A compound containing triazine group and an organic electroluminescent device

Abstract

The present invention discloses a compound containing a triazine group and an organic electroluminescent device. In all of the compounds described herein, the 3-position of dibenzofuran is linked to the triazine group, while the adjacent active position of the triazine is directly linked to the nitrogen of the carbazole. Another position of the triazine is linked to an aryl or deuterated aryl group. Experimental and device verification demonstrate that the compounds obtained using this linkage exhibit high luminescence efficiency.

Description

Technical Field

[0001] The present invention relates to the technical field of organic electroluminescence, and in particular to a compound containing a triazine group and an organic electroluminescent device. Background Art

[0002] Generally speaking, organic luminescence refers to the conversion of electrical energy into light using organic materials. Organic electronic devices utilizing organic luminescence typically have a structure comprising an anode and a cathode, with organic material layers between them. These organic layers, such as a hole injection layer, a hole transport layer, and a light-emitting layer, are typically formed from multiple layers of different materials to improve the efficiency and stability of the device.

[0003] Compared to the crystal layers of LEDs (light-emitting diodes) or LCDs (liquid crystal displays), OLED's organic plastic layers are thinner, lighter, and more flexible.

[0004] OLEDs are brighter than LEDs. OLED's organic layers are much thinner than the corresponding inorganic crystal layers in LEDs, allowing for a multi-layered structure for the conductive and emissive layers. Additionally, LEDs and LCDs require glass as a support, which absorbs some light, while OLEDs don't.

[0005] OLEDs don't require the backlighting system found in LCDs. While LCDs selectively block certain backlighting areas to allow images to appear, OLEDs rely on their own light. Because OLEDs don't require a backlighting system, they consume less power than LCDs (most of the power consumed by LCDs goes to the backlighting system). This is especially important for battery-powered devices.

[0006] The most vexing issues with organic electroluminescent devices are lifespan and efficiency. As display areas grow larger, these efficiency and lifespan issues must be addressed. Efficiency, lifespan, and driving voltage are interrelated. When efficiency increases, driving voltage decreases, leading to a trend toward increased lifespan.

[0007] However, it is impossible to maximize efficiency by simply improving the organic material layer. Generally speaking, electrons are transferred from the electron transport layer to the light-emitting layer, and holes are transferred from the hole transport layer to the light-emitting layer, and excitons are generated through recombination.

[0008] As far as the actual needs of the current organic electroluminescent industry are concerned, the current development of organic electroluminescent materials is far from enough and lags far behind the requirements of panel manufacturers. Summary of the Invention

[0009] The purpose of the present invention is to solve the above technical problems and provide a compound containing a triazine group and an organic electroluminescent device.

[0010] The purpose of the present invention can be achieved by the following measures:

[0011] A compound containing a triazine group, the structural formula of which is shown in the following formula (I):

[0012]

[0013] in,

[0014] X is O or S;

[0015] One of a, b, c and d is R1, and the others are H or D;

[0016] R1 and R2 are each independently a substituted or unsubstituted phenyl group, wherein the substituent is deuterium, phenyl or deuterated phenyl;

[0017] R3-R 10 are each independently hydrogen, deuterium or phenyl, and R3-R 10 The number of phenyl groups is 0 or 1;

[0018] R 11 -R 15 each independently hydrogen or deuterium;

[0019] and:

[0020] 1) When a is R1, R2 is phenyl, R 11 -R 15 When all are hydrogen, R6-R7 are hydrogen or deuterium; or

[0021] 2) When a is R1 and R2 is phenyl, R 11 -R 15 at least one of which is deuterium; or

[0022] 3) When a and R2 are phenyl, R3-R 10 When it is hydrogen, R 11 -R 15 Not simultaneously hydrogen;

[0023] 4) When a and R2 are phenyl, R 11 -R 15 When it is hydrogen, R6 or R7 is not phenyl, or R5 and R8 are not phenyl at the same time, or R4 and R9 are not phenyl at the same time.

[0024] Preferably, R1 is R 16 -R 20 Each is independently deuterium, phenyl or deuterated phenyl.

[0025] Preferably, the compound has the structural formula shown in the following formula (II) to formula (V):

[0026]

[0027]

[0028] In formulae (II) to (V), the substituents have the same meanings as in formula (I).

[0029] Preferably, when a is phenyl, R3-R 10 At least one of them is deuterium or phenyl, or R 11 -R 15 At least one of them is deuterium, or R2 is a substituted phenyl group.

[0030] Preferably, R 11 -R 15 The number of deuterated atoms is 3 to 5, and at least R 11 、R 13 、R 15 For deuterium.

[0031] Preferably, R 16 -R 20 The number of deuterated atoms is 3 to 5, and at least R 16 、R 18 、R 20 For deuterium.

[0032] More preferably, the compound of the present invention is any one of the following compounds:

[0033]

[0034]

[0035]

[0036]

[0037]

[0038]

[0039]

[0040]

[0041]

[0042]

[0043]

[0044]

[0045]

[0046]

[0047] A synthetic route of the compound of the present invention is as follows:

[0048]

[0049]

[0050] An organic electroluminescent device comprises a first electrode, a second electrode and an organic layer formed between the first electrode and the second electrode, wherein the organic layer contains the compound of the present invention.

[0051] Furthermore, the organic layer comprises a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer; wherein at least one of the hole injection layer, the hole transport layer, the electron blocking layer, the light-emitting layer, the hole blocking layer, the electron transport layer, and the electron injection layer contains the compound of the present invention.

[0052] Furthermore, the light-emitting layer contains the above-mentioned compound.

[0053] Furthermore, the light-emitting layer further contains at least one of formula (VI):

[0054]

[0055] wherein Y1 and Y2 are each independently a single bond or a substituted or unsubstituted C6 to C20 arylene group,

[0056] Ar1 and Ar2 are each independently a substituted or unsubstituted C6 to C20 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group, and

[0057] Ar3 to Ar 16 Each is independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C2 to C30 heterocyclyl group, a cyano group, or a combination thereof, and the substituent is a C6 to C12 aryl group.

[0058] Further, Y1 and Y2 are each independently a single bond or a substituted or unsubstituted C6 to C12 arylene group,

[0059] Ar1 and Ar2 are each independently a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C6 to C30 heterocyclic group, the substituent being a C6 to C12 aryl group and

[0060] Ar3 to Ar 16 are each independently hydrogen or deuterium.

[0061] Furthermore, the light-emitting layer further contains at least one of the following compounds G1-G72:

[0062]

[0063]

[0064]

[0065] An electronic display device containing the organic electroluminescent device.

[0066] An OLED lighting device containing the organic electroluminescent device.

[0067] The room temperature described in the present invention is 25±5°C.

[0068] The present invention designs a new type of organic electroluminescent material. This type of material has the following characteristics:

[0069] The compounds of the present invention all have a triazine group attached to the 3-position of dibenzofuran, while the adjacent active position of the triazine is directly connected to the nitrogen of the carbazole. Another position of the triazine is connected to an aryl or deuterated aryl group. Experimental and device verification have shown that the compounds obtained using this connection method have high luminescence efficiency.

[0070] In the compounds of the present invention, the hydrogen at the 2-position of dibenzofuran is replaced by a phenyl group or a deuterated phenyl group. The compounds obtained after such replacement have significantly increased steric hindrance and torque, which greatly improves the triplet energy level of such compounds, thereby effectively avoiding the reverse transfer of energy from the guest material to the host material, thereby further improving the luminous efficiency and life of the device.

[0071] In the compound of the present invention, one of the active positions of positions 6 to 9 of dibenzofuran is protected by an aryl group or a deuterated aryl group. This protection method effectively improves the chemical stability and thermal stability of the material, thereby increasing the life of the device.

[0072] The three sites at the ortho and para positions of the benzene ring on the benzofuran ring are relatively active sites. Using deuterium atoms to replace hydrogen atoms at these sites will more effectively improve the thermal stability and chemical stability of the compound. Therefore, the three hydrogen atoms at the ortho and para positions on the phenyl group connected to dibenzofuran are replaced by deuterium atoms, or the other 1-2 hydrogen atoms containing these three deuterium atoms are replaced by deuterium atoms. The resulting compounds have better thermal stability and chemical stability, thereby improving the lifespan and luminous efficiency of the device.

[0073] The present invention, based on the original materials C-1, G17 and other compounds, achieves the purpose of further improving the performance of organic electroluminescent materials while achieving economic efficiency by controlling specific deuteration positions and deuteration amounts, such as trideuteration at the meta-position of the dibenzofuran substituent and single or multiple deuteration at the 1st or 3rd position of the carbazole group.

[0074] Compared with current similar compounds, the material molecules designed in this invention have greater torque, effectively improving the solubility of the material, thereby significantly reducing the preparation cost of the material, and at the same time solving the problems of difficult material cleaning on the production line, large amount of cleaning fluid used, difficult material recovery, and low recovery rate. BRIEF DESCRIPTION OF THE DRAWINGS

[0075] Figure 1 Schematic diagram of the structure of the organic electroluminescent device of the present invention;

[0076] The numbers in the figure represent: 1-anode, 2-hole injection layer, 3-first hole transport layer, 4-second hole transport layer, 5-light-emitting layer, 6-hole blocking layer, 7-electron transport layer, 8-electron injection layer, 9-cathode.

[0077] Figure 2 It is the HPLC chart of compound 1 prepared in Example 1 of the present invention.

[0078] Figure 3 is the DSC spectrum of compound 1 prepared in Example 1 of the present invention, Figure 3 It can be seen that the Tm value of compound 1 is 259.67°C.

[0079] Figure 4 is the TGA spectrum of compound 1 prepared in Example 1 of the present invention, Figure 4 It can be seen that the thermal weight loss temperature Td value is 471.63℃.

[0080] Figure 5 is a life graph of the organic electroluminescent device in Application Example 1 and Comparative Example 1 of the present invention; Figure 5 It can be seen that the T97% lifespans of the organic electroluminescent devices prepared in Application Example 1 and Comparative Example 1 of the present invention are 723 h and 531 h, respectively.

[0081] Figure 6 is the NMR spectrum of compound 8 prepared in Example 5 of the present invention. DETAILED DESCRIPTION

[0082] The following further illustrates and describes embodiments of various aspects. It should be understood that the description herein is not intended to limit the claims to the specific aspects described. On the contrary, it is intended to cover alternatives, modifications, and equivalents that may be included within the spirit and scope of the present disclosure as defined by the appended claims.

[0083] As used herein, in the case of "substituted" or "unsubstituted", the term "substituted" means that at least one hydrogen in the group is re-coordinated with deuterium, a hydrocarbyl group, a hydrocarbon derivative group, a halogen, or a cyano group (-CN). The term "unsubstituted" means that at least one hydrogen in the group is not re-coordinated with deuterium, a hydrocarbyl group, a hydrocarbon derivative group, a halogen, or a cyano group (-CN). Examples of hydrocarbyl or hydrocarbon derivative groups may include C1 to C30 alkyl, C2 to C30 alkenyl, C2 to C30 alkynyl, C6 to C30 aryl, C5 to C30 heteroaryl, C1 to C30 alkylamino, C6 to C30 arylamino, C6 to C30 heteroarylamino, C6 to C30 arylheteroarylamino, etc., but are not limited thereto.

[0084] Among the compounds mentioned in the present invention, at least R 11 、R 13 、R 15 For deuterium, it refers to R 11 、R 13 、R 15 Deuterium or R 11 、R 12 、R 13 、R 15 Deuterium or R 11 、R 13 、R 14 、R 15 or R 11 、R 12 、R 13 、R 14 、R 15 For deuterium.

[0085] Deuterium in the present invention refers to a stable isotope of hydrogen, also known as heavy hydrogen, and its element symbol is D.

[0086] If the specific conditions are not specified in the examples, the experiments were carried out under conventional conditions or those recommended by the manufacturer. All reagents or instruments used, if the manufacturer is not specified, are commercially available conventional products.

[0087] Example 1:

[0088]

[0089] The synthesis method of compound 1 is as follows:

[0090]

[0091]

[0092] Under nitrogen, halide 1-a (23.95 g, 0.1 mol, 1 eq) and boronic acid 1-b (22.8 g, 0.1 mol, 1 eq) were added to a reaction flask. Toluene (300 ml), ethanol (150 ml), potassium carbonate (41.4 g, 0.3 mol, 3 eq) and water (150 ml) were added. After the addition of tetrakistriphenylphosphine palladium (1.155 g, 0.001 mol, 1% eq) was added, the reaction mixture was heated to reflux for 6 hours. The heat was turned off, the temperature was cooled to room temperature, 200 ml of water was added, and the layers were separated. The organic phase was dried over silica gel, concentrated to dryness, and then purified by column chromatography. Approximately 24.62 g of product 1-c was obtained, with a yield of 72.3%.

[0093] Intermediate 1-c (24.62 g, 0.0718 mol, 1 eq) was added to pyridine hydrochloride (276.6 g, 2.394 mol, 30 eq) and the mixture was heated to 190°C and allowed to react overnight. The reaction mixture was also added to water and stirred for 30 minutes before being filtered. The filter cake was dissolved in EA, separated, and concentrated to dryness. Approximately 15.3 g of product 1-d was obtained, with a yield of 68.4%.

[0094] Intermediate 1-d (10.63 g, 0.0337 mol, 1 eq) was added to a reaction flask, followed by NMP (350 ml) and potassium carbonate (13.97 g, 0.1013 mol, 3 eq). After addition, the reaction mixture was heated to 190°C and allowed to react for 4 h. Solids were washed out after addition of water and filtered. The filter cake was washed with water, dissolved in EA, separated, and concentrated to dryness. Approximately 6.84 g of product 1-e was obtained, with a yield of 69.1%.

[0095] Under nitrogen, intermediate 1-e (6.84 g, 0.023 mol, 1 eq) was added to 300 ml of dichloromethane. Triethylamine (7.04 g, 0.069 mol, 3 eq) was added, and the mixture was cooled to 0°C. Trifluoromethanesulfonic anhydride (8.5 g, 0.0301 mol, 1.3 eq) was added dropwise. The reaction was allowed to react for 2 h. Water was added, the mixture was separated with DCM, and the mixture was concentrated to dryness. Approximately 6.96 g of product 1-f was obtained, with a yield of 70.4%.

[0096] Under nitrogen, intermediate 1-f (6.96 g, 0.016 mol, 1 eq) and phenylboronic acid 1-g (1.99 g, 0.016 mol, 1 eq) were added to a reaction flask. Toluene (300 ml), 100 ml of ethanol, potassium carbonate (6.75 g, 0.048 mol, 3 eq) and water (100 ml) were then added. Tetrakistriphenylphosphine palladium (0.19 g, 0.00016 mol, 1 eq) was then added. The reaction mixture was then heated to reflux for 3 hours. The heat was turned off, the temperature was cooled to room temperature, 500 ml of water was added, and the layers were separated. The organic phase was dried over silica gel, concentrated to dryness, and purified by column chromatography. Approximately 4.07 g of product 1-h was obtained, with a yield of 72.1%.

[0097] Under nitrogen, intermediate 1-h (4.07 g, 0.0112 mol, 1 eq) and pinacol diboron (4.25 g, 0.0168 mol, 1.5 eq) were added to a reaction flask. 1,4-dioxane (300 ml) was then added, along with potassium acetate (2.75 g, 0.028 mol, 2.5 eq), palladium acetate (0.125 g, 0.00056 mol, 5% eq), and X-Phos (0.53 g, 0.00112 mol, 10% eq). The mixture was allowed to react overnight. While still hot, the mixture was passed through silica gel, concentrated to dryness, and purified by column chromatography. Approximately 3.4 g of product 1-i was obtained, with a yield of 69.7%.

[0098] Under nitrogen, intermediate 1-i (3.4 g, 0.0076 mol, 1 eq) and halide 1-j (2.72 g, 0.0076 mol, 1 eq) were added to a reaction flask. Toluene (300 ml), ethanol (60 ml), potassium carbonate (2.95 g, 0.0228 mol, 3 eq), water (60 ml), and tetrakistriphenylphosphine palladium (0.0877 g, 0.000076 mol, 1 eq) were also added. After the addition was complete, the reaction solution was heated to reflux for 3 hours. The heat was turned off, water was added, and the mixture was stirred, then filtered. The filter cake was washed with water and ethanol, dried at 85°C by forced air, and purified by recrystallization from toluene. Compound 1 (2.08 g, 42.7% yield) was obtained. ESI-MS (m / z) (M+): Calculated 640.73, Found 640.26; Elemental analysis (molecule C45H28N4O): Calculated C, 84.35; H, 4.40; N, 8.74; O, 2.50. Found C, 84.32; H, 4.43; N, 8.72; O, 2.53.

[0099] Example 2:

[0100]

[0101] The synthesis method of compound 6 is as follows:

[0102]

[0103] Under nitrogen, halide 2-a (24.96 g, 0.08 mol, 1 eq) and boronic acid compound 2-b (10.16 g, 0.08 mol, 1 eq) were added to a reaction flask. Toluene (300 ml), ethanol (150 ml), potassium carbonate (33.1 g, 0.24 mol, 3 eq) and water (150 ml) were then added. After the addition of tetrakistriphenylphosphine palladium (0.924 g, 0.0008 mol, 1% eq), the reaction mixture was heated to reflux for 6 hours. The heat was turned off, the temperature was cooled to room temperature, 200 ml of water was added, and the layers were separated. The organic phase was dried over silica gel, concentrated to dryness, and then purified by column chromatography. Approximately 19.3 g of product 2-c was obtained, with a yield of 73.5%.

[0104] Under nitrogen, halide 2-c (19.3 g, 0.0719 mol, 1 eq) was added to a reaction flask. 500 ml of THF was added, the temperature was cooled to -78°C, and 1.6 M n-butyl lithium (54 ml, 0.0862 mol, 1.2 eq) was added dropwise. After the addition was complete, the reaction was incubated at -78°C for 1 h. Triisopropyl borate (20.48 g, 0.10788 mol, 1.5 eq) was added dropwise. After the addition was complete, the mixture was allowed to warm to room temperature and stirred overnight. The reaction mixture was quenched with 200 ml of water, separated, and the organic phase concentrated to dryness to yield approximately 13.4 g of product 2-d, with a yield of 80.5%.

[0105] Under nitrogen, halide 2-e (13.4 g, 0.05605 mol, 1 eq) and boronic acid 2-d (13.06 g, 0.05605 mol, 1 eq) were added to a reaction flask. Toluene (300 ml), ethanol (100 ml), potassium carbonate (23.20 g, 0.1681 mol, 3 eq) and water (100 ml) were then added. After the addition of tetrakistriphenylphosphine palladium (0.58 g, 0.00054 mol, 1% eq), the reaction solution was heated to reflux for 6 h. The heat was turned off, the temperature was cooled to room temperature, 200 ml of water was added, and the layers were separated. The organic phase was dried over silica gel, concentrated to dryness, and purified by column chromatography to yield approximately 15.6 g of product 2-f, with a yield of 82.3%.

[0106] Intermediate 2-f (15 g, 0.0431 mol, 1 eq) was added to pyridine hydrochloride (150 g, 1.795 mol, 30 eq), the temperature was raised to 190°C and the reaction was allowed to proceed overnight. The reaction mixture was also added to water, stirred for 30 min and filtered. The filter cake was dissolved in EA and the liquid was separated and concentrated to dryness to obtain approximately 9.37 g of product 2-g, with a yield of 67.9%.

[0107] The intermediate 2-g (7.82 g, 0.0244 mol, 1 eq) was added to a reaction flask, and NMP (350 ml) and potassium carbonate (10.12 g, 0.0733 mol, 3 eq) were added. After the addition was completed, the reaction solution was heated to 190°C and reacted for 4 h. After adding water, solids were washed out and filtered. The filter cake was washed with water, dissolved in EA, separated, and concentrated to dryness to obtain approximately 5.0 g of product 2-h, with a yield of 66.5%.

[0108] Under nitrogen protection, intermediate 2-h (5.0 g, 0.0168 mol, 1 eq) was added to 200 ml of dichloromethane, and triethylamine (5.10 g, 0.0504 mol, 3 eq) was added. The temperature was cooled to 0°C, and trifluoromethanesulfonic anhydride (6.16 g, 0.0218 mol, 1.3 eq) was added dropwise. The reaction was allowed to proceed for 2 h. Water was added, the liquid was separated with DCM, and the mixture was concentrated to dryness to obtain approximately 5.11 g of product 2-i with a yield of 70.2%.

[0109] Under nitrogen, intermediate 2-i (5.11 g, 0.01183 mol, 1 eq) and phenylboronic acid 2-j (1.44 g, 0.01183 mol, 1 eq) were added to a reaction flask. Toluene (200 ml), 50 ml of ethanol, potassium carbonate (4.90 g, 0.03552 mol, 3 eq) and water (50 ml) were added. After the addition of tetrakistriphenylphosphine palladium (0.14 g, 0.000118 mol, 1 eq) was added, the reaction mixture was heated to reflux for 3 hours. The heat was turned off, the temperature was cooled to room temperature, 500 ml of water was added, and the layers were separated. The organic phase was dried over silica gel, concentrated to dryness, and purified by column chromatography. Approximately 3.37 g of product 2-k was obtained, with a yield of 79.8%.

[0110] Under nitrogen, intermediate 2-k (3.37 g, 0.0094 mol, 1 eq) and pinacol diboron (3.59 g, 0.0141 mol, 1.5 eq) were added to a reaction flask. 1,4-dioxane (300 ml) was then added, along with potassium acetate (2.32 g, 0.0236 mol, 2.5 eq), palladium acetate (0.104 g, 0.000471 mol, 5% eq), and x-Phos (0.449 g, 0.00094 mol, 10% eq). The mixture was allowed to react overnight. While still hot, the product was passed through silica gel and concentrated to dryness. Purification by column chromatography yielded approximately 3.2 g of product 2-1, with a yield of 75.2%.

[0111] Under nitrogen, intermediate 2-1 (3.2 g, 0.00728 mol, 1 eq) and halide 2-m (2.6 g, 0.00728 mol, 1 eq) were added to a reaction flask. Toluene (200 ml), ethanol (60 ml), potassium carbonate (3.01 g, 0.0218 mol, 3 eq), water (60 ml), and tetrakistriphenylphosphine palladium (0.084 g, 0.0000728 mol, 1% eq) were added. After the addition was complete, the reaction solution was heated to reflux for 3 hours. The heat was turned off, water was added, stirred, and filtered. The filter cake was washed with water and ethanol, dried at 85°C by forced air, and purified by recrystallization from toluene to obtain approximately 2.23 g of compound 6, with a yield of 47.6%. ESI-MS (m / z) (M+): Calculated 645.76, Found 646.18; Elemental analysis (molecule C45H23D5N4O): Calculated C, 83.70; H, 5.15; N, 8.68; O, 2.48. Found C, 83.73; H, 5.12; N, 8.70; O, 2.45.

[0112] Example 3:

[0113]

[0114] The synthesis method of compound 407 is as follows:

[0115]

[0116] Under nitrogen, halide 3-a (23.95 g, 0.1 mol, 1 eq) and boronic acid 3-b (22.8 g, 0.1 mol, 1 eq) were added to a reaction flask. Toluene (300 ml), ethanol (150 ml), potassium carbonate (41.4 g, 0.3 mol, 3 eq) and water (150 ml) were added. After the addition of tetrakistriphenylphosphine palladium (1.155 g, 0.001 mol, 1% eq) was added, the reaction mixture was heated to reflux for 6 hours. The heat was turned off, the temperature was cooled to room temperature, 200 ml of water was added, and the layers were separated. The organic phase was dried over silica gel, concentrated to dryness, and then purified by column chromatography. Approximately 25.86 g of product 3-c was obtained, with a yield of 75.6%.

[0117] Intermediate 3-c (22 g, 0.0638 mol, 1 eq) was added to pyridine hydrochloride (221.2 g, 1.915 mol, 30 eq) and the mixture was heated to 190°C and allowed to react overnight. The reaction mixture was added to water and stirred for 30 min before being filtered. The filter cake was dissolved in EA, separated, and concentrated to dryness. Approximately 13.8 g of product 3-d was obtained, with a yield of 68.7%.

[0118] Intermediate 3-d (13 g, 0.0411 mol, 1 eq) was added to a reaction flask, followed by NMP (350 ml) and potassium carbonate (17.046 g, 0.1235 mol, 3 eq). After addition, the reaction mixture was heated to 190°C and allowed to react for 4 h. Solids were washed out by addition of water and filtered. The filter cake was washed with water, dissolved in EA, separated, and concentrated to dryness. Approximately 8.73 g of product 3-e was obtained, with a yield of 72.1%.

[0119] Under nitrogen, intermediate 3-e (8.55 g, 0.029 mol, 1 eq) was added to 300 ml of dichloromethane. Triethylamine (8.8 g, 0.087 mol, 3 eq) was added, and the mixture was cooled to 0°C. Trifluoromethanesulfonic anhydride (10.635 g, 0.0377 mol, 1.3 eq) was added dropwise. The reaction was allowed to react for 2 h. Water was added, the mixture was separated with DCM, and the mixture was concentrated to dryness. Approximately 8.625 g of product 3-f was obtained, with a yield of 69.7%.

[0120] Under nitrogen, intermediate 3-f (8 g, 0.0189 mol, 1 eq) and phenylboronic acid 3-g (2.30 g, 0.0189 mol, 1 eq) were added to a reaction flask. Toluene (300 ml), 100 ml of ethanol, potassium carbonate (7.812 g, 0.0566 mol, 3 eq) and water (100 ml) were added. Tetrakistriphenylphosphine palladium (0.218 g, 0.000189 mol, 1 eq) were then added. After completion of the addition, the reaction mixture was heated to reflux for 3 hours. The heat was turned off, the temperature was cooled to room temperature, 500 ml of water was added, and the layers were separated. The organic phase was dried over silica gel, concentrated to dryness, and purified by column chromatography. Approximately 4.65 g of product 3-h was obtained, with a yield of 78.3%.

[0121] Under nitrogen, intermediate 3-h (4.65 g, 0.01343 mol, 1 eq) and pinacol diboron (5.1 g, 0.0201 mol, 1.5 eq) were added to a reaction flask. 1,4-dioxane (300 ml) was then added, along with potassium acetate (3.3 g, 0.0336 mol, 2.5 eq), palladium acetate (0.15 g, 0.00067 mol, 5% eq), and x-Phos (0.64 g, 0.00134 mol, 10% eq). The mixture was allowed to react overnight. While still hot, the mixture was passed through silica gel, concentrated to dryness, and purified by column chromatography. Approximately 4.8 g of product 3-i was obtained, with a yield of 80.2%.

[0122] Under nitrogen, intermediate 3-i (4.8 g, 0.0106 mol, 1 eq) and triazine compound 3-j (3.88 g, 0.0106 mol, 1 eq) were added to a reaction flask. Toluene (300 ml), ethanol (60 ml), potassium carbonate (4.405 g, 0.0319 mol, 3 eq), water (60 ml), and tetrakistriphenylphosphine palladium (0.12289 g, 0.000106 mol, 1% eq) were also added. After the addition was complete, the reaction solution was heated to reflux for 3 h. The heat was turned off, water was added, and the mixture was stirred, then filtered. The filter cake was washed with water and ethanol, dried at 85°C, and purified by recrystallization from toluene to obtain approximately 2.72 g of compound 407 in a 39.4% yield. ESI-MS (m / z) (M+): Calculated 648.78, Found 648.50; Elemental analysis (molecule C45H20D8N4O): Calculated C, 83.31; H, 5.59; N, 8.64; O, 2.47. Found C, 83.35; H, 5.60; N, 8.60; O, 2.45.

[0123] Example 85:

[0124]

[0125] The synthesis method of compound 408 is as follows:

[0126]

[0127] Under nitrogen protection, halide 85-a (47.9 g, 0.2 mol, 1 eq) and boronic acid compound 85-b (36.4 g, 0.2 mol, 1 eq) were added to a reaction flask, and toluene (600 ml) and ethanol (300 ml) were added. Potassium carbonate (82.8 g, 0.6 mol, 3 eq) was added to water (300 ml), and tetrakistriphenylphosphine palladium (2.31 g, 0.002 mol, 1% eq) were added. After the addition was completed, the reaction solution was heated to reflux for 6 h, the heating was turned off, the temperature was cooled to room temperature, 200 ml of water was added, the liquids were separated, and the organic phase was dried over silica gel, concentrated to dryness, and column chromatography was performed to obtain approximately 44.1 g of product 85-c in a yield of 74.3%.

[0128] Intermediate 85-c (44.1 g, 0.1486 mol, 1 eq) was added to pyridine hydrochloride (686.88 g, 5.944 mol, 40 eq), and the temperature was raised to 190°C for overnight reaction. The reaction mixture was also added to water, stirred for 30 min, and then filtered. The filter cake was dissolved in EA and the liquid was separated and concentrated to dryness to obtain approximately 29.28 g of product 85-d, with a yield of 77.4%.

[0129] Compound 85-d (29.28 g, 0.115 mol, 1 eq) was added to a reaction flask, followed by NMP (250 ml) and potassium carbonate (47.6 g, 0.345 mol, 3 eq). After the addition was complete, the reaction solution was heated to 190°C and reacted for 4 h. After the addition of water, a solid was washed out and filtered. The filter cake was washed with water, dissolved in EA, separated, and concentrated to dryness to obtain approximately 21.48 g of product 85-e, with a yield of 79.6%.

[0130] Under nitrogen protection, compound 85-e (21.48 g, 0.0916 mol, 1 eq) was added to 200 ml of dichloromethane, and triethylamine (55.6 g, 0.5496 mol, 6 eq) was added. The temperature was cooled to 0°C, and trifluoromethanesulfonic anhydride (67.14 g, 0.238 mol, 2.6 eq) was added dropwise. The reaction was carried out for 2 h, and water was added. The mixture was separated with DCM and concentrated to dryness to obtain approximately 33.8 g of product 85-f with a yield of 74.4%.

[0131] Under nitrogen protection, compound 85-f (33.8 g, 0.0678 mol, 1 eq) and borate compound 85-g (30.64 g, 0.148 mol, 2.18 eq) were added to a reaction flask, and toluene (400 ml), 200 ml of ethanol, potassium carbonate (28.06 g, 0.2034 mol, 3 eq) and water (200 ml) were added. After the addition of tetrakistriphenylphosphine palladium (0.78 g, 0.00068 mol, 1% eq) was completed, the reaction solution was heated to reflux for 3 h, the heating was turned off, the temperature was cooled to room temperature, 500 ml of water was added, the liquids were separated, the organic phase was dried over silica gel, concentrated to dryness, and purified by column chromatography to obtain approximately 19.24 g of product 85-h, with a yield of 78.6%.

[0132] Under nitrogen protection, compound 85-h (19.24 g, 0.0533 mol, 1 eq) and pinacol borate (20.29 g, 0.0799 mol, 1.5 eq) were added to a reaction flask, 1,4-dioxane 300 ml, potassium acetate (13 g, 0.133 mol, 2.5 eq), palladium acetate (0.59 g, 0.0027 mol, 5% eq), and X-Phos (2.54 g, 0.00533 mol, 10% eq) were added, and the reaction was allowed to proceed overnight. The mixture was passed through silica gel while hot, concentrated to dryness, and purified by column chromatography to obtain approximately 15.5 g of product 85-i in a yield of 64.3%.

[0133] Under nitrogen protection, compound 85-i (15.5 g, 0.03426 mol, 1 eq) and triazine compound 85-j (12.22 g, 0.03426 mol, 1 eq) were added to a reaction flask, and toluene (300 ml), 60 ml of ethanol, potassium carbonate (14.18 g, 0.1028 mol, 3 eq), water (60 ml) and tetrakistriphenylphosphine palladium (0.3927 g, 0.00034 mol, 1% eq) were added. After the addition was completed, the reaction solution was heated to reflux for 3 h, the heating was turned off, water was added, and the mixture was filtered after stirring. The filter cake was washed with water and ethanol, dried with air at 85°C, and purified by recrystallization from toluene to obtain about 16 g of compound 408 with a yield of 72.2%. ESI-MS (m / z) (M+): Calculated 646.77, Found 646.63; Elemental analysis (molecule C45H22D6N4O): Calculated C, 83.57; H, 5.30; N, 8.66; O, 2.47. Found C, 83.53; H, 5.34; N, 8.64; O, 2.49.

[0134] The following product compounds were obtained in a similar manner:

[0135] Table 1

[0136]

[0137]

[0138]

[0139]

[0140]

[0141]

[0142]

[0143]

[0144]

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

[0153] The synthesis and identification results of the compounds prepared above are shown in Table 2 below:

[0154] Table 2

[0155]

[0156]

[0157]

[0158] Material property testing:

[0159] Test compounds of the present invention 1, 5, 6, 8, 9, 17, 19, 20, 22, 33, 35, 36, 37, 38, 45, 49, 54, 62, 65, 66, 68, 69, 70, 73, 74, 77, 78, 81, 106, 121, 122, 123, 124, 125, 126, 129, 130, 137, 138, 142, 145, 146, 150, 161, 162, 169, 170, 173, 174, The thermal weight loss temperature Td and melting point Tm of 186, 201, 202, 217, 220, 221, 222, 233, 234, 249, 250, 253, 254, 265, 266, 270, 281, 282, 284, 285, 286, 298, 313, 317, 329, 333, 345, 347, 349, 358, 361, 365, 377, 393, 407, 408, and 416 are shown in Table 3 below.

[0160] Note: Thermogravimetric temperature (Td) is the temperature at which the weight loss is 5% in a nitrogen atmosphere, and was measured on a TGAN-1000 thermogravimetric analyzer with a nitrogen flow rate of 10 mL / min. The melting point (Tm) was determined by differential scanning calorimetry (DSC, Xinke DSC N-650) at a heating rate of 10°C / min.

[0161] Table 3:

[0162]

[0163]

[0164] From the above data, it can be seen that the compounds synthesized in the present invention have excellent thermal stability, which means that the compounds conforming to the general structural formula of the present invention all have excellent thermal stability and can meet the requirements for use as organic electroluminescent materials.

[0165] Device performance test:

[0166] Application Example 1:

[0167] ITO was used as the reflective layer anode substrate material, and its surface was treated with water, acetone, and N2 plasma in sequence;

[0168] On top of the ITO anode substrate, 10 nm of HT-1 doped with 3% by mass of NDP-9 was deposited to form a hole injection layer (HIL);

[0169] A 100 nm layer of HT-1 was evaporated on the hole injection layer (HIL) to form the first hole transport layer (HTL);

[0170] GP was vacuum evaporated on the first hole transport layer (HTL) to form a second hole transport layer (GPL) with a thickness of 30 nm;

[0171] Compound 1 and G1 designed by the present invention were co-evaporated at a mass ratio of 5:5 as green host materials, and GD-1 was evaporated as a doping material (the amount of GD-1 was 8% of the total mass of compound 1 and G1) on the second hole transport layer (GPL) to form a light-emitting layer with a thickness of 30 nm;

[0172] HB-1 was evaporated onto the light-emitting layer to obtain a hole blocking layer (HBL) with a thickness of 20 nm;

[0173] ET-1 and LiQ were co-evaporated onto the hole blocking layer (HBL) in a mass ratio of 5:5 to obtain an electron transport layer (ETL) with a thickness of 30 nm.

[0174] Magnesium (Mg) and silver (Ag) were mixed and evaporated onto the electron transport layer (ETL) in a mass ratio of 9:1 to form an electron injection layer (EIL) with a thickness of 50 nm.

[0175] Silver (Ag) is then evaporated onto the electron injection layer to form a 100nm-thick cathode. A 50nm-thick layer of DNTPD is deposited on the cathode sealing layer. Furthermore, the cathode surface is sealed with a UV-curable adhesive and a seal cap containing a desiccant to protect the organic electroluminescent device from atmospheric oxygen or moisture. Thus, an organic electroluminescent device is prepared.

[0176]

[0177] Application Example 2-86

[0178] Respectively, the compounds 5, 6, 8, 9, 17, 19, 20, 22, 33, 35, 36, 37, 38, 45, 49, 54, 62, 65, 66, 68, 69, 70, 73, 74, 77, 78, 81, 106, 121, 122, 123, 124, 125, 126, 129, 130, 137, 138, 142, 145, 146, 150, 161, 162, 169, 170, 173, 174, 186, 2 01, 202, 217, 220, 221, 222, 233, 234, 249, 250, 253, 254, 265, 266, 270, 281, 282, 284, 285, 286, 298, 313, 317, 329, 333, 345, 347, 349, 358, 361, 365, 377, 393, 407, 408, and 416 are used as green light main materials, and the other parts are consistent with those in Application Example 1. Based on this, the organic electroluminescent device of Application Example 2-86 is manufactured.

[0179] Comparative Examples 1-5:

[0180] The difference from Application Example 1 is that compound G17 in CN 112961145A, compound A-1 in CN112979624B, compound B-1 in CN113387939A, compound C-1 in KR102044943B1, and compound D-1 in KR1020190013139A are used instead of compound 1 as the green light host material, and the rest is the same as Application Example 1.

[0181] The characteristics of the organic electroluminescent device manufactured in the above application example and the organic electroluminescent device manufactured in the comparative example were measured under the condition of a current density of 10 mA / cm2. The results are shown in Table 4.

[0182] Table 4:

[0183]

[0184]

[0185]

[0186]

[0187] As shown in Table 4 above, when the compounds of the present invention are applied to organic electroluminescent devices, at the same current density, the luminous efficiency is significantly improved, the starting voltage of the device is reduced, the power consumption of the device is relatively reduced, and the life of the device is correspondingly increased.

[0188] The organic electroluminescent devices prepared in Control Examples 1-5 and Application Examples 1-20 were subjected to luminescence lifetime tests to obtain luminescence lifetime T97% data (the time it takes for the luminescence brightness to drop to 97% of the initial brightness). The test equipment was a TEO light-emitting device lifetime test system. The results are shown in Table 5:

[0189] Table 5:

[0190]

[0191]

[0192] As can be seen from Table 5 above, when the compound of the present invention is applied to an organic electroluminescent device, the service life is greatly improved at the same current density, and the compound has broad application prospects.

Claims

1. A compound containing a triazine group, characterized in that, Its structural formula is shown in the following formula (I): in, X is O or S; One of a, b, c and d is R1, and the others are H or D; R1 and R2 are each independently a substituted or unsubstituted phenyl group, wherein the substituent is deuterium, phenyl or deuterated phenyl; R3-R 10 are each independently hydrogen, deuterium or phenyl, and R3-R 10 The number of phenyl groups is 0 or 1; R 11 -R 15 each independently hydrogen or deuterium; And: When a and R2 are phenyl, R11-R15 are hydrogen, R3-R 10 At least one of them is deuterium or phenyl, and R6 or R7 is not phenyl.

2. The compound according to claim 1, wherein One of a, b, c and d is R1, and the others are H; R1 is R 16 -R 20 Each is independently deuterium, phenyl or deuterated phenyl.

3. The compound according to claim 1, wherein Its structural formula is shown in the following formula (II) to the following formula (V):

4. The compound according to claim 2, wherein R 11 -R 15 The number of deuterated atoms is 3 to 5, and at least R 11 、R 13 and R 15 is deuterium; or R 16 -R 20 The number of deuterated atoms is 3 to 5, and at least R 16 、R 18 and R 20 For deuterium.

5. The compound according to claim 1, wherein The compound is any one of the following compounds:

6. An organic electroluminescent device, characterized in that: The invention comprises a first electrode, a second electrode and an organic layer formed between the first electrode and the second electrode, wherein the organic layer contains the compound according to any one of claims 1 to 5.

7. An organic electroluminescent device, characterized in that: The method comprises a first electrode, a second electrode, and an organic layer formed between the first electrode and the second electrode, wherein the organic layer comprises a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer; and at least one of the hole injection layer, the hole transport layer, the electron blocking layer, the light-emitting layer, the hole blocking layer, the electron transport layer, and the electron injection layer contains the compound according to any one of claims 1 to 5.

8. An organic electroluminescent device, characterized in that: The invention comprises a first electrode, a second electrode and an organic layer formed between the first electrode and the second electrode, wherein the organic layer comprises a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer; and the light-emitting layer contains the compound according to any one of claims 1 to 5.

9. The organic electroluminescent device according to claim 8, wherein The light-emitting layer further contains at least one of the following formula (VI): Wherein, Y1 and Y2 are each independently a single bond or a C6 to C20 arylene group, Ar1 and Ar2 are each independently a C6 to C20 aryl group or a C2 to C30 heterocyclic group, and Ar3 to Ar 16 Each is independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C2 to C30 heterocyclyl group, a cyano group, or a combination thereof, and the substituent is a C6 to C12 aryl group.

10. The organic electroluminescent device according to claim 8, wherein The light-emitting layer contains a light-emitting host material, which is a mixture of the compound according to any one of claims 1 to 5 and any one or more of compounds G1 to G72. Compounds G1 to G72 are as follows:

11. An electronic display device or an OLED lighting device, characterized in that: Contains the organic electroluminescent device according to claim 6.

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