor, adding p-chlorophenylboric acid, potassium carbonate, palladium acetate, toluene, ethanol and deionized water, introducing nitrogen to replace the air and then performing a reflux reaction, and purifying to obtain S2 after the reaction is completed; S3: placing the S2 in a reactor, adding diboric acid pinacol ester, potassium acetate, a metal catalyst, a metal catalyst ligand and 1,4-dioxane, introducing nitrogen to replace the air and then performing a reflux reaction, and purifying to obtain the compound 1 after the reaction is completed.

7. A triazine-based aromatic fused ring electron transport material according to claim 6, characterized in that: The metal catalyst is Pd2(dba)3.

8. A triazine-based aromatic fused ring electron transport material according to claim 6, characterized in that: The metal catalyst ligand is X-phos.

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