Triazinyl organic electroluminescent compound and organic light-emitting device

Abstract

The invention discloses a triazinyl organic electroluminescent compound and an organic light-emitting device. The compound comprises a first part structure as shown in a formula A and a second part structure as shown in a formula B: # imgabs0 #. Through the structure innovation that deuterated carbazole, carbazole and a triazinyl group are connected in a para-position / meta-position mode, and an ortho-position phenyl group of the triazinyl group is arranged on a transition phenyl group, the triazinyl organic electroluminescent compound has the advantages that the triazinyl organic electroluminescent compound is high in luminous efficiency and high in luminous efficiency. The stability, charge transfer efficiency, molecular accumulation control and the like are obviously superior to those in the prior art, and the performance and the service life of the device are improved.

Description

Technical Field

[0001] The present invention relates to the technical field of organic electroluminescence, and particularly relates to a triazine-based organic electroluminescent compound and an organic light-emitting device. Background Art

[0002] An organic light-emitting device (OLED) is a display technology that uses an electric field to excite a fluorescent material to emit light. Its working principle is that under the action of an electric field, holes injected from the positive electrode and electrons injected from the negative electrode recombine in the light-emitting layer to generate light. OLEDs have wide applications in mobile phones, tablet computers, television displays, lighting, and other fields due to their advantages such as low-voltage startup, high brightness, wide viewing angle, fast response, and good temperature adaptability.

[0003] The composition structure of an organic light-emitting device includes a cathode, an anode, and an organic layer disposed therebetween. Currently, the organic layer structure of OLED devices applied in the industry is usually a multi-layer structure, for example, including a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and other film layers. For an OLED device including the above film layers, when a voltage is applied between the two electrodes, holes are injected from the anode into the organic layer, and electrons are injected from the cathode into the organic layer. When the holes and electrons meet, excitons are formed. When the excitons transfer energy to the doped material, light is emitted through the radiative transition of the doped material.

[0004] A compound is disclosed in the invention patent with the patent number of 《US12029120B2》, which contains a deuterated carbazole group and a phenyl group connected to the N in the carbazole, and other substituents are provided on the phenyl group, and the following specific structure is disclosed in this patent This patent applies the above compound to the host material of a delayed fluorescence compound in the specification.

[0005] A compound is disclosed in the invention patent with the patent number of 《US20180248127》, which contains carbazole, phenyl, and triazine, where carbazole and triazine are connected in a para position, and the following specific structure is specifically disclosed This patent applies the above compound to the fluorescent host material in the specification.

[0006] A compound is disclosed in the invention patent with the patent number of 《CN119384416A》 And the following specific structure is specifically disclosed And it is applied to the light-emitting host material.

[0007] A compound is disclosed in the invention patent with the patent number of 《CN116457351A》 And the following specific structure is specifically disclosed This compound is applied to a two-component light-emitting host material.

[0008] When the above materials are applied to an organic electroluminescent device, the compatibility between the green light hosts is poor, resulting in inefficient energy transfer to the doped material and a decrease in the efficiency of the conductor OLED device. At the same time, since deuteration is not carried out at the active sites and the sites with high electron density of the material molecules, its chemical stability, thermal stability and optoelectronic stability are poor, thus affecting the lifetime of the device. Moreover, for the current green light hosts, as the evaporation time prolongs, the P / N ratio changes greatly, resulting in large fluctuations in device performance, poor stability and low yield. Summary of the Invention

[0009] The object of the present invention is to solve the above technical problems. The present invention provides a compound comprising a first partial structure shown in Formula A and a second partial structure shown in Formula B:

[0010] In Formula A, one of the bonds of Ar1 and Ar2 is bonded to the * position of Formula B, and the other of Ar1 and Ar2 is hydrogen or deuterium. R1-R 25 is independently selected from hydrogen, deuterium, hydroxyl group, cyano group, C1-C4 straight-chain or branched-chain alkyl group, C5-C6 cycloalkyl group, substituted or unsubstituted C5-C40 aryl group, substituted or unsubstituted C5-C40 heteroaryl group, and the substituents are selected from at least one of the following atoms or groups: deuterium, hydroxyl group, cyano group, monodeuteriomethyl group, dideuteriomethyl group, trideuteriomethyl group, C1-C4 straight-chain or branched-chain alkyl group, C6-C18 aryl group, C5-C24 heteroaryl group, and at least one of R1-R8 is deuterium.

[0011] As a preferred embodiment of the present invention, R1-R 25 are each independently selected from hydrogen, deuterium, cyano group, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, phenyl group, anthryl group, naphthyl group, phenanthryl group; the methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, phenyl group, anthryl group, naphthyl group, phenanthryl group are unsubstituted or a group obtained by substituting at least one hydrogen therein with deuterium, deuterated or non-deuterated C1-C4 straight-chain or branched-chain alkyl group, deuterated or non-deuterated phenyl group, and at least one of R1-R8 is deuterium.

[0012] As a preferred embodiment of the present invention, R1-R8 are selected from deuterium, phenyl group, deuterated phenyl group and at least 7 of R1-R8 are deuterium; R9-R 10 are each independently selected from hydrogen, deuterium; R 11 -R 15 are each independently selected from hydrogen, deuterium, phenyl group, deuterated phenyl group; R 16 -R 25 are each independently selected from hydrogen, deuterium, phenyl group, deuterated phenyl group.

[0013] As an alternative embodiment of the present invention, the triazine-based organic electroluminescent compound is as shown in Formula C: R1-R8 are selected from deuterium, phenyl, deuterated phenyl and at least 7 of R1-R8 are deuterium; R9, R 10 , R 26 are each independently selected from hydrogen, deuterium; R 11 -R 15 are each independently selected from hydrogen, deuterium, phenyl, deuterated phenyl; R 16 -R 25 are each independently selected from hydrogen, deuterium, phenyl, deuterated phenyl.

[0014] As an alternative embodiment of the present invention, the triazine-based organic electroluminescent compound is as shown in Formula D: R1-R8 are selected from deuterium, phenyl, deuterated phenyl and at least 7 of R1-R8 are deuterium; R9, R 10 , R 26 are each independently selected from hydrogen, deuterium; R 11 -R 15 are each independently selected from hydrogen, deuterium, phenyl, deuterated phenyl; R 16 -R 25 are each independently selected from hydrogen, deuterium, phenyl, deuterated phenyl.

[0015] As a preferred embodiment of the present invention, the triazine-based organic electroluminescent compound is one of the compounds with the following structural formulas:

[0016]

[0017]

[0018]

[0019]

[0020]

[0021]

[0022]

[0023]

[0024]

[0025] An organic electroluminescent device, comprising 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 organic electroluminescent compound of any one of the above.

[0026] As a preferred embodiment of the present invention, the organic layer includes 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; 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 organic electroluminescent compound of any one of the above.

[0027] As a preferred embodiment of the present invention, the light-emitting layer further contains at least one of the following formula E or formula F: Wherein, Y1 and Y2 are each independently a single bond, a substituted or unsubstituted C6-C20 arylene group; Y3 and Y4 are each independently a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C2-C24 heteroaryl group; Ar3 to Ar 16 are each independently hydrogen, deuterium, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C2-C24 heteroaryl group, a cyano group or a combination thereof, and the substituent is a C6-C20 aryl group.

[0028] As a preferred embodiment of the present invention, the light-emitting layer contains a light-emitting host material, and the light-emitting host material is composed of a compound described in any one of claims 1-6 and one or more of compounds P1-P78, and the compounds P1-P78 are as follows:

[0029]

[0030]

[0031]

[0032] Advantages of the present invention:

[0033] The compound of the present invention contains a triazine group and a carbazole group, wherein all the electron-rich groups of carbazole are deuterated, and carbazole is connected to the excessive phenyl group at the para-position or meta-position of the triazine group, and a phenyl group adjacent to the triazine group is also provided on the excessive phenyl group; all the electron-rich groups of carbazole being deuterated improves the thermal stability, reduces the C-H vibration, and enhances the light-emitting efficiency (reduces non-radiative decay);

[0034] Further combined with the new connection site and phenyl modification, when carbazole is at the para-position of the triazine group, the conjugation is better, which is beneficial to charge transport; when carbazole is at the meta-position of the triazine group, the molecular symmetry can be adjusted to avoid excessive rigidity;

[0035] The ortho-phenyl group with a triazine group on the excessive phenyl group provides steric hindrance to inhibit molecular aggregation (reduce exciton quenching); at the same time, it promotes π-π stacking, improving the film uniformity and carrier mobility.

[0036] Through the structural innovation of deuterated carbazole, the para / meta connection of carbazole and triazine group, and the ortho-phenyl group with a triazine group on the excessive phenyl group, the present invention is significantly superior to the prior art in terms of stability, charge transport efficiency, molecular packing control, etc.

[0037] In the N-type material structure of the present invention, all the electron-rich groups of carbazole are deuterated, and at the same time, the core region (HOMO electron distribution region) of the paired P-type is also deuterated. The simultaneous deuteration of the two types of materials greatly improves the chemical stability, optoelectronic stability and thermal stability of the material structure, improves the stability of the device, and thus improves the lifespan.

[0038] It can form a good Premix material with the P-type compound of the present invention, has good P / N stability and mass production stability during the evaporation process, improves the production yield of the device, and the formed Premix material has a more balanced carrier mobility, thus greatly improving the efficiency and lifespan of the device.

[0039] The compound of the present invention has good solubility, effectively reducing the preparation cost of the material and the cleaning cost of the Mask. Brief Description of the Drawings

[0040] Figure 1 It is a schematic structural diagram of the organic electroluminescent device provided by the present invention;

[0041] The reference numerals in the figure respectively represent: 1 - anode, 2 - hole injection layer, 3 - 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.

[0042] Figure 2 It is the HPLC spectrum of Compound 1 of the present invention.

[0043] Figure 3 It is the DSC spectrum of Compound 1 of the present invention. From Figure 3 it can be seen that the Tg value of Compound 1 is 105.52 °C.

[0044] Figure 4 It is the TGA spectrum of Compound 1 of the present invention. From Figure 4 it can be seen that the thermal weight loss temperature Td value of Compound 1 is 386.60 °C. Detailed Description of the Invention

[0045] Embodiments of various aspects are further illustrated and described below. It should be understood that the description herein is not intended to limit the claims to the specific aspects described. Instead, 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.

[0046] As used herein, in "deuterated" or "non-deuterated", the term "deuterated" means that at least one hydrogen in the group is re-coordinated with deuterium. The term "non-deuterated" means that all hydrogens in the group are not re-coordinated with deuterium.

[0047] The "aromatic group", "aryl", or "aromatic radical" herein refers to a group containing one or more aromatic rings, where the aromatic rings include, but are not limited to, benzene, naphthalene, phenanthrene, fluorene, acenaphthene, pyridine, pyrimidine, pyrrole, furan, thiophene, etc. C5-C40 in the C5-C40 aromatic group means that the group contains 5-40 carbon atoms. Aromatic groups can be divided into monocyclic aryls and polycyclic aryls. Specific aromatic groups in the present invention include, but are not limited to, phenyl, biphenyl, terphenyl, anthryl, naphthyl, phenanthryl, fluorenyl, dibenzofuranyl, dibenzothiophenyl, 9,9-spirobifluorenyl, 9,9-dimethylfluorenyl, or 9,9-diphenylfluorenyl, etc. Aromatic groups can be substituted and unsubstituted.

[0048] The "cycloalkyl" herein refers to a monocyclic or fused ring (a "fused" ring means that each ring in the system shares an adjacent pair of carbon atoms with other rings in the system) group consisting entirely of carbon, where one or more rings are saturated alicyclic rings, which generally have 3-20 carbon atoms, preferably 3-12 carbon atoms, more preferably 3-10 carbon atoms. Cycloalkyls can be divided into monocyclic alkyls having only one ring and fused cycloalkyls having multiple rings. Examples of monocyclic alkyls include, but are not limited to, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane. Cycloalkyls can be substituted and unsubstituted.

[0049] The "cycloalkenyl" herein refers to a monocyclic or fused ring (a "fused" ring means that each ring in the system shares an adjacent pair of carbon atoms with other rings in the system) group consisting entirely of carbon, where one or more rings do not have a completely conjugated π-electron system and contain at least one alkenyl group, which generally has 3-20 carbon atoms, preferably 3-12 carbon atoms, more preferably 3-10 carbon atoms. Examples of cycloalkenyls include, but are not limited to, cyclopentene, cyclohexene, cyclohexadiene, cycloheptatriene. Cycloalkenyls can be substituted and unsubstituted.

[0050] The "deuterated aromatic group" herein refers to a group in which one or more hydrogen atoms in the aromatic group are replaced by deuterium.

[0051] The "deuterated phenyl" herein refers to a group in which 1 or more hydrogens in the phenyl are replaced by deuterium.

[0052] "Heteroaryl" as used herein refers to a heteroaryl group obtained by substituting one or more C in the structure of "aryl" with one or more heteroatoms (such as N, O, or S).

[0053] For those without specific conditions noted in the examples, they are carried out under conventional conditions or conditions recommended by the manufacturer. For reagents or instruments without the manufacturer noted, they are all conventional products that can be obtained by purchasing in the market.

[0054] Example 1

[0055] Compound 1

[0056]

[0057] Compound 1 was prepared according to the following method:

[0058] Step S1:

[0059] Procedure: Add SM2 (50 g, 0.2855 mol, 1 eq), SM1 (89.7 g, 0.4282 mol, 1.5 eq), cesium carbonate (279 g, 0.8565 mol, 3 eq) and DMF (500 ml) into a 1 L three-necked flask, heat to 100 °C and stir for reaction for 24 h, monitor by HPLC until SM2 ≤ 1%.

[0060] Work-up: Stop the reaction, filter while it is hot, add 1.5 L of water to the filtrate, stir for crystallization for 2 - 3 h, filter by suction, add 200 ml of ethanol to the filter cake and stir for pulping for 2 h, filter by suction, dry the filter cake in a blast dryer at 85 °C to obtain 94.9 g of a off-white solid, with a yield of 91.2%.

[0061] Step S2:

[0062] Procedure: Add ZJ1 (85 g, 0.233 mol, 1 eq), SM3 (29.85 g, 0.2448 mol, 1.05 eq), potassium carbonate (64.4 g, 0.466 mol, 2 eq) and toluene / ethanol / water (850 ml + 425 ml + 255 ml) into a 2 L three-necked flask, under N2 protection, add tetrakis(triphenylphosphine)palladium (5.38 g, 4.66 mmol, 0.02 eq), heat to reflux and stir for reaction, monitor by HPLC until ZJ1 ≤ 1%.

[0063] Work-up: Stop the reaction, add 200 ml of water, stir and separate the layers, extract the aqueous phase with DCM, combine the organic phases, filter through silica gel by suction, concentrate the filtrate under reduced pressure to dryness, add 150 ml of ethanol, heat and stir for pulping for 2 h, cool to room temperature for crystallization, filter by suction, dry the filter cake in a blast dryer at 85 °C to obtain 72.2 g of a off-white solid, with a yield of 85.6%.

[0064] Step S3:

[0065] Procedure: Add ZJ2 (72 g, 0.199 mol, 1 eq), bis(pinacolato)diboron (65.7 g, 0.2587 mol, 1.3 eq), potassium acetate (57.4 g, 0.597 mol, 3 eq), XPhos (5.69 g, 11.94 mmol, 0.06 eq) and 1,4-dioxane (700 ml) into a 1 L three-necked flask. Under N2 protection, add palladium acetate (1.34 g, 5.97 mmol, 0.03 eq), heat up to 110 °C and stir for reaction. Monitor the reaction by HPLC until ZJ2 ≤ 1%.

[0066] Workup: Stop the reaction, filter through silica gel while it is hot under suction. Wash the filter cake with DCM. Concentrate the filtrate under reduced pressure to dryness. Add 150 ml of ethanol, heat and stir to form a slurry for 2 h. Cool down to room temperature for crystallization, then filter under suction. Dry the filter cake in a blast dryer at 85 °C to obtain 70 g of gray solid with a yield of 77.6%.

[0067] Step S4:

[0068] Procedure: Add ZJ3 (50 g, 0.11 mol, 1.1 eq), SM4 (26.8 g, 0.1 mol, 1 eq), potassium carbonate (27.64 g, 0.2 mol, 2 eq) and toluene / ethanol / water (500 ml + 250 ml + 150 ml) into a 2 L three-necked flask. Under N2 protection, add tetrakis(triphenylphosphine)palladium(0) (2.3 g, 2 mmol, 0.02 eq), heat up to reflux and stir for reaction. Monitor the reaction by HPLC until SM3 ≤ 1%.

[0069] Workup: Stop the reaction, add 200 ml of water, stir and separate the layers. Extract the aqueous layer with DCM. Combine the organic phases, filter through silica gel under suction. Concentrate the filtrate under reduced pressure to dryness. Add 150 ml of ethanol, heat and stir to form a slurry for 2 h. Cool down to room temperature for crystallization, then filter under suction. Recrystallize the filter cake 5 times with toluene / ethanol, filter under suction. Dry the filter cake in a blast dryer at 85 °C to obtain 32.5 g of off-white solid with a yield of 58.2%.

[0070] Compounds 2, 4, 6, 7, 8, 9, 11, 13, 16, 21, 23, 31, 38, 42, 46, 51, 52, 56, 57, 58, 61, 62, 63, 71, 74, 76, 77, 79, 81, 83, 86, 88, 91, 96, 98, 101, 106 are obtained in a similar method. See Table 1 below:

[0071] Table 1

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079] Example 39

[0080] Compound 116

[0081]

[0082] Compound 116 was prepared according to the following method:

[0083] Step S1:

[0084] Procedure: Add SM2 (50 g, 0.2855 mol, 1 eq), SM1 (89.7 g, 0.4282 mol, 1.5 eq), cesium carbonate (279 g, 0.8565 mol, 3 eq) and DMF (500 ml) into a 1 L three-necked flask, heat up to 100 °C and stir for reaction for 24 h, monitor by HPLC until SM2 ≤ 1%.

[0085] Work-up: Stop the reaction, filter while it is hot, add 1.5 L of water to the filtrate, stir for crystallization for 2 - 3 h, filter by suction, add 200 ml of ethanol to the filter cake and stir for pulping for 2 h, filter by suction, dry the filter cake in a blast dryer at 85 °C to obtain 91.6 g of a white solid, with a yield of 88%.

[0086] Step S2:

[0087] Procedure: Add ZJ1 (85 g, 0.233 mol, 1 eq), SM3 (29.85 g, 0.2448 mol, 1.05 eq), potassium carbonate (64.4 g, 0.466 mol, 2 eq) and toluene / ethanol / water (850 ml + 425 ml + 255 ml) into a 2 L three-necked flask, under N2 protection, add tetrakis(triphenylphosphine)palladium (5.38 g, 4.66 mmol, 0.02 eq), heat up to reflux and stir for reaction, monitor by HPLC until ZJ1 ≤ 1%.

[0088] Workup: Stop the reaction, add 200 ml of water, stir and separate the layers. Extract the aqueous phase with DCM, combine the organic phases, filter through silica gel by suction, concentrate the filtrate under reduced pressure to dryness, add 150 ml of ethanol, heat and stir to form a slurry for 2 h, cool to room temperature for crystallization, filter by suction, and dry the filter cake in a blast dryer at 85 °C to obtain 70.9 g of a white solid, with a yield of 84.1%.

[0089] Step S3:

[0090] Procedure: Add ZJ2 (70 g, 0.1935 mol, 1 eq), bis(pinacolato)diboron (63.9 g, 0.2515 mol, 1.3 eq), potassium acetate (57 g, 0.5805 mol, 3 eq), XPhos (5.53 g, 11.61 mmol, 0.06 eq) and 1,4-dioxane (700 ml) into a 1 L three-necked flask. Under N2 protection, add palladium acetate (1.3 g, 5.805 mmol, 0.03 eq), heat to 110 °C and stir for reaction, monitor by HPLC until ZJ2 ≤ 1%.

[0091] Workup: Stop the reaction, filter through silica gel by suction while it is hot, wash the filter cake with DCM, concentrate the filtrate under reduced pressure to dryness, add 150 ml of ethanol, heat and stir to form a slurry for 2 h, cool to room temperature for crystallization, filter by suction, and dry the filter cake in a blast dryer at 85 °C to obtain 68.9 g of a grey solid, with a yield of 78.6%.

[0092] Step S4:

[0093] Procedure: Add ZJ3 (50 g, 0.11 mol, 1.1 eq), SM4 (26.8 g, 0.1 mol, 1 eq), potassium carbonate (27.64 g, 0.2 mol, 2 eq) and toluene / ethanol / water (500 ml + 250 ml + 150 ml) into a 2 L three-necked flask. Under N2 protection, add tetrakis(triphenylphosphine)palladium(0) (2.3 g, 2 mmol, 0.02 eq), heat to reflux and stir for reaction, monitor by HPLC until SM3 ≤ 1%.

[0094] Workup: Stop the reaction, add 200 ml of water, stir and separate the layers. Extract the aqueous phase with DCM, combine the organic phases, filter through silica gel by suction, concentrate the filtrate under reduced pressure to dryness, add 150 ml of ethanol, heat and stir to form a slurry for 2 h, cool to room temperature for crystallization, filter by suction, recrystallize the filter cake 5 times with toluene / ethanol, filter by suction, and dry the filter cake in a blast dryer at 85 °C to obtain 34 g of a white solid, with a yield of 60.9%.

[0095] Compounds were obtained in a similar manner: 117, 121, 122, 123, 124, 126, 128, 129, 136, 138, 141, 166, 167, 171, 172, 173, 176, 177, 178, 181, 186, 189, 191, 192, 194, 196, 198, 201, 203, 211, 221, 226. See Table 2 below:

[0096] Table 2

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104] Example 71 Compound 3

[0105]

[0106] Step S1:

[0107] Procedure: Add SM1 (100 g, 0.4775 mol, 1 eq), silver carbonate (26.3 g, 95.5 mmol, 0.2 eq), dicyclohexylphenylphosphine (64.06 g, 0.239 mol, 0.5 eq), heavy water (191 g, 9.55 mol, 20 eq) and toluene (48 ml) into a 1 L single-necked flask, heat up to 120 °C and stir for reaction for 24 h.

[0108] Workup: Stop the reaction, filter by silica gel suction filtration, add DCM to the filtrate and stir for liquid separation, extract the aqueous phase with DCM, combine the organic phases and concentrate under reduced pressure to dryness, purify by column chromatography (rinsed with pure PE), collect the product spots, concentrate to dryness under reduced pressure, and then continue deuteration (recharge according to the above feeding amount and perform workup), finally obtaining 91.2 g of colorless oil, with a yield of 89.9%.

[0109] Step S2:

[0110] Procedure: Add SM2 (50 g, 0.2855 mol, 1 eq), SM1 (91 g, 0.4282 mol, 1.5 eq), cesium carbonate (279 g, 0.8565 mol, 3 eq) and DMF (500 ml) into a 1 L three-necked flask. Heat up to 100 °C and stir for reaction for 24 h. Monitor by HPLC with SM2 ≤ 1%.

[0111] Work-up: Stop the reaction, filter while it is hot. Add 1.5 L of water to the filtrate, stir for crystallization for 2 - 3 h, then filter by suction. Add 200 ml of ethanol to the filter cake, stir and slurry for 2 h, then filter by suction again. Dry the filter cake in a blast dryer at 85 °C to obtain 93.6 g of off-white solid, with a yield of 89.2%.

[0112] Step S3:

[0113] Procedure: Add ZJ2 (85.65 g, 0.233 mol, 1 eq), SM3 (31.1 g, 0.2448 mol, 1.05 eq), potassium carbonate (64.4 g, 0.466 mol, 2 eq) and toluene / ethanol / water (850 ml + 425 ml + 255 ml) into a 2 L three-necked flask. Under N2 protection, add tetrakis(triphenylphosphine)palladium (5.38 g, 4.66 mmol, 0.02 eq). Heat up to reflux and stir for reaction. Monitor by HPLC with ZJ2 ≤ 1%.

[0114] Work-up: Stop the reaction, add 200 ml of water, stir and separate the layers. Extract the aqueous phase with DCM. Combine the organic phases, filter through silica gel by suction. Concentrate the filtrate under reduced pressure to dryness. Add 150 ml of ethanol, heat and stir for slurrying for 2 h. Cool down to room temperature for crystallization, then filter by suction. Dry the filter cake in a blast dryer at 85 °C to obtain 72.1 g of off-white solid, with a yield of 83.7%.

[0115] Step S4:

[0116] Procedure: Add ZJ2 (71.6 g, 0.1935 mol, 1 eq), bis(pinacolato)diboron (63.9 g, 0.2515 mol, 1.3 eq), potassium acetate (57 g, 0.5805 mol, 3 eq), XPhos (5.53 g, 11.61 mmol, 0.06 eq) and 1,4-dioxane (700 ml) into a 1 L three-necked flask. Under N2 protection, add palladium acetate (1.3 g, 5.805 mmol, 0.03 eq). Heat up to 110 °C and stir for reaction. Monitor by HPLC with ZJ2 ≤ 1%.

[0117] Workup: Stop the reaction, filter through silica gel while it is still hot by suction filtration. Wash the filter cake with DCM. Concentrate the filtrate under reduced pressure until dry. Add 150 ml of ethanol, heat and stir to form a slurry for 2 h. Cool down to room temperature for crystallization. Filter by suction. Dry the filter cake in a forced-air oven at 85 °C to obtain 70.2 g of a gray solid with a yield of 78.6%.

[0118] Step S5:

[0119] Procedure: Add ZJ3 (50.7 g, 0.11 mol, 1.1 eq), SM4 (26.8 g, 0.1 mol, 1 eq), potassium carbonate (27.64 g, 0.2 mol, 2 eq) and toluene / ethanol / water (500 ml + 250 ml + 150 ml) into a 2 L three-necked flask. Under N2 protection, add tetrakis(triphenylphosphine)palladium (2.3 g, 2 mmol, 0.02 eq). Heat up to reflux and stir for reaction, monitor by HPLC until SM3 ≤ 1%.

[0120] Workup: Stop the reaction, add 200 ml of water, stir and separate the layers. Extract the aqueous phase with DCM. Combine the organic phases, filter through silica gel by suction. Concentrate the filtrate under reduced pressure until dry. Add 150 ml of ethanol, heat and stir to form a slurry for 2 h. Cool down to room temperature for crystallization. Filter by suction. Recrystallize the filter cake 5 times with toluene / ethanol. Filter by suction. Dry the filter cake in a forced-air oven at 85 °C to obtain 31.9 g of an off-white solid with a yield of 56.5%.

[0121] Compounds 5, 10, 35, 53, 55, 60, 78, 80, 85, 103, 105, 108, 118, 120, 125, 130, 168, 175, 193, 218, 223, 225 were obtained in a similar manner. See Table 3 below:

[0122] Table 3

[0123]

[0124]

[0125]

[0126]

[0127]

[0128]

[0129]

[0130] The synthesized compounds above were identified, and the results are shown in Table 4 below:

[0131] Table 4

[0132]

[0133]

[0134]

[0135]

[0136] The basic performance tests were carried out on the above materials, and the thermal decomposition temperature Td and the glass transition temperature Tg were tested respectively. The test results are shown in Table 5 below.

[0137] Note: The thermal decomposition temperature Td is the temperature at which the mass loss ratio is 5% in a nitrogen atmosphere, and it is measured on a TGA N-1000 thermogravimetric analyzer. The nitrogen flow rate is 10 mL / min during the measurement. The Tg (glass transition temperature) is measured by differential scanning calorimetry (DSC, Shinke DSC N-650), and the heating rate is 10 °C / min.

[0138] Table 5

[0139]

[0140]

[0141]

[0142] According to the above data, it can be seen that the compound synthesized by the present invention has excellent thermal stability, indicating 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.

[0143] Device performance test:

[0144] Application Example 1:

[0145] ITO was used as the anode substrate material of the reflective layer, and its surface was treated with water, acetone, and N2 plasma in sequence;

[0146] Above the ITO anode substrate, 10 nm of HT-1 doped with 5% NDP-9 was deposited to form a hole injection layer (HIL);

[0147] Above the hole injection layer (HIL), 100 nm of HT-1 was evaporated to form a hole transport layer (HTL);

[0148] Above the hole transport layer (HTL), GP-1 was vacuum-evaporated to form an electron blocking layer (GPL) with a thickness of 10 nm;

[0149] The compound 1 prepared in Example 1 of the present invention and compound P-1 were co-evaporated as a light-emitting host material in a ratio of 5:5, and GD-1 was evaporated as a doping material (the amount of GD-1 was 8% of the total weight of compound 1 and P-1) on the electron blocking layer (GPL) to form a light-emitting layer with a thickness of 20 nm;

[0150] HB-1 was evaporated onto the light-emitting layer to obtain a hole blocking layer (HBL) with a thickness of 20 nm;

[0151] ET-1 and LiQ were co-evaporated onto the hole blocking layer (HBL) in a ratio of 5:5 to obtain an electron transport layer (ETL) with a thickness of 30 nm;

[0152] Magnesium (Mg) and silver (Ag) were co-evaporated in a ratio of 9:1 above the electron transport layer (ETL) to form an electron injection layer (EIL) with a thickness of 50 nm;

[0153] Thereafter, silver (Ag) was evaporated above the electron injection layer to form a cathode with a thickness of 100 nm. DNTPD with a thickness of 50 nm was deposited on the above cathode sealing layer. In addition, the cathode surface was sealed with a UV-curable adhesive and a packaging film (seal cap) containing a dehumidifying agent to protect the organic electroluminescent device from being affected by oxygen or moisture in the atmosphere. Thus, the organic electroluminescent device was prepared.

[0154]

[0155]

[0156]

[0157] Application Example 2 - 45:

[0158] Using the compounds 2, 4, 6, 7, 8, 9, 11, 13, 16, 21, 23, 31, 38, 42, 46, 51, 52, 56, 57, 58, 61, 62, 63, 71, 74, 76, 77, 79, 81, 83, 86, 88, 91, 96, 98, 101, 106, 116, 117, 121, 122, 123, 124, 126, 128, 129, 136, 138, 141, 166, 167, 171, 172, 173, 176, 177, 178, 181, 186, 189, 191, 192, 194, 196, 198, 201, 203, 211, 221, 226, 3, 5, 10, 35, 53, 55, 60, 78, 80, 85, 103, 105, 108, 118, 120, 125, 130, 168, 175, 193, 218, 223, 225 in Example 2 - 93 of the present invention to replace compound 1 in Application Example 1 as the green light host material for co-evaporation, and the other parts are the same as those in Application Example 1. Accordingly, the organic electroluminescent devices of Application Examples 2 - 93 are fabricated.

[0159] Comparative Examples 1 - 9:

[0160] Differing from Application Example 1, D1 - 1, D1 - 2, D1 - 3, D1 - 4, D1 - 5, D1 - 6 in 《US12029120B2》 are respectively used to replace compound 1 in Application Example 1 as the green light host material for co-evaporation, and the rest are the same as those in Application Example 1. Accordingly, the organic electroluminescent devices of Comparative Examples 1 - 6 are fabricated.

[0161] Differing from Application Example 1, D2 - 1, D2 - 2 in 《CN119384416A》 are respectively used to replace compound 1 in Application Example 1 as the green light host material for co-evaporation, and the rest are the same as those in Application Example 1. Accordingly, the organic electroluminescent devices of Comparative Examples 7 and 8 are fabricated.

[0162] Differing from Application Example 1, D3 - 1 in 《CN116457351A》 is used to replace compound 1 in Application Example 1 as the green light host material for co-evaporation, and the rest are the same as those in Application Example 1. Accordingly, the organic electroluminescent device of Comparative Example 9 is fabricated.

[0163] The characteristics of the organic electroluminescent devices fabricated in the above Application Examples and the organic electroluminescent devices fabricated in the Comparative Examples were measured under the condition of a current density of 10 mA / cm2, and the results are shown in Table 6 below.

[0164] Table 6

[0165]

[0166]

[0167]

[0168]

[0169] As can be seen from Table 6 above, when the compound of the present invention is applied to an organic electroluminescent device, at the same current density, the luminous efficiency is greatly improved, the turn-on voltage of the device decreases, and the power consumption of the device is relatively reduced.

[0170] The organic electroluminescent devices prepared in Comparative Examples 1-9 and Application Examples 1, 2, 38, 39, 40, 69, 71, 83, 84, and 92 were respectively subjected to a luminous lifetime test to obtain the luminous lifetime T97% data (the time when the luminous brightness decreased to 97% of the initial brightness). The test equipment was a TEO luminous device lifetime test system. The results are shown in Table 7:

[0171] Table 7:

[0172]

[0173]

[0174] As can be seen from Table 7 above, when the compound of the present invention is applied to an organic electroluminescent device, at the same current density, the service life is greatly improved, and it has broad application prospects.

[0175] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present invention can be modified or equivalently replaced without departing from the spirit and scope of the technical solutions of the present invention, and they should all be covered within the scope of the claims of the present invention.

Claims

1. A triazine-based organic electroluminescent compound, characterized in that, The first partial structure shown by formula A and the second partial structure shown by formula B: In formula A, one of the bonds of Ar1 and Ar2 is bonded to the * position of formula B, and the other of Ar1 and Ar2 is hydrogen or deuterium, and R1-R 25 is selected from hydrogen, deuterium, hydroxyl, cyano, a straight-chain or branched alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, a substituted or unsubstituted aryl group having 5 to 40 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 40 carbon atoms, and the substituent is selected from at least one of the following atoms or groups: deuterium, hydroxyl, cyano, monodeuteriomethyl, dideuteriomethyl, trideuteriomethyl, a straight-chain or branched alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 18 carbon atoms, and a heteroaryl group having 5 to 24 carbon atoms, and at least one of R1-R8 is deuterium.

2. The triazine-based organic electroluminescent compound according to claim 1, characterized in that, R1-R 25 Each independently selected from hydrogen, deuterium, cyano, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, phenyl, anthryl, naphthyl, phenanthryl; the methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, phenyl, anthryl, naphthyl, phenanthryl are unsubstituted or at least one hydrogen thereof is replaced by deuterium, deuterated or non-deuterated C1-C4 straight-chain or branched-chain alkyl, deuterated or non-deuterated phenyl-substituted group, and at least one of R1-R8 is deuterium.

3. A triazine-based organic electroluminescent compound according to claim 1, wherein R1-R8 are selected from deuterium, phenyl, deuterated phenyl and at least 7 of R1-R8 are deuterium; R9-R 10 are each independently selected from hydrogen, deuterium; R 11 -R 15 are each independently selected from hydrogen, deuterium, phenyl, deuterated phenyl; R 16 -R 25 are each independently selected from hydrogen, deuterium, phenyl, deuterated phenyl.

4. A triazine-based organic electroluminescent compound as claimed in claim 1, characterized in that, The triazine-based organic electroluminescent compound is as shown by formula C: R1 - R8 are selected from deuterium, phenyl, deuterated phenyl and at least 7 of R1 - R8 are deuterium; R9, R 10 , R 26 are each independently selected from hydrogen, deuterium; R 11 -R 15 are each independently selected from hydrogen, deuterium, phenyl, deuterated phenyl; R 16 -R 25 are each independently selected from hydrogen, deuterium, phenyl, deuterated phenyl.

5. A triazine-based organic electroluminescent compound according to claim 1, characterized in that, The triazine-based organic electroluminescent compound is as shown by formula D: R1-R8 are selected from deuterium, phenyl, deuterated phenyl and at least 7 of R1-R8 are deuterium; R9, R 10 , R 26 are each independently selected from hydrogen, deuterium; R 11 -R 15 are each independently selected from hydrogen, deuterium, phenyl, deuterated phenyl; R 16 -R 25 are each independently selected from hydrogen, deuterium, phenyl, deuterated phenyl.

6. The organic electroluminescent compound with a triazine group as claimed in claim 1, wherein, The triazine-based organic electroluminescent compound is one of the compounds with the following structural formulas:

7. An organic electroluminescent device, characterized in that, Comprising 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 organic electroluminescent compound according to any one of claims 1-6.

8. An organic electroluminescent device according to claim 7, characterized in that, The organic layer includes 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; 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 organic electroluminescent compound according to any one of claims 1-6.

9. An organic electroluminescent device according to claim 8, wherein, The light-emitting layer further contains at least one of the following formula E or formula F: Wherein, Y1 and Y2 are each independently a single bond, a substituted or unsubstituted C6-C20 arylene group; Y3 and Y4 are each independently a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C2-C24 heteroaryl group; Ar3 to Ar 16 are each independently hydrogen, deuterium, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C2-C24 heteroaryl group, a cyano group or a combination thereof, and the substituent is a C6-C20 aryl group.

10. An organic electroluminescent device according to claim 9, characterized in that, The light-emitting layer contains a light-emitting host material, which is composed of a compound according to any one of claims 1-6 and one or more of the compounds P1-P78 mixed together, and the compounds P1-P78 are as follows:

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