Bis-triazine compound and organic electroluminescent device thereof
By designing bistriazine compounds with triazine groups and nitrogen-containing heteroaromatic rings, the problem of low electron mobility in traditional OLED electroluminescent devices is solved, and higher electron mobility and longer device life is achieved.
Patent Information
- Application Number
- CN202411819419.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-11
- Publication Date
- 2025-03-21
AI Technical Summary
The electron transport material Alq3 used in traditional OLED electroluminescent devices has a low electron mobility, resulting in uneven carrier transmission and is difficult to meet the needs of medium and large screen applications.
A bistriazine compound was designed, and its structure was connected to ortho-position bonds of a triazine group to biphenyl or fluorene derivatives, and combined with intramolecular hydrogen bonds of nitrogen-containing heteroaromatic rings, enhancing the dipole moment and planarity of the compound.
The electron mobility and glass transition temperature are improved, and the film formation and life of organic electroluminescent devices are enhanced.
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Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of organic electroluminescent materials, and in particular relates to a bistriazine compound and an organic electroluminescent device thereof. Background Art
[0002] The electron transport material used in traditional electroluminescent devices is Alq3, but the electron mobility of Alq3 is relatively low (about 10-6cm 2 / Vs), which makes the carrier transmission of the device unbalanced. With the official announcement of the investment in the 8.6-generation panel production line of several major domestic panel manufacturers, the application field of OLED has begun to rapidly advance from the small and medium-sized screen field to the medium and large screen field, and the application scenarios are becoming more and more abundant. Therefore, people hope to obtain electron transport materials with higher electron mobility and better performance. In this field, researchers have done a lot of exploratory work.
[0003] Electron transport materials are responsible for regulating the injection speed and amount of electrons. In order to improve the injection and transport of electrons, high-mobility electron injection and transport materials are needed. Although a large number of organic electron transport materials have been reported, it has always been challenging to design and synthesize organic small molecule electron transport materials with excellent comprehensive performance. Summary of the invention
[0004] In order to solve the problems existing in the background technology, the first object of the present invention is to provide a bistriazine compound, and the technical scheme is as follows:
[0005] A bistriazine compound, the structure of which is shown in the following general formula I:
[0006]
[0007] In the general formula I, Indicates the presence or absence of a bond relationship of Y. When there is no bond relationship of Y, the structure of general formula I becomes the following formulas I-1 and I-2; when there is a bond relationship of Y, the structure of general formula I becomes the following formulas I-3 and I-4:
[0008]
[0009] Y is O or S;
[0010] Ar1 is independently selected from substituted or unsubstituted C6 to C 30 Aryl, when substituted, the substituent is selected from C1 to C 10 Alkyl, cyano, C6~C 18 Aryl, C3~C 18 heteroaryl;
[0011] L is selected from C6~C 30Aryl, one of V1, V2, and V3 is nitrogen and the other two are carbon;
[0012] Ar2 is selected from substituted or unsubstituted C6~C 30 Aryl, substituent selected from C1~C 10 Alkyl, silane, C6~C 18 Aryl, C3~C 18 Heteroaryl.
[0013] As a preferred embodiment of the present invention, Ar1 is selected from substituted or unsubstituted C6 to C 18 When aryl is substituted, the substituent is selected from C1-C4 alkyl, cyano, phenyl, and nitrogen-containing six-membered heteroaryl.
[0014] As a preferred embodiment of the present invention, Ar2 is selected from substituted or unsubstituted C6 to C 18 When aryl is substituted, the substituent is selected from C1-C4 alkyl, silyl, phenyl, and nitrogen-containing six-membered heteroaryl.
[0015] As a preferred embodiment of the present invention, the above-mentioned bistriazine compound has a structure of any one of the following structures:
[0016]
[0017]
[0018]
[0019]
[0020]
[0021]
[0022]
[0023] Another object of the present invention is to provide an organic electroluminescent device, comprising a substrate layer, a first electrode located on the substrate layer, and an organic light-emitting functional layer located on the first electrode, wherein the organic light-emitting functional layer comprises the above-mentioned bistriazine compound.
[0024] As a preferred embodiment of the present invention, the organic light-emitting functional layer includes an electron transport layer, and the electron transport layer contains the above-mentioned bistriazine compound.
[0025] As a preferred embodiment of the present invention, the organic electroluminescent device is used to manufacture display devices, lighting sources, signal lights, and signboards. The display devices include mobile phone displays, computer displays, television displays, smart watch displays, smart car display panels, VR or AR helmet displays.
[0026] The beneficial effects of the present invention are as follows:
[0027] The present invention provides a bistriazine compound and an organic electroluminescent device thereof, wherein a triazine group with electron transport property at one end is bonded to a central biphenyl or fluorene derivative at an ortho position, while a comparative example is bonded to a meta position or a para position, and a rigid ortho position bonding mode with strong steric hindrance increases the dipole moment of the compound structure; on the other hand, a nitrogen-containing heteroaromatic ring connected to an L group can form an intramolecular hydrogen bond with hydrogen adjacent to the L group, thereby increasing the planarity of the entire molecule, improving the electron mobility, and further increasing the glass transition temperature of the compound, so that the compound has excellent film-forming property during the device preparation process, and thus the service life of the prepared device is greatly improved. DETAILED DESCRIPTION
[0028] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. 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.
[0029] If the specific conditions are not specified in the embodiments, they are carried out under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used without indicating the manufacturer are all conventional products that can be purchased commercially. Some reaction compounds are purchased from commodity suppliers (Zhengzhou Alpha Chemical Co., Ltd.), and some compounds that cannot be directly purchased are prepared by simple reactions of commercially available raw materials. The percentages all refer to mass percentages, and the temperatures are degrees Celsius (℃). Such method principles, operating procedures, conventional post-treatments, silica gel columns, recrystallization purification and other means are well known to synthesizers in the art, and the synthesis process can be fully realized to obtain the target product. The reactions in each preparation embodiment are generally carried out under positive pressure of nitrogen or argon.
[0030] Preparation Example
[0031] Example 1: Synthesis of Compound 1
[0032]
[0033] Synthesis of compound 1-3: Compound 1-1 (3.4 g, 15 mmol) and compound 1-2 (4.2 g, 15 mmol) were completely dissolved in tetrahydrofuran (THF) (50 mL), and 2M potassium carbonate aqueous solution (30 mL) and tetrakis-(triphenylphosphine) palladium (Pd(PPh3)4) (0.6 g, 0.5 mmol) were added thereto, and the mixture was heated and stirred for 6 h. Then, the mixture was cooled to room temperature to complete the reaction, and after removing the potassium carbonate solution, the solid was filtered out and washed once with ethanol to obtain compound 1-3 (4.7 g, yield 91%);
[0034] Synthesis of compound 1-5: Compound 1-3 (5.2 g, 15 mmol) and compound 1-4 (4.7 g, 15 mmol) were completely dissolved in tetrahydrofuran (THF) (50 mL), and 2M potassium carbonate aqueous solution (30 mL) and tetrakis-(triphenylphosphine) palladium (Pd(PPh3)4) (0.6 g, 0.5 mmol) were added thereto, and the mixture was heated and stirred for 10 h. Then, the mixture was cooled to room temperature to complete the reaction, and after removing the potassium carbonate solution, the solid was filtered out and washed once with ethanol to obtain compound 1-5 (6.5 g, yield 88%);
[0035] Synthesis of compound 1-7: Compound 1-5 (3.6 g, 7.2 mmol), compound 1-6 (1.8 g, 7.2 mmol), potassium acetate (AcOK) (4.7 g, 48 mmol) and [1,1'-bis(diphenylphosphino)ferrocene] palladium dichloride (Pd(dppf)2Cl2) (0.13 g, 0.18 mmol) were placed in a dry reaction bottle with a condenser, and after more than three vacuum and nitrogen ventilation operations, they were dissolved in 200 mL of dry dioxane (1,4-Dioxane). Then the temperature was raised to 100°C and reacted for 12 hours. After the reaction was completed, the reaction mixture was put into water, and the aqueous phase was extracted three times with dichloromethane (500 mL). The obtained dichloromethane phase was washed once with water and dried over anhydrous sodium sulfate. After dichloromethane was removed by reduced pressure distillation, the crude product was washed twice with methanol to obtain compound 1-7 (2.1 g, yield 49%);
[0036] Synthesis of compound 1: Compound 1-7 (8.8 g, 15 mmol) and compound 1-8 (5.8 g, 15 mmol) were completely dissolved in tetrahydrofuran (THF) (50 mL), and 2M potassium carbonate aqueous solution (30 mL) and tetrakis-(triphenylphosphine) palladium (Pd(PPh3)4) (0.6 g, 0.5 mmol) were added thereto, and the mixture was heated and stirred for 5 h. Then, the mixture was cooled to room temperature to complete the reaction, and after removing the potassium carbonate solution, the solid was filtered out and washed once with toluene to obtain compound 1 (10.4 g, yield 90%), MS: 769.43.
[0037] Example 2: Synthesis of Compound 20
[0038]
[0039] The synthesis method of compound 20-2 is the same as that of compound 1-3, except that compound 20-1 is used to replace compound 1-2; the synthesis method of compound 20-4 is the same as that of compound 1-5, except that compound 20-2 is used to replace compound 1-3, and compound 20-3 is used to replace compound 1-4; the synthesis method of compound 20-5 is the same as that of compound 1-7, except that compound 20-4 is used to replace compound 1-5;
[0040] The synthesis method of compound 20 is the same as that of compound 1, except that compound 20-5 is used to replace compound 1-7, MS: 847.45.
[0041] Example 3: Synthesis of Compound 61
[0042]
[0043] The synthesis method of compound 61-2 is the same as that of compound 1-3, except that compound 61-1 is used to replace compound 1-2; the synthesis method of compound 61-3 is the same as that of compound 1-5, except that compound 61-2 is used to replace compound 1-3; the synthesis method of compound 61-4 is the same as that of compound 1-7, except that compound 61-3 is used to replace compound 1-5;
[0044] The synthesis method of compound 61 is the same as that of compound 1, except that compound 61-4 is used to replace compound 1-7, MS: 769.48.
[0045] Example 4: Synthesis of Compound 80
[0046]
[0047]
[0048] The synthesis method of compound 80-2 is the same as that of compound 1-3, except that compound 80-1 is used to replace compound 1-2; the synthesis method of compound 80-4 is the same as that of compound 1-5, except that compound 80-2 is used to replace compound 1-3, and compound 80-3 is used to replace compound 1-4; the synthesis method of compound 80-5 is the same as that of compound 1-7, except that compound 80-4 is used to replace compound 1-5;
[0049] The synthesis method of compound 80 is the same as that of compound 1, except that compound 80-5 is used to replace compound 1-7, MS: 847.17.
[0050] Example 5: Synthesis of Compound 91
[0051]
[0052] The synthesis method of compound 91-2 is the same as that of compound 1-7, except that compound 91-1 is used to replace compound 1-5; the synthesis method of compound 91-4 is the same as that of compound 1-3, except that compound 91-2 is used to replace compound 1-2, and compound 91-3 is used to replace compound 1-1; the synthesis method of compound 91-5 is the same as that of compound 1-7, except that compound 91-4 is used to replace compound 1-5;
[0053] The synthesis method of compound 91 is the same as that of compound 1, except that compound 1-7 is replaced by compound 91-5, and compound 1-8 is replaced by compound 91-6. MS: 783.38.
[0054] Example 6: Synthesis of Compound 101
[0055]
[0056] The synthesis method of compound 101-2 is the same as that of compound 1-7, except that compound 101-1 is used to replace compound 1-5; the synthesis method of compound 101-4 is the same as that of compound 1-3, except that compound 101-2 is used to replace compound 1-2, and compound 101-3 is used to replace compound 1-1; the synthesis method of compound 101-5 is the same as that of compound 1-7, except that compound 101-4 is used to replace compound 1-5;
[0057] The synthesis method of compound 101 is the same as that of compound 1, except that compound 101-5 is used to replace compound 1-7, and compound 91-6 is used to replace compound 1-8. MS: 784.43.
[0058] Example 7: Synthesis of Compound 130
[0059]
[0060] The synthesis method of compound 130-3 is the same as that of compound 1-3, except that compound 130-1 is used to replace compound 1-1, and compound 130-2 is used to replace compound 1-2; the synthesis method of compound 130-5 is the same as that of compound 1-5, except that compound 130-3 is used to replace compound 1-3, and compound 130-4 is used to replace compound 1-4; the synthesis method of compound 130-6 is the same as that of compound 1-7, except that compound 130-5 is used to replace compound 1-5;
[0061] The synthesis of compound 130 was the same as that of compound 1, except that compound 130-6 was used to replace compound 1-7, MS: 873.20.
[0062] Example 8: Synthesis of Compound 151
[0063]
[0064] The synthesis method of compound 151-3 is the same as that of compound 1-3, except that compound 151-1 is used to replace compound 1-1, and compound 151-2 is used to replace compound 1-2; the synthesis method of compound 151-4 is the same as that of compound 1-5, except that compound 151-3 is used to replace compound 1-3; the synthesis method of compound 151-5 is the same as that of compound 1-7, except that compound 151-4 is used to replace compound 1-5;
[0065] The synthesis method of compound 151 is the same as that of compound 1, except that compound 151-5 is used to replace compound 1-7, MS: 847.19.
[0066] Example 9: Synthesis of Compound 170
[0067]
[0068]
[0069] The synthesis method of compound 170-2 is the same as that of compound 1-3, except that compound 170-1 is used to replace compound 1-1, and compound 151-2 is used to replace compound 1-2; the synthesis method of compound 170-4 is the same as that of compound 1-5, except that compound 170-2 is used to replace compound 1-3, and compound 170-3 is used to replace compound 1-4; the synthesis method of compound 170-5 is the same as that of compound 1-7, except that compound 170-4 is used to replace compound 1-5;
[0070] The synthesis method of compound 170 is the same as that of compound 1, except that compound 1-7 is replaced by compound 170-5, MS: 1002.21.
[0071] Example 10: Synthesis of Compound 180
[0072]
[0073]
[0074] The synthesis method of compound 180-1 is the same as that of compound 1-3, except that compound 151-2 is used to replace compound 1-2; the synthesis method of compound 180-2 is the same as that of compound 1-5, except that compound 180-1 is used to replace compound 1-3, and compound 80-3 is used to replace compound 1-4; the synthesis method of compound 180-3 is the same as that of compound 1-7, except that compound 180-2 is used to replace compound 1-5;
[0075] The synthesis method of compound 180 is the same as that of compound 1, except that compound 1-7 is replaced by compound 180-3, and compound 1-8 is replaced by compound 180-4. MS: 948.49.
[0076] In addition, it should be noted that other compounds of the present application can be obtained by referring to the preparation methods of the above-mentioned embodiments, so they will not be listed one by one here.
[0077] Device Embodiment
[0078] Preparation of Example 1:
[0079] A glass substrate coated with ITO (indium tin oxide) as a thin film with a thickness of 1000 angstroms was placed in distilled water in which a detergent was dissolved and ultrasonically cleaned. After the ITO was cleaned for 30 minutes, ultrasonic cleaning was repeated twice with distilled water for 10 minutes, and then the substrate was ultrasonically cleaned with isopropyl alcohol, acetone and methanol solvents, dried, transferred to a plasma cleaner for cleaning for 5 minutes, and then transferred to a vacuum deposition device;
[0080] On the ITO transparent electrode, a compound [HI]: [HT] (3:97) was thermally vacuum deposited to a thickness of 100 angstroms to form a hole injection layer; a compound [HT] was vacuum deposited to 800 angstroms on the hole injection layer to form a hole transport layer; a compound [B-prime] was vacuum deposited to 50 angstroms on the hole transport layer to form an electron blocking layer (also called a buffer layer); a compound [BH] and a compound [BD] were vacuum deposited to a thickness of 200 angstroms on the electron blocking layer at a ratio of 100:2 to form a light-emitting layer; a compound 1 and LiQ were vacuum deposited to a thickness of 300 angstroms on the light-emitting layer at a ratio of 1:1 to form an electron transport layer; yttrium (Yb) and magnesium silver (1:9) were sequentially deposited on the electron transport layer to a thickness of 10 angstroms and 1000 angstroms, respectively, to form a cathode, thereby obtaining the device of Example 1, and the vacuum degree during deposition was maintained at 1×10 -7 Up to 5×10 -8 To support;
[0081] Example 2-10 is obtained by replacing the electron transport layer in the device structure of Example 1 with the corresponding compound in the following table and LiQ vacuum deposited at a ratio of 1:1 to a thickness of 300 angstroms;
[0082] The comparative example was prepared by the same method as in Example 1, except that the comparative compound 1 and the comparative compound 2 were used instead of the compound 1 in Example 1 when forming the electron transport.
[0083] The structure of the compound used in the above preparation process is as follows:
[0084]
[0085] Comparative Compound 1 vs. Compound 2.
[0086] At 10mA / cm 2 The driving voltage and current efficiency of the device embodiments and comparative examples were measured at a current density of 50 mA / cm 2 The time required for the brightness to decrease to 97% of the initial brightness (LT97) was measured at a current density of , wherein the dipole moment was calculated by Gaussian calculation software for the corresponding compound, and the results are shown in Table 1 below:
[0087] Table 1
[0088]
[0089] As can be seen from the above table, compared with Examples 1-10, the driving voltage and current efficiency of Comparative Examples 1 and 2 are basically equivalent, but the life of the embodiment is obviously better than that of the comparative example. On the one hand, this is because the triazine group at one end of the compound of the present application is bonded to the central biphenyl or fluorene derivative in the ortho position, while the comparative example is bonded in the meta or para position, and the rigid ortho-bonding mode with strong steric hindrance increases the dipole moment of the structure of this type of compound; on the other hand, the nitrogen-containing heteroaromatic ring connected to the L group can form an intramolecular hydrogen bond with the adjacent hydrogen on the L group, which increases the planarity of the entire molecule, improves the electron mobility, and further improves the glass transition temperature of the compound, so that the compound has excellent film-forming properties during the preparation of the device, so the life of the prepared device is greatly improved.
Claims
1. A bistriazine compound, characterized in that: The structure is shown in the following general formula I: In the general formula I, Indicates the presence or absence of a bond relationship of Y. When there is no bond relationship of Y, the structure of general formula I becomes the following formulas I-1 and I-2; when there is a bond relationship of Y, the structure of general formula I becomes the following formulas I-3 and I-4: Y is O or S; Ar1 is independently selected from substituted or unsubstituted C6 to C 30 Aryl, when substituted, the substituent is selected from C1 to C 10 Alkyl, cyano, C6~C 18 Aryl, C3~C 18 heteroaryl; L is selected from C6~C 30 Aryl, one of V1, V2, and V3 is nitrogen, and the other two are carbon; Ar2 is selected from substituted or unsubstituted C6~C 30 Aryl, substituent selected from C1~C 10 Alkyl, silane, C6~C 18 Aryl, C3~C 18 Heteroaryl.
2. The bistriazine compound according to claim 1, characterized in that: Ar1 is selected from substituted or unsubstituted C6~C 18 When aryl is substituted, the substituent is selected from C1-C4 alkyl, cyano, phenyl, and nitrogen-containing six-membered heteroaryl.
3. The bistriazine compound according to claim 1, characterized in that: Ar2 is selected from substituted or unsubstituted C6~C 18 When aryl is substituted, the substituent is selected from C1-C4 alkyl, silyl, phenyl, and nitrogen-containing six-membered heteroaryl.
4. The bistriazine compound according to claim 1, characterized in that: Its structure is one of the following:
5. An organic electroluminescent device, comprising a substrate layer, a first electrode located on the substrate layer, and an organic light-emitting functional layer located on the first electrode, characterized in that: The organic light-emitting functional layer comprises the bistriazine compound according to any one of claims 1 to 4.
6. The organic electroluminescent device according to claim 5, characterized in that: The organic light-emitting functional layer comprises an electron transport layer, and the electron transport layer comprises the bistriazine compound according to any one of claims 1 to 4.
7. The organic electroluminescent device according to claim 6, characterized in that: The organic electroluminescent device is used to manufacture display devices, lighting sources, signal lights, and signboards. The display devices include mobile phone display screens, computer display screens, television display screens, smart watch display screens, smart car display panels, and VR or AR helmet display screens.