Compound for organic light-emitting material and application thereof

Abstract

The invention belongs to the technical field of organic light-emitting materials, and relates to a compound for an organic light-emitting material and application of the compound. According to the compound provided by the invention, a naphtho six-membered heterocyclic ring is used as a parent nucleus, then a five-membered heterocyclic ring is added to enhance the rigidity of a parent nucleus structure, and other different electron-donating groups are connected to a specific position, so that the constructed novel compound has relatively high glass transition temperature, good thermal stability and film-forming property, and proper orbital energy level and triplet energy; the compound can be used as a second hole transport material and a light-emitting main body material to be applied to an organic light-emitting device, and the light-emitting efficiency and the service life of the device can be obviously improved.

Description

Technical Field

[0001] The invention belongs to the technical field of organic luminescent materials and relates to a compound used for organic luminescent materials and application thereof. Background Art

[0002] The OLED material system includes key components such as hole transport materials (HTM), luminescent materials and electron transport materials. Hole transport materials are an important component of the multi-layer composite OLED structure. They can more efficiently transport the hole carriers generated by the positive electrode of the device to the light-emitting layer, effectively improve the imbalance of carrier transport, avoid energy waste, and improve luminous efficiency. The hole carrier mobility is the core indicator for measuring the performance of hole transport materials. Its value directly reflects the ability of the material to transport holes. In addition, when designing and synthesizing hole transport materials, researchers are also committed to pursuing high chemical stability, excellent film-forming properties and appropriate HOMO energy levels.

[0003] It is worth noting that hole transport materials usually have a lower HOMO value, which is often accompanied by a lower T1 (triplet energy level) value. This characteristic may cause the excitons generated in the light-emitting layer to easily diffuse to the hole transport layer interface or its vicinity, thereby causing luminescence or uneven charge distribution at the interface within the light-emitting layer, and ultimately generating luminescence at the hole transport layer interface. This will not only reduce the color purity and luminescence efficiency of the organic electroluminescent device, but also shorten its service life. The above problems can be effectively avoided by introducing a luminescent auxiliary layer between the light-emitting layer and the hole transport layer.

[0004] At present, there are limited materials for light-emitting auxiliary layers. Most of these materials have a high hole mobility and a high Tl energy to block the excitons after recombination from diffusing to the transport layer, thereby improving the overall efficiency of the device. At the same time, a suitable HOMO value reduces the transmission barrier of holes from the transport layer to the light-emitting layer, thereby reducing the device driving voltage and improving the lifespan.

[0005] Therefore, in the field of organic electroluminescent material technology, it is very important to construct a new compound that can not only enhance the stability of organic electroluminescent materials but also improve the photoelectric properties of organic electroluminescent devices. Summary of the invention

[0006] In view of this, the purpose of the present invention is to provide a compound for organic light-emitting materials and its application. The present invention uses a naphtho-hexacyclic heterocyclic mother core and then incorporates a five-membered heterocyclic ring to enhance the rigidity of the mother core. Different electron-donating groups are connected at specific positions to effectively improve the carrier migration ability. The constructed new organic compound has a higher glass transition temperature, suitable orbital energy levels and triplet energy. As a second hole transport material or a light-emitting main material, it can effectively improve the brightness efficiency and lifespan, and significantly improve the photoelectric performance of organic electroluminescent devices.

[0007] In a first aspect, the present invention provides a compound having a structure as shown in Formula 1, ; Wherein, W is selected from N-L1-(NAr1Ar2) m , O; X1, X2, X3, and X4 are all C, and bonded to X5 and X6 in Formula 2. , Wherein, Y is selected from O, N-L2-(NAr3Ar4) n One of; At least one of W and Y is N; N-L1-(NAr1Ar2) m and N-L2-(NAr3Ar4) n Ar1, Ar2, Ar3, Ar4 are substituted or unsubstituted C6-C30 aromatic groups, or heteroaryl groups containing N, O, S heteroatoms and having carbon numbers in the range of C3-C30; N-L1-(NAr1Ar2) m The m in which is selected from one of the integers 0, 1, and 2; N-L2-(NAr3Ar4) n Where n is selected from one of the integers 0, 1, and 2; N-L1-(NAr1Ar2) m and N-L2-(NAr3Ar4) n L1 and L2 in are bridging groups, respectively, and L1 and L2 may be the same or different; N-L1-(NAr1Ar2) m and N-L2-(NAr3Ar4) n The hydrogen in L1, L2, Ar1, Ar2, Ar3, and Ar4 can all be deuterated.

[0008] Furthermore, in the compound provided by the present invention, the compound is one of Formula 3 to Formula 6, .

[0009] Furthermore, in the compound provided by the present invention, the bridging group is selected from one or a combination of two of benzene, naphthalene, biphenyl, terphenyl and N-phenylcarbazole.

[0010] Furthermore, in the compounds provided by the present invention, the substituted or unsubstituted C6-C30 aromatic group includes benzene, p-biphenyl, m-biphenyl, terphenyl, naphthalene, 1-phenylnaphthalene, 2-phenylnaphthalene; The heteroaryl group containing N, O, S heteroatoms and having a carbon number of C3-C30 includes dibenzofuran, dibenzothiophene, N-phenylcarbazole, 9,9-dimethylfluorene, and 4-phenyldibenzofuran.

[0011] Furthermore, in the compound provided by the present invention, the compound is one of Formula 7 to Formula 18,

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[0015] Furthermore, the compounds provided by the present invention have the following structure:

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[0114] Furthermore, in the compound provided by the present invention, the intermediate for synthesizing the compound is selected from one of the following intermediates:

[0115]

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[0117] .

[0118] In a second aspect, the present invention provides use of the compound in an organic electroluminescent device.

[0119] In a third aspect, the present invention provides the use of the compound in the preparation of hole transport materials or light-emitting host materials.

[0120] In a fourth aspect, the present invention provides an organic electroluminescent device, comprising an anode layer, a cathode layer, and an organic thin film layer located between the anode layer and the cathode layer, wherein the organic thin film layer comprises a hole injection layer, a first hole transport layer, a second hole transport layer, a light-emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer, and the second hole blocking layer or the light-emitting layer contains the compound described in the present invention.

[0121] Compared with the prior art, the technical solution provided by the present invention has at least the following beneficial effects or advantages: The invention further enhances the rigidity of the parent nucleus by adding a five-membered heterocycle to the parent nucleus of the naphtho-hexacyclic heterocycle, and connects other electron-donating groups at specific positions to construct a new compound with high glass transition temperature, good thermal stability, good film-forming property, and the life of OLED devices. The new compound has suitable HOMO / LUMO energy levels and triplet energy, and has high carrier transport performance when used as a hole transport material, so that the efficiency of the new compound applied to OLED devices is improved. When used as a light-emitting main material, the energy transfer between the host and the guest is guaranteed, the driving voltage is reduced, and the device performance can be greatly improved. The new compound is a new organic OLED functional material with relatively good development prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0122] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0123] Figure 1 Schematic diagram of the structure of an organic electroluminescent element, wherein 1 is a substrate, 2 is an anode layer, 3 is a hole injection layer, 4 is a first hole transport layer, 5 is a second hole transport layer, 6 is a light-emitting layer, 7 is a hole blocking layer, 8 is an electron transport layer, 9 is an electron injection layer, and 10 is a cathode layer. DETAILED DESCRIPTION

[0124] The technical scheme of the present invention is described below in conjunction with the examples, but the present invention is not limited to the following examples. The experimental methods and detection methods described in each example are conventional methods unless otherwise specified; the reagents and materials are available on the market unless otherwise specified, and the % in the following examples are all mass percentages unless otherwise specified.

[0125] The structure of the naphtho-hexacyclic heterocycle involved in the present invention is as follows: , Wherein, W is selected from N-L1-(NAr1Ar2) m , O; X1, X2, X3, and X4 are all C.

[0126] Preparation Example This preparation example provides the synthesis methods of some intermediates and compounds. The synthesis methods of the remaining intermediates and compounds are similar methods and can be easily synthesized. The specific synthesis routes are shown below.

[0127] Synthesis of intermediate 1:

[0128]

[0129] Synthesis of intermediate 1-1: Under nitrogen protection, raw material 1 (224 g, 1 mol), methyl 2-hydroxybenzoate (152 g, 1 mol), cesium carbonate (390 g, 1.2 mol) and DMF solvent (1500 mL) were added to the reaction bottle in sequence, and heated to 147 ° C for reflux reaction for 8 h. After the reaction was completed, it was cooled to room temperature, the reaction solution was filtered, and the filtrate was added to 3000 mL of water while stirring to generate a white solid. After the white solid was filtered, the filter cake was washed with water and ethanol in sequence, and then recrystallized and purified with a mixed solvent of toluene and n-heptane to obtain 206.5 g of intermediate 1 with a yield of 58%.

[0130] Synthesis of intermediate 1-2: Under nitrogen protection, add intermediate 1-1 (178 g, 0.5 mol) and tetrahydrofuran (600 mL) to a three-necked flask, slowly add 1.0 M tetrahydrofuran solution of methylmagnesium bromide (1.0 M-THF, 800 mL) under stirring at room temperature 24°C, and heat to 50°C to continue the reaction for 5 h. After the reaction solution is cooled to room temperature, add aqueous ammonium chloride solution to quench the reaction, adjust pH to 3 with dilute hydrochloric acid, add 1000 mL of dichloroethane to extract, stir evenly, and wash repeatedly with water, dry the organic phase with anhydrous magnesium sulfate, filter and concentrate, precipitate the solid with ethanol, and purify to obtain 142 g of intermediate 1-2 with a yield of 80%.

[0131] Synthesis of intermediate 1-3: Under nitrogen protection, add intermediate 1-2 (106.8 g, 0.3 mol), methanesulfonic acid (57.6 g, 0.6 mol), and toluene (600 mL) to a three-necked flask, and heat to 108°C for 3 h. After cooling the reaction solution to room temperature, wash with water until neutral, dry the organic phase with anhydrous magnesium sulfate, filter and concentrate, and recrystallize and purify with a mixed solvent of toluene and ethanol to obtain 73 g of intermediate 1-3 with a yield of 72%.

[0132] Synthesis of intermediate 1-4: Under nitrogen protection, intermediate 1-3 (67.6 g, 0.2 mol), o-nitrobenzeneboric acid (33.4 g, 0.2 mol), Pd(PPh3)4 (tetrakis(triphenylphosphine)palladium, 4.6 g, 4 mmol), K2CO3 (potassium carbonate, 55.2 g, 0.4 mol), TBAB (tetrabutylammonium bromide, 6.5 g, 20 mmol), toluene (600 mL), ethanol (300 mL), and water (150 mL) were added to a three-necked flask. The mixture was heated to 76 °C and stirred for 6 h, then cooled to room temperature and washed with water until neutral. The organic phase was dried over anhydrous magnesium sulfate, passed through a silica gel column, and then recrystallized and purified using a mixed volume of toluene and n-heptane to obtain 61 g of intermediate 1-4 with a yield of 80%.

[0133] Synthesis of intermediate 1: Under nitrogen protection, add intermediate 1-4 (38.1 g, 0.1 mol), PPh3 (triphenylphosphine, 52.4 g, 0.2 mol), o-dichlorobenzene (200 mL) into a three-necked flask, stir and heat to 160°C for 18 h. After the reaction solution was cooled to room temperature, n-heptane was added to precipitate a solid product, which was filtered and purified by recrystallization with toluene to obtain 22 g of intermediate 1 with a yield of 63%.

[0134] Synthesis of intermediate 2:

[0135]

[0136] Synthesis of intermediate 2-1: Under nitrogen protection, add raw material 2 (192g, 1mol) and 800mL tetrahydrofuran solvent to a three-necked flask, stir and cool the system to -50°C with liquid nitrogen, then drop butyl lithium (1250mL, 2mol, 1.6M) and keep warm for 1h, then drop trimethyl borate (345g, 1.5mol), keep warm for 1h and then naturally warm to room temperature and continue to react for 2h. After the reaction is completed, quench the reaction with aqueous ammonium chloride solution, add dilute hydrochloric acid to adjust pH=3, then wash with water, dry, concentrate, add ethanol to precipitate the product, and filter to obtain 130g of intermediate 2-1 with a yield of 55%.

[0137] The synthesis of intermediate 2-2 refers to the synthesis of intermediate 1-4, except that intermediate 1-3 and o-nitrobenzene boronic acid are replaced by intermediate 2-1 and 2-fluoroiodobenzene.

[0138] Synthesis of intermediate 2-3: Under nitrogen protection, add intermediate 2-2 (114.4 g, 0.4 mol) and dichloromethane (600 mL) to a dry three-necked flask, cool the reaction system to -5~0°C using an ice-salt bath, add boron tribromide (396.3 g, 1.6 mol), stir at room temperature for 6 hours, and then pour into ice water to quench the reaction. The organic phase is washed with water until neutral, dried over anhydrous magnesium sulfate, filtered, and purified by silica gel column to obtain 98 g of intermediate 2-3 with a yield of 90%.

[0139] The synthesis of intermediate 2-4 refers to the synthesis of intermediate 1-1, except that raw material 1 and methyl 2-hydroxybenzoate are replaced by intermediate 2-3.

[0140] Synthesis of intermediate 2-5: Under nitrogen protection, add intermediate 2-4 (100.8 g, 0.4 mol), methyl 2-aminobenzoate (60.4 g, 0.4 mol), Pd2(dba)3 (tri(dibenzylideneacetone)dipalladium, 3.6 g, 4 mmol), P(t-Bu)3 (tri-tert-butylphosphine, 1.6 g, 8 mmol), sodium tert-butoxide (76.8 g, 0.8 mol), toluene (600 mL) to a three-necked flask, stir and heat to 110°C for reflux reaction for 2 h. After the reaction is complete, cool to room temperature, wash with water until neutral, dry the organic phase with anhydrous magnesium sulfate and filter, pass the filtrate through a silica gel column, concentrate the column liquid and recrystallize and purify with a mixed solvent of toluene and ethanol to obtain 120.4 g of intermediate 2-5, with a yield of 82%.

[0141] The synthesis of intermediate 2-6 refers to the synthesis of intermediate 1-2, except that intermediate 1-1 is replaced by intermediate 2-5.

[0142] The synthesis of intermediate 2 refers to the synthesis of intermediate 1-3, except that intermediate 1-2 is replaced by intermediate 2-6.

[0143] Synthesis of intermediate 3:

[0144]

[0145] Synthesis of intermediate 3-1: Under nitrogen protection, raw material 3 (224 g, 1 mol), benzamidine hydrochloride (188 g, 1.2 mol), and ethanol (2000 mL) were added to a three-necked flask. After stirring until the system was completely dissolved, 120 mL of hydrochloric acid was added dropwise, and the mixture was heated to 88 ° C for 10 h. The reaction was monitored by TCL. After the raw material 3 was completely reacted, the solvent was removed by reduced pressure distillation, 800 mL of dichloromethane was added, and the organic phase was repeatedly washed with water and extracted. It was dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated and recrystallized with a mixed solvent of ethanol and n-heptane to obtain 227 g of intermediate 3-1 with a yield of 76%.

[0146] Synthesis of intermediate 3-2: Under nitrogen protection, add intermediate 3-1 (179.4 g, 0.6 mol), DDQ (2,3-dichloro-5,6-dicyano-1,4-benzoquinone, 454 g, 2 mol), and 900 mL of toluene into a three-necked flask, stir and heat to 90 °C for 10 h, and concentrate under reduced pressure until about 300 mL remains. Add 400 mL of n-heptane, stir evenly, and let stand. After cooling to room temperature, a solid precipitated and filtered to obtain 118.7 g of intermediate 3-2 with a yield of 67%.

[0147] Synthesis of intermediate 3-3: Under nitrogen protection, intermediate 3-2 (88.5 g, 0.3 mol), iodobenzene (67.3 g, 0.33 mol), cuprous chloride (5.9 g, 0.06 mol), K2CO3 (82.8 g, 0.6 mol), 1,10-phenanthroline (4.8 g, 0.03 mol), 18-crown ether-6 (2.6 g, 0.01 mol), and diphenyl ether (600 mL) were added to a three-necked flask. The mixture was stirred and heated to 180°C for 10 h. The reaction solution was distilled under reduced pressure. After the solvent was removed, toluene (800 mL) was added. The system was repeatedly washed with water until neutral. The organic phase was separated, dried over anhydrous magnesium sulfate, and then filtered. The filtrate was passed through a silica gel column, the column liquid was concentrated, and then recrystallized with a mixed solvent of toluene and petroleum ether to obtain 89 g of intermediate 3-3 with a yield of 80%.

[0148] The synthesis of intermediate 3-4 refers to the synthesis of intermediate 2-5, except that intermediate 2-4 is replaced by intermediate 3-3.

[0149] The synthesis of intermediate 3-5 refers to the synthesis of intermediate 1-2, except that intermediate 1-1 is replaced by intermediate 3-4.

[0150] The synthesis of intermediate 3 refers to the synthesis of intermediate 1-3, except that intermediate 1-2 is replaced by intermediate 3-5.

[0151] Synthesis of intermediate 4:

[0152]

[0153] The synthesis of intermediate 4-1 refers to the synthesis of intermediate 2-5, except that intermediate 2-4 is replaced by starting material 4.

[0154] The synthesis of intermediate 4-2 refers to the synthesis of intermediate 1-2, except that intermediate 1-1 is replaced by intermediate 4-1.

[0155] The synthesis of intermediate 4-3 refers to the synthesis of intermediate 1-3, except that intermediate 1-2 is replaced by intermediate 4-2.

[0156] The synthesis of intermediate 4-4 refers to the synthesis of intermediate 3-3, except that intermediate 3-2 is replaced by intermediate 4-3.

[0157] The synthesis of intermediate 4-5 refers to the synthesis of intermediate 1-4, except that intermediate 1-3 is replaced by intermediate 4-4.

[0158] The synthesis of intermediate 4 was based on the synthesis of intermediate 1, except that intermediate 1-4 was replaced by intermediate 4-5.

[0159] Synthesis of intermediate 5:

[0160]

[0161] The synthesis of intermediate 5-1 refers to the synthesis of intermediate 1-1, except that raw material 1 is replaced by raw material 5.

[0162] The synthesis of intermediate 5-2 refers to the synthesis of intermediate 1-2, except that intermediate 1-1 is replaced by intermediate 5-1.

[0163] The synthesis of intermediate 5-3 refers to the synthesis of intermediate 1-3, except that intermediate 1-2 is replaced by intermediate 5-2.

[0164] The synthesis of intermediate 5-4 refers to the synthesis of intermediate 1-4, except that intermediate 1-3 is replaced by intermediate 5-3.

[0165] The synthesis of intermediate 5 refers to the synthesis of intermediate 1, except that intermediate 1-4 is replaced by intermediate 5-4.

[0166] Synthesis of intermediate 6:

[0167]

[0168] The synthesis of intermediate 6-1 refers to the synthesis of intermediate 2-1, except that raw material 2 is replaced by raw material 6.

[0169] The synthesis of intermediate 6-2 refers to the synthesis of intermediate 2-2, except that intermediate 2-1 is replaced by intermediate 5-1.

[0170] The synthesis of intermediate 6-3 refers to the synthesis of intermediate 2-3, except that intermediate 2-2 is replaced by intermediate 5-2.

[0171] The synthesis of intermediate 6-4 refers to the synthesis of intermediate 2-4, except that intermediate 2-3 is replaced by intermediate 5-3.

[0172] The synthesis of intermediate 6-5 refers to the synthesis of intermediate 2-5, except that intermediate 2-4 is replaced by intermediate 5-4.

[0173] The synthesis of intermediate 6-6 refers to the synthesis of intermediate 2-6, except that intermediate 2-5 is replaced by intermediate 5-5.

[0174] The synthesis of intermediate 6 refers to the synthesis of intermediate 2, except that intermediate 2-6 is replaced by intermediate 6-6.

[0175] Synthesis of intermediate 7:

[0176]

[0177] The synthesis of intermediate 7-1 refers to the synthesis of intermediate 3-1, except that raw material 3 is replaced by raw material 7.

[0178] The synthesis of intermediate 7-2 refers to the synthesis of intermediate 3-2, except that intermediate 3-1 is replaced by intermediate 7-1.

[0179] The synthesis of intermediate 7-3 refers to the synthesis of intermediate 3-3, except that intermediate 3-2 is replaced by intermediate 7-2.

[0180] The synthesis of intermediate 7-4 refers to the synthesis of intermediate 3-4, except that intermediate 3-3 is replaced by intermediate 7-3.

[0181] The synthesis of intermediate 7-5 refers to the synthesis of intermediate 3-5, except that intermediate 3-4 is replaced by intermediate 7-4.

[0182] The synthesis of intermediate 7 was based on the synthesis of intermediate 3, except that intermediate 3-5 was replaced by intermediate 7-5.

[0183] Synthesis of intermediate 8:

[0184]

[0185] The synthesis of intermediate 8-1 refers to the synthesis of intermediate 4-1, except that raw material 4 is replaced by raw material 8.

[0186] The synthesis of intermediate 8-2 refers to the synthesis of intermediate 4-2, except that intermediate 4-1 is replaced by intermediate 8-1.

[0187] The synthesis of intermediate 8-3 refers to the synthesis of intermediate 4-3, except that intermediate 4-2 is replaced by intermediate 8-2.

[0188] The synthesis of intermediate 8-4 refers to the synthesis of intermediate 4-4, except that intermediate 4-3 is replaced by intermediate 8-3.

[0189] The synthesis of intermediate 8-5 refers to the synthesis of intermediate 4-5, except that intermediate 4-4 is replaced by intermediate 8-4.

[0190] The synthesis of intermediate 8 refers to the synthesis of intermediate 4, except that intermediate 4-5 is replaced by intermediate 8-5.

[0191] Synthesis of compound 1-1:

[0192] Under nitrogen protection, intermediate 1 (14 g, 0.04 mol), bromobenzene (6.2 g, 0.04 mol), Pd2(dba)3 (tri(dibenzylideneacetone)dipalladium, 0.4 g, 0.4 mmol), P(t-Bu)3 (tri-tert-butylphosphine, 0.3 g, 0.9 mmol), sodium tert-butoxide (7.7 g, 0.08 mol), toluene (150 mL) were added to a three-necked flask, stirred and heated to 110°C for reflux reaction for 2 h. After the reaction was complete, it was cooled to room temperature and washed with water until neutral. The organic phase was dried with 10 g of anhydrous magnesium sulfate for 1 h and then filtered. The filtrate was passed through a silica gel column. After the column liquid was concentrated, it was recrystallized with a mixed solvent of toluene and ethanol and sublimed at 300°C in high vacuum to obtain 11.4 g of white crystalline compound 1-1 with a yield of 67%. The results of mass spectrometry detection of the obtained sample were: HR-MS (APCI): m / z 425.1780 [M+H] + ; C 31 H 23 NO (%) calculated value: C, 87.5003; H, 5.4483; N, 3.2917; O, 3.7598; found value (%): C, 87.5150; H, 5.4442; N, 3.2885; O, 3.7523.

[0193] Synthesis of compound 1-4:

[0194] The synthesis of compound 1-4 was based on the synthesis of compound 1-1, except that bromobenzene was replaced by 4-bromoterphenyl. After synthesis and purification, the compound 1-4 was sublimed under high vacuum at 315°C to obtain a white molten compound with a yield of 64%. The mass spectrometry results of the obtained sample were: HR-MS (APCI): m / z 577.2406 [M+H] + ; C 43 H 31 NO (%) calculated value: C, 89.3974; H, 5.4088; N, 2.4245; O, 2.7693; found value (%): C, 89.3998; H, 5.4120; N, 2.4223; O, 2.7659.

[0195] Synthesis of compound 1-6:

[0196]

[0197] The synthesis of intermediate A refers to the synthesis of intermediate 3-3, except that intermediate 3-2 and iodobenzene are replaced by N-phenyl-4-benzidine and m-bromoiodobenzene.

[0198] The synthesis of compound 1-6 was based on the synthesis of compound 1-1, except that bromobenzene was replaced by intermediate A. After synthesis and purification, the compound 1-6 was sublimed at 335°C in high vacuum to obtain a white molten compound with a yield of 70%. The mass spectrometry results of the obtained sample were: HR-MS (APCI): m / z 668.2828 [M+H] + ; C 49 H 36 Calculated value of N2O (%): C, 87.9940; H, 5.4255; N, 4.1884; O, 2.3921; Found value (%): C, 87.9993; H, 5.4180; N, 4.1856; O, 2.3971.

[0199] Synthesis of compound 1-22:

[0200]

[0201] The synthesis of intermediate A-1 was carried out according to the synthesis of intermediate A, except that m-bromoiodobenzene was replaced by 3,5-dibromoiodobenzene.

[0202] The synthesis of intermediate A-2 was carried out by referring to the synthesis of compound 1-1, and intermediate A-1 and diphenylamine were used as the reaction raw materials.

[0203] The synthesis of compound 1-22 was based on the synthesis of compound 1-1, except that bromobenzene was replaced by intermediate A-2. After synthesis and purification, the compound 1-22 was sublimed under high vacuum at 340°C to obtain a white molten compound with a yield of 53%. The mass spectrometry results of the obtained sample were: HR-MS (APCI): m / z 835.3563 [M+H] + ; C 61 H 45 Calculated value of N3O (%): C, 87.6347; H, 5.4255; N, 5.0261; O, 1.9136; Found value (%): C, 87.6422; H, 5.4211; N, 5.0271; O, 1.9096.

[0204] Synthesis of compound 2-18:

[0205] The synthesis of compound 2-18 was based on the synthesis method of compound 1-1, with intermediate 1 and bromobenzene replaced by intermediate 2 and 9-(4-bromophenyl)carbazole. After synthesis and purification, the compound 2-18 was sublimated at 350°C in high vacuum to obtain a white molten compound with a yield of 62%. The mass spectrometry results of the obtained sample were: HR-MS (APCI): m / z 590.2358 [M+H] + ; C 43 H30 Calculated value of N2O (%): C, 87.4302; H, 5.1191; N, 4.7423; O, 2.7084; Found value (%): C, 87.4391; H, 5.1165; N, 4.7412; O, 2.7032.

[0206] Synthesis of compound 2-66:

[0207] The synthesis of compound 2-66 was carried out by referring to the synthesis method of compound 1-1, except that intermediate 1 and bromobenzene were replaced by intermediate 10 and intermediate A. After synthesis and purification, the compound 2-66 was sublimated under high vacuum at 330°C to obtain white crystalline compound 2-66 with a yield of 61%. The mass spectrometry results of the obtained sample were: HR-MS (APCI): m / z 668.2828 [M+H] + ; C 49 H 36 Calculated value of N2O (%): C, 87.9940; H, 5.4255; N, 4.1884; O, 2.3921; Found value (%): C, 87.9879; H, 5.4248; N, 4.1892; O, 2.3981.

[0208] Synthesis of compound 3-6:

[0209]

[0210] The synthesis of intermediate B was carried out according to the synthesis of intermediate A, except that N-phenyl-4-benzidine was replaced by di(4-biphenylyl)amine.

[0211] The synthesis of compound 3-6 was carried out by referring to the synthesis method of compound 1-1, except that intermediate 1 and bromobenzene were replaced by intermediate 4 and intermediate B. After synthesis and purification, the compound 3-6 was sublimed under high vacuum at 355°C to obtain a white molten compound with a yield of 61%. The mass spectrometry results of the obtained sample were: HR-MS (APCI): m / z 819.3613 [M+H] + ; C 61 H 45 Calculated value for N3 (%): C, 89.3445; H, 5.5314; N, 5.1242; Found value (%): C, 89.3422; H, 5.5327; N, 5.1251.

[0212] Synthesis of compound 3-11:

[0213]

[0214] The synthesis of intermediate C was similar to that of intermediate 1-1, except that 4-aminobiphenyl and 4-bromodibenzofuran were used as the reaction raw materials.

[0215] The synthesis of intermediate D was based on the synthesis of intermediate A, except that N-phenyl-4-benzidine was replaced by intermediate C.

[0216] The synthesis of compound 3-11 was carried out by referring to the synthesis method of compound 1-1, and intermediate 1 and bromobenzene were replaced by intermediate 4 and intermediate D. After synthesis and purification, the compound 3-11 was obtained by high vacuum sublimation at 340°C as a white crystal with a yield of 58%. The mass spectrometry results of the obtained sample were: HR-MS (APCI): m / z 833.3406 [M+H] + ; C 61 H 43 Calculated value of N3O (%): C, 87.8466; H, 5.1969; N, 5.0383; O, 1.9183; Found value (%): C, 87.8425; H, 5.2089; N, 5.0293; O, 1.9193.

[0217] Synthesis of compound 3-49:

[0218] The synthesis of compound 3-49 was carried out by referring to the synthesis method of compound 1-1, replacing intermediate 1 with intermediate 16. After synthesis and purification, it was sublimated under high vacuum at 300°C to obtain white crystalline compound 3-49 with a yield of 68%. The mass spectrometry results of the obtained sample were: HR-MS (APCI): m / z 500.2252 [M+H] + ; C 37 H 28 Calculated value for N2 (%): C, 88.7669; H, 5.6375; N, 5.5956; Found value (%): C, 88.7712; H, 5.6306; N, 5.5982.

[0219] Synthesis of compound 3-125:

[0220] The synthesis of compound 3-125 was carried out by referring to the synthesis method of compound 1-1, and intermediate 1 and bromobenzene were replaced by intermediate 11 and intermediate B. After synthesis and purification, the compound 3-125 was sublimated under high vacuum at 340°C to obtain a white molten compound with a yield of 68%. The mass spectrometry results of the obtained sample were: HR-MS (APCI): m / z 819.3613 [M+H] + ; C 61 H 45Calculated value for N3 (%): C, 89.3445; H, 5.5314; N, 5.1242; Found value (%): C, 89.3462; H, 5.5326; N, 5.1212.

[0221] With reference to the synthesis methods of the above compounds, all compounds in the present invention can be synthesized. The only difference is that different parent core intermediates and intermediates corresponding to the modifying groups need to be used to replace the products, and the mass dosage of the intermediates is changed according to the molar amount. The replacement relationship between the parent core intermediates and the intermediates corresponding to the modifying groups, reactants and compounds is shown in Table 1.

[0222] Table 1 The substitution relationship between the intermediates, reactants and compounds corresponding to the parent core intermediates and the modified groups

[0223] The performance parameters (including Tg temperature, HOMO energy level and LUMO energy level, triplet energy T1) of the compound synthesized by the present invention and the existing OLED materials HT2, H1 (Comparative Example 1) and H2 (Comparative Example 2) were measured, and the results are shown in Table 2.

[0224] Table 2 Performance parameter measurement results of compounds and existing materials

[0225] Note: The highest occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO), and the triplet energy T1 are the data obtained by simulation calculation in Gaussian 09 software, and the calculation method adopts B3LYP hybrid functional, basis set 6-31g(d). Tg temperature is the experimental measured value, which is measured on DSC-60 differential thermal scanning analyzer (Shimadzu Corporation, Japan), and the nitrogen flow rate is 10ml / min.

[0226] As can be seen from Table 2, the compound provided by the present invention has a higher glass transition temperature and better film-forming properties, so that the life of the OLED device containing the material of the present invention is improved; it has suitable triplet energy, HOMO energy level and LUMO energy level, which is beneficial to the transport of carriers and the transfer of energy between the host and the guest in the OLED device. The compound of the present invention is suitable for use as a second hole transport material and a light-emitting host material.

[0227] Taking some compounds provided by the present invention as examples, they are applied to organic electroluminescent devices as second hole transport materials and luminescent host materials to verify the excellent effects achieved.

[0228] Example 1 This embodiment provides an organic electroluminescent device, the structure of which is as follows: Figure 1 As shown, it includes a substrate 1, an anode layer 2, a hole injection layer 3, a first hole transport layer 4, a second hole transport layer 5, a light emitting layer 6, a hole blocking layer 7, an electron transport layer 8, an electron injection layer 9 and a cathode layer 10 which are stacked in sequence.

[0229] Among them, the substrate 1 is a glass substrate with a thickness of 0.7 mm, the material of the anode layer 2 is indium tin oxide (ITO) with a high work function, the material of the hole injection layer 3 is HAT-CN with a thickness of 5 nm; the material of the first hole transport layer 4 is NPB with a thickness of 60 nm; the material of the second hole transport layer 5 is compound 1-4 with a thickness of 10 nm; the light-emitting layer 6 uses RD01 as the light-emitting material and H1 as the main material, with a doping mass ratio of 6% and a thickness of 30 nm; the material of the hole blocking layer 7 is HB1 with a thickness of 10 nm; the material of the electron transport layer 8 is ET1 with a thickness of 35 nm; the material of the electron injection layer 9 is Liq with a thickness of 2 nm; the material of the cathode layer is Al with a thickness of 100 nm.

[0230] The basic material structure used in each functional layer of the device is as follows:

[0231]

[0232]

[0233] The specific preparation steps of the above organic electroluminescent device are as follows: (1) Clean the ITO anode layer on the transparent glass or plastic substrate by ultrasonic cleaning with deionized water, acetone, and ethanol for 20 minutes each, and then perform plasma treatment in an oxygen atmosphere for 5 minutes; (2) On the ITO anode layer, the hole injection layer material HAT-CN is deposited by vacuum evaporation with a thickness of 5 nm. This layer serves as the hole injection layer. (3) Vacuum evaporation of a hole transport material NPB with a thickness of 60 nm on the hole injection layer, which serves as the first hole transport layer; (4) depositing the hole transport material compound 1-4 on the first hole transport layer HT1 by vacuum evaporation to a thickness of 15 nm, and this layer serves as the second hole transport layer; (5) On the second hole transport layer, a light-emitting layer was co-deposited by vacuum evaporation, using H1 as the main material and RD01 as the doping material, with a doping mass ratio of 6% and a thickness of 30 nm; (6) On the light-emitting layer, a hole blocking material HB1 is deposited by vacuum evaporation with a thickness of 10 nm. This layer serves as a hole blocking layer. (7) On the hole blocking layer, the electron transport material ET1 is evaporated by vacuum evaporation with a thickness of 35 nm. This layer serves as the electron transport layer; (8) On the electron transport layer, the electron injection material Liq is evaporated by vacuum evaporation with a thickness of 2 nm. This layer serves as the electron injection layer; (9) On the electron injection layer, cathode Al is deposited by vacuum evaporation with a thickness of 100 nm. This layer is used as a cathode conductive electrode and is referred to as the cathode layer.

[0234] The most conductive electrode is used, and this layer is the cathode layer.

[0235] Embodiments 2 to 27 The preparation process of Examples 2 to 27 is the same as that of Example 1, except that the second hole transport material adopts compound 1-6, compound 1-13, compound 1-22, compound 1-29, compound 1-66, compound 1-81, compound 2-6, compound 2-13, compound 2-18, compound 2-28, compound 2-41, compound 2-43, compound 2-66, compound 2-91, compound 3-6, compound 3-11, compound 3-23, compound 3-25, compound 3-40, compound 3-49, compound 3-55, compound 3-81, compound 3-110, compound 3-123, compound 3-125, compound 3-147, and compound 3-158 synthesized by the preparation example of the present invention.

[0236] Embodiments 28 to 46 The preparation process of Examples 28 to 46 is the same as that of Example 1, except that HT2 is used as the second hole transport material instead of compound 1-4, and the light-emitting main material H1 is replaced by compound 1-1, compound 1-25, compound 1-53, compound 1-73, compound 2-1, compound 2-2, compound 2-4, compound 2-29, compound 2-57, compound 2-85, compound 3-1, compound 3-2, compound 3-17, compound 3-33, compound 3-49, compound 3-76, compound 3-118, compound 3-120, and compound 3-121 synthesized in the preparation example of the present invention.

[0237] Comparative Example 1 Comparative Example 1 is the same as Example 1, except that the second hole transport material uses compound HT2 instead of compound 1-4.

[0238] Comparative Example 2 Comparative Example 2 is the same as Comparative Example 1, except that the light-emitting host material H2 replaces H1.

[0239] The components of the different devices prepared in device embodiments 1 to 46 of the present invention and comparative examples 1 to 2 are shown in Table 3.

[0240] Table 3 Comparison of organic electroluminescent device components of various device examples

[0241] The cathode and anode of each group of organic electroluminescent devices were connected by a known driving circuit, and the voltage-efficiency-current density relationship of the OLED device was tested by a standard method using a Keithley 2400 power supply combined with a PR670 photometer; the life of the device was tested by a constant current method under the test condition of a constant current density of 10 mA / cm 2 The time it takes for the brightness to decay to 95% of the initial brightness is the LT95 life of the device. The results are shown in Table 4.

[0242] Table 4 Comparison of performance results of organic electroluminescent devices in each group

[0243] As can be seen from Table 4, the compounds provided by the present invention are applied as hole transport materials and luminescent main materials to OLED red light devices, and the performance is improved. For example, the compound 2-18 in Example 10 is used as a hole transport material, compared with HT2 in Comparative Example 1, and the turn-on voltage is slightly reduced, and the luminous efficiency and service life are significantly improved, the brightness efficiency is increased by 57%, and the service life is increased by 37%; the compound 3-76 in Example 43 is used as a luminescent main material, compared with H1 and H2 in Comparative Examples 1~2, and the brightness efficiency and life are also significantly improved, especially compared with H2 in Comparative Example 2, the brightness efficiency is increased by 65%, and the service life is increased by 86%.

[0244] It can be seen that the compounds of the present invention are used as hole transport materials and light-emitting main materials, the efficiency and life of the device are good, and the synthesis process of the material is simple. It has great application value in the application of OLED devices and has good industrialization prospects.

[0245] As described above, the basic principle, main features and advantages of the present invention are well described. The above embodiments and descriptions are only descriptions of the preferred implementation modes of the present invention, and the present invention is not limited by the above embodiments. Without departing from the spirit and scope of the present invention, various changes and improvements made by ordinary technicians in this field to the technical solution of the present invention should fall within the protection scope determined by the present invention.

Claims

1. A compound, characterized in that Having a structure as shown in Formula 1, ； Wherein, W is selected from N-L1-(NAr1Ar2) m , O; X1, X2, X3, and X4 are all C, and bonded to X5 and X6 in Formula 2. ， Wherein, Y is selected from O, N-L2-(NAr3Ar4) n One of; At least one of W and Y is N; N-L1-(NAr1Ar2) m and N-L2-(NAr3Ar4) n Ar1, Ar2, Ar3, Ar4 are substituted or unsubstituted C6-C30 aromatic groups, or heteroaryl groups containing N, O, S heteroatoms and having carbon numbers in the range of C3-C30; N-L1-(NAr1Ar2) m The m in which is selected from one of the integers 0, 1, and 2; N-L2-(NAr3Ar4) n Where n is selected from one of the integers 0, 1, and 2; N-L1-(NAr1Ar2) m and N-L2-(NAr3Ar4) n L1 and L2 in are bridging groups, respectively, and L1 and L2 may be the same or different; N-L1-(NAr1Ar2) m and N-L2-(NAr3Ar4) n The hydrogen in L1, L2, Ar1, Ar2, Ar3, and Ar4 can all be deuterated.

2. The compound according to claim 1, characterized in that The compound is selected from one of Formula 3 to Formula 6, 。 3. The compound according to claim 1, characterized in that The bridging group is selected from one or a combination of two of benzene, naphthalene, biphenyl, terphenyl and N-phenylcarbazole.

4. The compound according to claim 1, characterized in that The substituted or unsubstituted C6-C30 aromatic group includes benzene, p-biphenyl, m-biphenyl, terphenyl, naphthalene, 1-phenylnaphthalene, and 2-phenylnaphthalene; The heteroaryl group containing N, O, S heteroatoms and having a carbon number of C3-C30 includes dibenzofuran, dibenzothiophene, N-phenylcarbazole, 9,9-dimethylfluorene, and 4-phenyldibenzofuran.

5. The compound according to claim 1, characterized in that The compound is selected from one of Formula 7 to Formula 18, 。 6. The compound according to claim 1, characterized in that The compound has the structure shown below: 。 7. The compound according to claim 6, characterized in that The intermediate for synthesizing the compound is selected from one of the following intermediates, 。 8. Use of the compound according to any one of claims 1 to 7 in an organic electroluminescent device.

9. Use of the compound according to any one of claims 1 to 7 in the preparation of hole transport materials or light-emitting host materials.

10. An organic electroluminescent device, comprising an anode layer, a cathode layer and an organic thin film layer located between the anode layer and the cathode layer, wherein the organic thin film layer comprises a hole injection layer, a first hole transport layer, a second hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer, characterized in that: The second hole transport layer or the light-emitting layer contains the compound according to any one of claims 1 to 7.

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