An organic compound and its application

Abstract

The present invention belongs to the technical field of electroluminescent materials, and relates to an organic compound and its application. The seven-membered ring structure composed of two naphthalene rings and a N atom can well restrict the rotation and vibration of the naphthalene ring, greatly improve the rigidity of the material, and enhance the stability of the material. The electron-donating ability of the parent nucleus is further enhanced by combining the naphthalene ring with a six-membered nitrogen or oxygen heterocycle. The electron-donating group or the electron-withdrawing group is connected by the N atom to construct a new compound, which can effectively improve the carrier migration ability. The organic compound has a suitable orbital energy level, can be used to prepare an electroluminescent material, can effectively reduce the driving voltage, and improve the brightness efficiency and lifespan.

Description

Technical Field

[0001] The invention belongs to the technical field of electroluminescent materials and relates to an organic compound and application thereof. Background Art

[0002] The luminescence mechanism of organic electroluminescent (OLED) display devices and lighting elements is a new optoelectronic information technology that directly converts electrical energy into light energy with the help of organic semiconductor functional materials under the action of a DC electric field. Its luminescent colors can be single red, green, blue, yellow light or combined white light.

[0003] Holes and electrons injected from the positive and negative electrodes on the organic film are combined to form excitons. When the excitons return from the excited state to the stable ground state, they release energy in the form of light to emit light. Due to the limitations of the spin quantum statistics, traditional fluorescent materials can only utilize singlet excitons, which account for 25% of the total number of excitons, during the electroluminescence process. The remaining 75% of triplet excitons are inactivated through non-radiative transitions, resulting in a maximum internal quantum efficiency (IQE) of 25%. However, due to the heavy atom effect, phosphorescent metal complexes can utilize both singlet excitons and triplet excitons at the same time, so that the internal quantum efficiency of the device can reach 100%. In order to maximize the performance of phosphorescent materials, it is necessary to dope phosphorescent materials into the host material to reduce the quenching effect of the luminescent material itself, thereby obtaining higher device performance.

[0004] Phosphorescent materials have high triplet energy. As the main body of phosphorescent materials, their energy must be greater than that of luminescent materials, otherwise energy backflow will occur, thereby reducing luminous efficiency. In recent years, phosphorescent main body materials have made great progress, but high triplet state and good stability of the main body materials are rare. The development of new high-performance phosphorescent main body materials has always been a hot topic in the industry. In addition, the main body material is required to have a high glass transition temperature and pyrolysis temperature to achieve thermal stability, high electrochemical stability, easy film formation, and long life.

[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 an organic electroluminescent material, wherein the seven-membered ring structure can well restrict the rotation and vibration of the naphthalene ring, greatly improve the rigidity of the material, and enhance the stability of the material, especially by combining the naphthalene ring with a six-membered nitrogen or oxygen heterocycle, further enhancing the electron donating ability of the parent core, and constructing a new compound by connecting electron donating groups or strong electron pulling groups, which can effectively improve the carrier migration ability. The organic compound has a suitable orbital energy level, and as a hole transport material or a phosphorescent host material, can effectively reduce the driving voltage, improve the brightness efficiency and lifespan, and significantly improve the photoelectric performance of the organic electroluminescent device.

[0007] In order to achieve the above object, the present invention provides the following technical solutions:

[0008] In a first aspect, the present invention provides an organic compound having a structure as shown in formula (I):

[0009]

[0010] in,

[0011] Y is selected from one of a single bond, O, NAr2 and CR1R2;

[0012] R1 and R2 are independently selected from one of hydrogen, C1-C6 alkyl, C1-C6 isoalkyl and phenyl;

[0013] Ar1 and Ar2 are independently selected from one or more of a substituted or unsubstituted aryl group containing C6 to C60, and a substituted or unsubstituted heteroaryl group containing N, O, S, Si, or P heteroatoms and having a carbon number of C6 to C60.

[0014] Preferably, the organic compound is selected from any one of Formula 1 to Formula 4:

[0015] .

[0016] Preferably,

[0017] The C6-C60 substituted or unsubstituted aromatic group includes one or more of a benzene ring, a naphthalene ring, an anthracene group, a biphenyl group, a phenanthryl group, a fluoranthenyl group, a 3,5-diphenyltriazine group, a diphenylfuran group, a dimethylfluorene group, a diphenylthiophene group, a spirobifluorenyl group, a dibenzocarbazole group, a silanyl group, a sulfoxide group, a phosphorus oxide group, a pyrazinyl group, and a quinolyl group;

[0018] The substituted or unsubstituted heteroaryl group containing N, O, S, Si, P heteroatoms and having a carbon number of C6 to C60 includes one or more of a benzene ring, a naphthalene ring, an anthracene group, a biphenyl group, a phenanthryl group, a fluoranthenyl group, a 3,5-diphenyltriazine, a diphenylfuran group, a dimethylfluorene group, a diphenylthiophene group, a spirobifluorenyl group, a dibenzocarbazole group, a silanyl group, a sulfoxide group, a phosphorus oxide group, and a quinolyl group in a pyrazinyl group.

[0019] Preferably,

[0020] The substituted or unsubstituted aryl group containing C6 to C60 and the substituted or unsubstituted heteroaryl group containing N, O, S, Si, P heteroatoms and having a carbon number of C6 to C60 are independently selected from the following groups:

[0021]

[0022]

[0023]

[0024] Wherein, * indicates that the substituent is connected to the main structure or the bridging group.

[0025] Preferably, the C1-C6 alkyl group and the C1-C6 isoalkyl group are independently selected from one or more of methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl and tert-butyl.

[0026] Preferably, the organic compound is selected from any one of Compound 1 to Compound 96:

[0027]

[0028]

[0029]

[0030]

[0031]

[0032]

[0033] In a second aspect, there is provided a use of the organic compound described in the present invention in preparing a hole transport material or a phosphorescent light-emitting host material.

[0034] In a third aspect, there is provided a use of the organic compound of the present invention in an organic electroluminescent device or an organic electroluminescent display apparatus.

[0035] In a fourth aspect, a compound for an organic electroluminescent device is provided, wherein the compound comprises the organic compound described in the present invention.

[0036] In a fifth aspect, an organic electroluminescent device is provided, the 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, the organic thin film layer comprising 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; wherein,

[0037] The first hole transport layer, the second hole transport layer or the light emitting layer contains the organic compound described in the present invention.

[0038] In a sixth aspect, an organic electroluminescent display device is provided, the organic electroluminescent display device comprising an anode layer, a cathode layer, and an organic thin film layer located between the anode layer and the cathode layer, the organic thin film layer comprising 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; wherein,

[0039] The first hole transport layer, the second hole transport layer or the light emitting layer contains the organic compound described in the present invention.

[0040] In a seventh aspect, there is provided the use of the organic compound described in the present invention in the preparation of electroluminescent materials.

[0041] Compared with the prior art, the beneficial effects of the present invention are:

[0042] 1. The present invention further enhances the electron-donating ability of the parent core by adding a six-membered nitrogen or oxygen heterocycle to the seven-membered nitrogen naphthalene ring, and can construct a bipolar material by connecting an electron-donating group or an electron-withdrawing group.

[0043] 2. The seven-membered nitrogen-fused ring compound (organic compound) provided by the present invention has a high glass transition temperature, good thermal stability, good film-forming properties, and can increase the life of OLED devices.

[0044] 3. The organic compound provided by the present invention has suitable HOMO / LUMO energy levels and triplet energy. When used as a hole transport material, it has a high carrier transport performance, which improves the efficiency of its application in OLED devices. When used as a red phosphorescent light-emitting main material, it can significantly improve the device performance. It is a new type of organic OLED functional material with relatively promising development prospects.

[0045] The organic compound provided by the present invention has a seven-membered ring structure which can well restrict the rotation and vibration of the naphthalene ring, greatly improve the rigidity of the material, and enhance the stability of the material. The electron-donating ability of the parent core is further enhanced by combining the naphthalene ring with a six-membered nitrogen or oxygen heterocycle. The novel compound constructed by the present invention can effectively improve the carrier migration ability by connecting an electron-donating group or a strong electron-pulling group. The organic compound has a suitable orbital energy level and can be used as a hole transport material or a phosphorescent host material to effectively reduce the driving voltage, improve the brightness efficiency and lifespan, and significantly improve the photoelectric performance of an organic electroluminescent device. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] In order to more clearly illustrate the technical solution of the present invention, the drawings involved in the description of the embodiments will be briefly introduced below. Obviously, the drawings in the description 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.

[0047] Figure 1 The figure is a schematic diagram of the structure of an organic electroluminescent device provided in an embodiment of the present invention.

[0048] Description of reference numerals:

[0049] 1-substrate, 2-anode layer, 3-hole injection layer, 4-first hole transport layer, 5-second hole transport layer, 6-light-emitting layer, 7-hole blocking layer, 8-electron transport layer, 9-electron injection layer, 10-cathode layer. DETAILED DESCRIPTION

[0050] 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 described are commercially available unless otherwise specified.

[0051] Preparation Example

[0052] The synthesis methods of some intermediates and compounds are provided below. The synthesis methods of the remaining intermediates and compounds are similar and can be easily synthesized. The specific synthesis routes are shown below.

[0053] Synthesis of compound 1:

[0054]

[0055]

[0056] Synthesis of intermediate 1-2: Under nitrogen protection, add intermediate 1-1 (100.1g, 269mmol), iodobenzene (54.6g, 269mmol), Pd2(dba)3 (tri(dibenzylideneacetone)dipalladium, 2.5g, 2.7mmol), P(t-Bu)3 (tri-tert-butylphosphine, 1g, 5mmol), sodium tert-butoxide (96g, 1mol), 1000mL of toluene solvent to a three-necked flask, stir and reflux at 110℃ for 2h. After the reaction is complete, the reaction solution is cooled to room temperature, washed with water until neutral, the organic phase is dried with 160g of anhydrous magnesium sulfate for 3h and filtered, the filtrate is passed through a silica gel column, the column liquid is concentrated, and recrystallized to finally purify 90.5g of intermediate 1-2 with a yield of 75%.

[0057] Synthesis of intermediate 1-3: Under nitrogen protection, intermediate 1-2 (85.3 g, 190 mmol), 8-amino-1-naphthylboronic acid (35.5 g, 190 mmol), Pd(PPh3)4 (tetrakis(triphenylphosphine)palladium, 11.5 g, 1 mmol), K2CO3 (potassium carbonate, 52.4 g, 380 mmol), TBAB (tetrabutylammonium bromide, 6.1 g, 19 mmol), toluene (600 mL), ethanol (300 mL), water (150 mL) were added to a three-necked flask, heated to 77 ° C and stirred for 8 h, then cooled to room temperature, washed with water until neutral, the organic phase was dried over 100 g of anhydrous magnesium sulfate and filtered, the filtrate was passed through a silica gel column, and then purified by recrystallization from toluene to obtain 69.1 g of intermediate 1-3, with a yield of 71%.

[0058] Synthesis of intermediate 1-4: Under nitrogen protection, intermediate 1-3 (50 g, 98 mmol), copper powder (3.1 g, 49 mmol), K2CO3 (40.6 g, 294 mmol), and 400 ml of DMF solvent were added to a three-necked flask, heated to 147 ° C with stirring for 6 h, and then cooled to room temperature. The reaction solution was filtered and the filtrate was poured into 3 L of water while stirring. A large amount of white solid precipitated. After stirring for 30 min, it was filtered and the filter cake was recrystallized from toluene to obtain 35.1 g of intermediate 1-4 with a yield of 83%.

[0059] The synthesis method of compound 1 is based on the synthesis of intermediate 1-2, except that intermediate 1-1 and iodobenzene are replaced by intermediate 1-4 and 2-bromo-4,6-diphenyl-1,3,5-triazine, with a yield of 73%. The mass spectrometry results of the obtained sample are: HR-MS (APCI): m / z 663.2423 [M+H] + ; C 47 H 29N5(%) calculated value: C, 85.0453; H, 4.4038; N, 10.5509; measured value: C, 85.0481; H, 4.4053; N, 10.5466.

[0060] Synthesis of compound 7:

[0061]

[0062] The synthesis method of compound 7 refers to the synthesis of compound 1, and the intermediate 2-bromo-4,6-diphenyl-1,3,5-triazine is replaced by the intermediate 9-(3-bromophenyl)carbazole, with a yield of 74%. The mass spectrometry results of the obtained sample are: HR-MS (APCI): m / z 673.2518 [M+H] + ; C 50 H 31 N3(%) calculated value: C, 89.1291; H, 4.6374; N, 6.2292; measured value: C, 89.1237; H, 4.6400; N, 6.2363.

[0063] Synthesis of compound 25:

[0064]

[0065]

[0066] The synthesis method of intermediate 1-5 refers to the synthesis of intermediate 1-2, except that the intermediate iodobenzene is replaced by the intermediate 2-iodo-4,6-diphenyl-1,3,5-triazine, with a yield of 70%.

[0067] The synthesis method of intermediate 1-6 refers to the synthesis of intermediate 1-3, replacing intermediate 1-2 with intermediate 1-5, with a yield of 72%.

[0068] The synthesis method of intermediate 1-7 refers to the synthesis of intermediate 1-4, replacing intermediate 1-3 with intermediate 1-6, with a yield of 78%.

[0069] The synthesis of compound 25 was based on the synthesis of compound 1, except that intermediate 1-4 was replaced by 1-7, with a yield of 72%. The mass spectrometry results of the obtained sample were: HR-MS (APCI): m / z 663.2423 [M+H] + ; C 47 H 29 N5(%) calculated value: C, 85.0453; H, 4.4038; N, 10.5509; measured value: C, 85.0393; H, 4.4092; N, 10.5515.

[0070] Synthesis of compound 39:

[0071]

[0072]

[0073] The synthesis method of intermediate 1-8 refers to the synthesis of intermediate 1-2, except that the intermediate iodobenzene is replaced by the intermediate 9-(4-iodophenyl)carbazole, with a yield of 77%.

[0074] The synthesis method of intermediate 1-9 refers to the synthesis of intermediate 1-3, replacing intermediate 1-2 with intermediate 1-8, with a yield of 74%.

[0075] The synthesis method of intermediate 1-10 refers to the synthesis of intermediate 1-4, replacing intermediate 1-3 with intermediate 1-9, with a yield of 69%.

[0076] The synthesis method of compound 39 refers to the synthesis of compound 1, and intermediate 1-4 and iodobenzene are replaced by intermediate 1-10 and 9-(3-bromophenyl)carbazole, with a yield of 65%. The result of mass spectrometry detection of the obtained sample is: HR-MS (APCI): m / z838.3096 [M+H] + ; C 62 H 38 N4(%) calculated value: C, 88.7568; H, 4.5654; ​​N, 6.6778; measured value: C, 88.7473; H, 4.5736; N, 6.6791.

[0077] Synthesis of compound 41:

[0078]

[0079]

[0080] The synthesis method of intermediate 2-2 refers to the synthesis of intermediate 1-3, replacing intermediate 1-2 and 8-amino-1-naphthylboronic acid with intermediate 2-1 and 2-(methoxycarbonyl)phenylboronic acid, with a yield of 62%.

[0081] Synthesis of intermediate 2-3: Under nitrogen protection, add intermediate 2-2 (56.4 g, 135 mmol) and tetrahydrofuran (200 mL) to a three-necked flask, slowly add 1.0M tetrahydrofuran solution of methylmagnesium bromide (1.0M-THF, 355 mL) under stirring at room temperature of 23°C, and heat to 50°C after completion of the addition to continue the reaction for 6 h. After the reaction solution was cooled to room temperature, an aqueous solution of ammonium chloride was added to quench the reaction, the pH was adjusted to 3 with dilute hydrochloric acid, and then washed with water until neutral, the organic phase was dried with 100g of anhydrous magnesium sulfate, filtered, and purified by silica gel column to obtain 39.5 g of intermediate 2-3 with a yield of 70%.

[0082] Synthesis of intermediate 2-4: Under nitrogen protection, add intermediate 2-3 (30.0 g, 72 mmol), methanesulfonic acid (13.8 g, 144 mmol), and toluene (300 mL) to a three-necked flask, stir and heat to 108°C for 3 h. The reaction solution was cooled to room temperature, washed with water until neutral, and the organic phase was dried with 80 g of anhydrous magnesium sulfate and filtered, and purified by silica gel column to obtain 23.9 g of intermediate 2-4 with a yield of 83%.

[0083] The synthesis method of intermediate 2-5 refers to the synthesis of intermediate 1-3, replacing intermediate 1-2 with intermediate 2-4, with a yield of 71%.

[0084] The synthesis method of intermediate 2-6 refers to the synthesis of intermediate 1-4, replacing intermediate 1-3 with intermediate 2-5, with a yield of 75%.

[0085] The synthesis method of compound 41 refers to the synthesis of compound 1, and intermediate 1-4 and iodobenzene are replaced by intermediate 2-6 and 9-(3-bromophenyl)carbazole, with a yield of 69%. The result of mass spectrometry detection of the obtained sample is: HR-MS (APCI): m / z 624.2565 [M+H] + ; C 47 H 32 N2(%) calculated value: C, 90.3535; H, 5.1627; N, 4.4838; measured value: C, 90.3553; H, 5.1623; N, 4.4824.

[0086] Synthesis of compound 43:

[0087]

[0088] The synthesis method of compound 43 refers to the synthesis of compound 1, and intermediate 1-4 and iodobenzene are replaced by intermediate 2-6 and 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine, with a yield of 67%. The mass spectrometry results of the obtained sample are: HR-MS (APCI): m / z 690.2783 [M+H]+ ; C 50 H 34 N4(%) calculated value: C, 86.9291; H, 4.9608; N, 8.1100; measured value: C, 86.9192; H, 4.9656; N, 8.1152.

[0089] Synthesis of compound 46:

[0090]

[0091]

[0092] The synthesis method of intermediate 2-7 refers to the synthesis of intermediate 2-3, except that the intermediate methylmagnesium bromide is replaced by the intermediate phenylmagnesium bromide, with a yield of 67%.

[0093] The synthesis method of intermediate 2-8 refers to the synthesis of intermediate 2-4, replacing intermediate 2-3 with intermediate 2-7, with a yield of 81%.

[0094] The synthesis method of intermediate 2-9 refers to the synthesis of intermediate 1-3, replacing intermediate 1-2 with intermediate 2-8, with a yield of 67%.

[0095] The synthesis method of intermediate 2-10 refers to the synthesis of intermediate 1-4, replacing intermediate 1-3 with intermediate 2-9, with a yield of 72%.

[0096] The synthesis method of compound 46 refers to the synthesis of compound 1, and intermediate 1-4 and iodobenzene are replaced by intermediate 2-10 and 8-bromofluoranthene, with a yield of 64%. The mass spectrometry results of the obtained sample are: HR-MS (APCI): m / z 707.2613 [M+H] + ; C 55 H 33 Calculated value of N (%): C, 93.3221; H, 4.6991; N, 1.9787; Found: C, 93.3281; H, 4.7082; N, 1.9637.

[0097] Synthesis of compound 48:

[0098]

[0099] The synthesis method of compound 48 refers to the synthesis of compound 1, and intermediate 1-4 and iodobenzene are replaced by intermediate 2-10 and intermediate 2-11, with a yield of 70%. The result of mass spectrometry detection of the obtained sample is: HR-MS (APCI): m / z 799.2875 [M+H] + ; C 61 H 37NO (%) calculated: C, 91.5870; H, 4.6622; N, 1.7509; O, 1.999; found: C, 91.5792; H, 4.6848; N, 1.7532; O, 1.9828.

[0100] Synthesis of compound 54:

[0101]

[0102] The synthesis method of compound 54 was based on the synthesis of compound 1, except that intermediate 1-4 was replaced by intermediate 2-10, with a yield of 80%. The mass spectrometry results of the obtained sample were: HR-MS (APCI): m / z 583.2300 [M+H] + ; C 45 H 29 Calculated value of N (%): C, 92.5927; H, 5.0078; N, 2.3996; Found: C, 92.5874; H, 5.0153; N, 2.3973.

[0103] Synthesis of compound 55:

[0104]

[0105] The synthesis method of compound 55 refers to the synthesis of compound 1, and intermediate 1-4 and iodobenzene are replaced by intermediate 2-10 and intermediate 2-11, with a yield of 72%. The result of mass spectrometry detection of the obtained sample is: HR-MS (APCI): m / z 887.3552 [M+H] + ; C 69 H 45 Calculated value for N (%): C, 93.3155; H, 5.1074; N, 1.5771; Found: C, 93.3087; H, 5.1175; N, 1.5738.

[0106] Synthesis of compound 62:

[0107]

[0108]

[0109] The synthesis method of intermediate 3-2 refers to the synthesis of intermediate 1-3, replacing intermediate 1-2 with intermediate 3-1, with a yield of 72%.

[0110] The synthesis method of intermediate 3-3 refers to the synthesis of intermediate 1-4, replacing intermediate 1-3 with intermediate 3-2, with a yield of 68%.

[0111] The synthesis method of compound 62 refers to the synthesis of compound 1, except that intermediate 1-4 and iodobenzene are replaced by intermediate 3-3 and intermediate 3-4, with a yield of 63%. The mass spectrometry result of the obtained sample is: HR-MS (APCI): m / z 561.1841 [M+H] + ; C 40 H 23 Calculated value for N3O (%): C, 85.5417; H, 4.1279; N, 7.4818; O, 2.8486; Found: C, 85.5395; H, 4.1307; N, 7.4836; O, 2.8462.

[0112] Synthesis of compound 63:

[0113]

[0114] The synthesis method of compound 63 refers to the synthesis of compound 1, except that intermediate 1-4 and iodobenzene are replaced by intermediate 3-3 and 4-bromotetraphenylsilane, with a yield of 68%. The mass spectrometry results of the obtained sample are: HR-MS (APCI): m / z 691.2331 [M+H] + ; C 50 H 33 NOSi (%) calculated: C, 86.7966; H, 4.8076; N, 2.0244; O, 2.3123; Si, 4.0591; found: C, 86.7988; H, 4.8126; N, 2.0194; O, 2.3111; Si, 4.0581.

[0115] Synthesis of compound 65:

[0116]

[0117] The synthesis method of compound 65 refers to the synthesis of compound 1, and intermediate 1-4 and iodobenzene are replaced by intermediate 3-3 and 9-(3-bromophenyl)carbazole, with a yield of 72%. The result of mass spectrometry of the obtained sample is: HR-MS (APCI): m / z598.2045 [M+H] + ; C 44 H 26 Calculated value for N2O (%): C, 88.2712; H, 4.3774; N, 4.6791; O, 2.6723; Found: C, 88.2667; H, 4.3828; N, 4.6748; O, 2.6757.

[0118] Synthesis of compound 66:

[0119]

[0120] The synthesis method of compound 66 refers to the synthesis of compound 1, and intermediate 1-4 and iodobenzene are replaced by intermediate 3-3 and 9-bromo-10-phenylanthracene, with a yield of 70%. The result of mass spectrometry detection of the obtained sample is: HR-MS (APCI): m / z 609.2093[M+H] + ; C 46 H 27 NO (%) Calculated: C, 90.6152; H, 4.4636; N, 2.2973; O, 2.6240; Found: C, 90.6097; H, 4.4685; N, 2.2946; O, 2.6272.

[0121] Synthesis of compound 73:

[0122]

[0123] The synthesis method of compound 73 refers to the synthesis of compound 1, and intermediate 1-4 and iodobenzene are replaced by intermediate 3-3 and 4-(4-bromophenyl)-dibenzofuran, with a yield of 67%. The result of mass spectrometry detection of the obtained sample is: HR-MS (APCI): m / z599.1885 [M+H] + ; C 44 H 25 NO2(%) calculated value: C,88.1263; H,4.2022; N,2.3357; O,5.3358; found value: C,88.1169; H,4.2073; N,2.3383; O,5.3375.

[0124] Synthesis of compound 80:

[0125]

[0126]

[0127] The synthesis method of intermediate 4-2 refers to the synthesis of intermediate 1-3, replacing intermediate 1-2 with intermediate 4-1, with a yield of 73%.

[0128] The synthesis method of intermediate 4-3 refers to the synthesis of intermediate 1-4, replacing intermediate 1-3 with intermediate 4-2, with a yield of 67%.

[0129] The synthesis method of compound 80 refers to the synthesis of compound 1, and intermediate 1-4 and iodobenzene are replaced by intermediate 4-3 and (4-bromophenyl) diphenylphosphine oxide, with a yield of 65%. The result of mass spectrometry of the obtained sample is: HR-MS (APCI): m / z 617.1909 [M+H] + ; C 44 H 28 NOP (%) calculated value: C, 85.5584; H, 4.5693; N, 2.2677; O, 2.5901; P, 5.0145; measured value: C, 85.5617; H, 4.5650; N, 2.2639; O, 2.5961; P, 5.0133.

[0130] Synthesis of compound 84:

[0131]

[0132] The synthesis method of compound 84 was based on the synthesis of compound 1, except that intermediate 1-4 and iodobenzene were replaced by intermediate 4-3 and intermediate 4-4, with a yield of 62%. The mass spectrometry results of the obtained sample were: HR-MS (APCI): m / z 557.1780 [M+H] + ; C 42 H 23 NO (%) Calculated value: C, 90.4618; H, 4.1574; N, 2.5118; O, 2.8690; Found: C, 90.4682; H, 4.1543; N, 2.5101; O, 2.8674.

[0133] Synthesis of compound 89:

[0134]

[0135] The synthesis method of compound 89 refers to the synthesis of compound 1, and intermediate 1-4 and iodobenzene are replaced by intermediate 4-3 and 2-bromo-9,9'-spirobifluorene, with a yield of 63%. The mass spectrometry result of the obtained sample is: HR-MS (APCI): m / z655.2300 [M+H] + ; C 51 H 29 N (%) calculated: C, 93.4067; H, 4.4575; N, 2.1359; found: C, 93.4002; H, 4.4737; N, 2.1261.

[0136] Synthesis of compound 90:

[0137]

[0138] The synthesis method of compound 90 refers to the synthesis of compound 1, and intermediate 1-4 and iodobenzene are replaced by intermediate 4-3 and 2-bromo-N-phenylcarbazole, with a yield of 71%. The result of mass spectrometry detection of the obtained sample is: HR-MS (APCI): m / z 582.2096 [M+H] + ; C 44 H 26 N2(%) calculated value: C, 90.6948; H, 4.4976; N, 4.8076; measured value: C, 90.6885; H, 4.5011; N, 4.8104.

[0139] All other compounds can be prepared by referring to the synthesis method of compound 1. The only difference is that different intermediates need to be used to replace the reactant intermediates in the synthesis of compound 1 according to different products, and the mass amount of the compound is changed according to different molar amounts. The intermediate compounds that are connected can be directly purchased or easily prepared.

[0140] The performance parameters (including Tg temperature, HOMO energy level and LUMO energy level, triplet energy T1, Eg) of the compounds synthesized in the embodiments of the present invention and the existing OLED materials HT2 (Comparative Example 1) and H1 (Comparative Example 2) are measured below. The results are shown in Table 1.

[0141] Table 1: Performance parameter measurement results of the compounds of the present invention and existing materials

[0142]

[0143] 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, the calculation method adopts B3LYP hybrid functional, basis set 6-31g(d); Eg=absolute value of HOMO-LUMO; Tg temperature is the experimental measured value, which is measured on a DSC-60 differential scanning calorimeter (Shimadzu Corporation, Japan), and the nitrogen flow rate is 10 ml / min.

[0144] As can be seen from Table 1, the compounds provided by the present invention have a higher glass transition temperature and better film-forming properties, so that the life of the OLED device containing the materials of the present invention is improved; they have suitable triplet energy and HOMO / LUMO energy levels, which are beneficial to the transport of carriers and the transfer of energy in OLED devices. The compounds of the present invention are suitable for use as hole transport materials or phosphorescent host materials.

[0145] Device Examples

[0146] Taking some compounds provided by the present invention as examples, they are respectively applied as the second hole transport material or the main material of the light-emitting layer in an organic electroluminescent device to verify the excellent effects achieved.

[0147] Example 1

[0148] 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.

[0149] 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 HT1 with a thickness of 60 nm; the material of the second hole transport layer 5 is HT2 with a thickness of 10 nm; the light-emitting layer 6 uses RD01 as the light-emitting material and compound 1 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.

[0150] The basic material structure used in each functional layer of the device is as follows:

[0151]

[0152] The specific preparation steps of the above organic electroluminescent device are as follows:

[0153] 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;

[0154] 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;

[0155] 3) Vacuum evaporation of hole transport material HT1 on the hole injection layer with a thickness of 60 nm, which serves as the first hole transport layer;

[0156] 4) Vacuum evaporation is performed on the first hole transport layer HT1 to deposit a hole transport material HT2 with a thickness of 15 nm, and this layer serves as the second hole transport layer;

[0157] 5) On the second hole transport layer, a light-emitting layer was co-deposited by vacuum evaporation, using compound 1 as the main material and RD01 as the doping material, with a doping mass ratio of 6% and a thickness of 30 nm;

[0158] 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.

[0159] 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;

[0160] 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;

[0161] 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 the cathode layer.

[0162] Embodiment 2 to Embodiment 12

[0163] The implementation process is the same as that of Example 1, except that the main material of the light-emitting layer is replaced by other compounds synthesized in the examples of the present invention instead of Compound 1.

[0164] Embodiment 13~embodiment 20

[0165] The implementation process is the same as that of Example 1, except that the second hole transport material is replaced by other compounds synthesized in the examples of the present invention instead of HT2, and H1 is used as the main material of the light-emitting layer instead of Compound 1.

[0166] Comparative Example 1

[0167] The implementation process is the same as that of Example 1, except that H1 is used as the main material of the light-emitting layer instead of Compound 1.

[0168] 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 initial brightness of the device is 3000cd / m 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 2.

[0169] Table 2: Comparison of performance results of organic electroluminescent devices in each group

[0170]

[0171] As can be seen from Table 2, the compounds provided by the present invention are applied to OLED red light devices as the second hole transport layer material or as the main material of the light-emitting layer, and the performance is improved. For example, the compound 73 in Example 10 is used as the main material, compared with H1 in the comparative example, the luminous efficiency and service life are significantly improved, the brightness efficiency is increased by 38%, and the service life is increased by 48%; the compound 7 in Example 13 is used as the second hole transport material, compared with HT2 in the comparative example, the luminous efficiency and service life are also significantly improved. It can be seen that the efficiency and life of the device are well performed by selecting the compounds of the present invention, and the synthesis process of the material is simple, which has great application value in the application of OLED devices and has good industrialization prospects.

[0172] In the organic compound provided by the present invention, the seven-membered ring structure can well restrict the rotation and vibration of the naphthalene ring, greatly improve the rigidity of the material, enhance the stability of the material, further enhance the electron-donating ability of the parent core by combining the naphthalene ring with a six-membered nitrogen or oxygen heterocycle, and effectively improve the carrier migration ability of the novel compound constructed by the present invention by connecting an electron-donating group or a strong electron-pulling group. The organic compound has a suitable orbital energy level and can effectively reduce the driving voltage, improve the brightness efficiency and lifespan, and significantly improve the photoelectric performance of the organic electroluminescent device as a hole transport material or a phosphorescent host material.

[0173] It should be understood that the disclosed invention is not limited only to the specific method, scheme and material of description, because these all can change.It should also be understood that the terminology used herein is only for the purpose of describing specific embodiment scheme, rather than being intended to limit the scope of the present invention, and the scope of the present invention is only limited to the appended claims.

[0174] Those skilled in the art will also recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the invention described herein. Such equivalents are also intended to be encompassed by the appended claims.

Claims

1. An organic compound, characterized in that The organic compound is selected from any one of the following compounds:

2. Use of the organic compound according to claim 1 in the preparation of electroluminescent materials.

3. Use of the organic compound according to claim 1 in the preparation of hole transport materials or phosphorescent light-emitting host materials.

4. Use of the organic compound according to claim 1 in an organic electroluminescent device or an organic electroluminescent display device.

5. A compound for an organic electroluminescent device, characterized in that: The compound comprises the organic compound according to claim 1.

6. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises 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; wherein, The first hole transport layer, the second hole transport layer or the light emitting layer contains the organic compound according to claim 1 .

Images