Compound taking aza-fluoranthene aza-five-membered ring as mother nucleus and application of compound

Abstract

The invention belongs to the technical field of organic light-emitting materials, and relates to a compound with aza-fluoranthene aza-five-membered ring as a mother nucleus and application of the compound. According to the compound provided by the invention, an aza-fluoranthene aza-five-membered ring is used as a parent nucleus, and a group with a specific property is selected for substitution at a specific position, so that the pi-pi conjugation ability of the compound is enhanced. The compound has an appropriate orbital energy level, relatively high triplet energy and glass transition temperature, effectively improved carrier mobility, and good thermal stability and film-forming property, can be used as a luminescent layer main body and an electron transport material to be applied to an organic electroluminescent device, can reduce the driving voltage of the device, and can improve the efficiency of the device. And the luminous efficiency and the service life of the device are improved.

Description

Technical Field

[0001] The invention belongs to the technical field of organic luminescent materials and relates to a compound with an azafluoranthene and azapentacyclic ring as a parent core and application thereof. Background Art

[0002] At present, organic electroluminescent devices have been applied in the industry, but the low efficiency and low life of the devices are fatal factors, which seriously restrict their application. To obtain OLED devices with excellent performance, it is necessary to first select hole / electron transport materials with excellent mobility to ensure that electrons and holes can achieve carrier balance in the light-emitting layer. Since it is difficult for organic molecules to obtain high electron mobility, the recombination area in the device is often close to the side of the electron transport layer, which requires the electron transport material to have a high triplet energy level to confine the excitons. High triplet (weak conjugation) and high mobility (strong conjugation) have always been an irreconcilable contradiction in the design of organic molecules. Since the production of OLED devices requires multiple processes such as photolithography, evaporation, and packaging, it needs to withstand high temperature treatment, and the device will also generate a lot of Joule heat when working. High temperature environment will cause fatal damage to OLED devices, not only in that high temperature causes the organic film with poor thermal stability to begin to crystallize from an amorphous film, resulting in device attenuation; the temperature increase will also cause uneven local currents in the light-emitting area of ​​the OLED device, resulting in uneven light emission. At the same time, a wider band gap will also have poor thermal stability. These problems have always restricted the development of OLED transmission materials. The thermal stability of organic materials can be measured by the glass transition temperature Tg. Currently, researchers generally obtain organic materials with higher Tg by rationally designing the molecular structure (such as increasing the molecular weight or adopting a rigid molecular structure). According to the current industrial application of OLED devices, in order to meet the requirements of the optoelectronic properties of the device, it is necessary to select OLED functional materials or material combinations with high performance to achieve the comprehensive characteristics of high efficiency, long life and low voltage of the device. At present, the development of OLED materials is still significantly behind the requirements of panel manufacturers and the needs of actual applications. The development of higher performance organic functional materials is particularly important and urgent in the face of current market demand. Summary of the invention

[0003] In view of the deficiencies in the prior art and the need for improvement, the present invention provides a compound having an azafluoranthene and aza-five-membered ring as a parent core and modified with different electronegative groups at specific substitution positions, which has relatively balanced carrier transport performance, suitable frontier orbital energy levels and relatively high triplet energy. Such compounds can be applied to organic electroluminescent devices as the main material of the light-emitting layer or the electron transport material, and can significantly improve the device performance of the organic electroluminescent device, thereby achieving the purposes of high efficiency and long life.

[0004] In one aspect, the present invention relates to a class of compounds having a structure as shown in formula (I),

[0005]

[0006] Wherein, X is selected from one of NR1, O, and S;

[0007] Y1-Y5 are independently selected from one of C or N;

[0008] At least one of Y1 or Y2 is N;

[0009] The L1 or L2 is independently a bridging group;

[0010] Ar1, Ar2, and R1 are each independently selected from a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl group having 6 to 30 carbon atoms and containing a heteroatom of N, O, S, Si, or P.

[0011] Furthermore, in the compounds provided by the present invention, the bridging group is a combination of one or more of a single bond, an arylene group, a heteroaryl group, a phosphorus oxide group, and a sulfoxide group.

[0012] Further, in the compounds provided by the present invention, the L1 or L2 contains an arylene group and / or a heteroaryl group;

[0013] The arylene group and / or heteroaryl group has no more than 30 carbon atoms.

[0014] Furthermore, in the compounds provided by the present invention, Y1 to Y5 are the same or different when they appear each time, representing C or N, and each time one of Y1 and Y2 must be a N atom, having structures shown in Formulas 1 to 12,

[0015]

[0016] Furthermore, in the compounds provided by the present invention, X is one of NR1, O, and S, and has a structure as shown in Formula 13 to Formula 48,

[0017]

[0018] Furthermore, in the compound provided by the present invention, the bridging group is selected from one of a single bond, a phenyl group, a pyridyl group, a triazine group, a fluoranthenyl group, and a spirobifluorenyl group.

[0019] Specifically, the bridging group is selected from one of the following structures:

[0020]

[0021] Further, in the compounds provided by the present invention, Ar1, Ar2, and R1 are independently selected from pyridyl, pyrrolyl, pyrazinyl, pyrimidinyl, azanaphthyl, quinolyl, azadiphenyl, terphenyl, azaterphenyl, anthracenyl, triphenylene, fluoranthene, dicyanobenzene, fluorophenyl, tert-butylbenzene, benzofuranyl, benzocarbazolyl, benzothiophenyl, dimethylfluorenyl, benzimidazolyl, phenanthroimidazolyl, naphthioimidazolyl, azophenyl-3-ylcarbazolyl, triazolyl, benzoxazolyl, indolyl, naphthoxazolyl, naphthiothiazolyl, 3,5-diphenyltriazine, 3,5-dipyridyltriazine, and one of the amino derivatives.

[0022] Specifically, Ar1, Ar2, and R1 are independently selected from one of the following structures:

[0023]

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

[0025] Furthermore, in the compounds provided by the present invention, the compounds have a structure as shown in any one of Compounds 1 to 156,

[0026]

[0027]

[0028]

[0029]

[0030]

[0031] On the other hand, the present invention relates to an intermediate for synthesizing the compound, which is selected from intermediate 1 to intermediate 48.

[0032]

[0033]

[0034] In another aspect, the present invention relates to use of the compound in an organic electroluminescent device or an organic electroluminescent apparatus.

[0035] Compared with the prior art, the technical solution provided by the present invention has at least the following beneficial effects or advantages:

[0036] The present invention introduces nitrogen atoms at specific positions on the fluoranthene ring, obtains different π-π conjugation capabilities at the 2 and 3 positions of the fluoranthene and aza-five-membered rings, enhances the electron-pulling ability of the parent core, and modifies the obtained compounds at specific positions with different electronegative groups, which can be used as OLED functional materials. The aza-fluoranthene and aza-five-membered ring compounds provided by the present invention have high glass transition temperature, good thermal stability, good film-forming properties, and improve the life of OLED devices. The aza-fluoranthene and aza-five-membered ring compounds provided by the present invention also have high carrier transport performance and suitable HOMO / LUMO energy levels, and when used as electron transport materials, the efficiency of the OLED devices is improved. The aza-fluoranthene and aza-five-membered ring compounds provided by the present invention also have relatively balanced carrier transport performance and high triplet energy levels through modification with electron-donating groups, and can significantly improve device performance when used as a main material, and are relatively promising organic OLED functional materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] 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.

[0038] Figure 1 Schematic diagram of the structure of an organic electroluminescent element.

[0039] Among them, 1 is the substrate, 2 is the anode layer, 3 is the hole injection layer, 4 is the first hole transport layer, 5 is the second hole transport layer, 6 is the light emitting layer, 7 is the hole blocking layer, 8 is the electron transport layer, 9 is the electron injection layer, and 10 is the cathode layer. DETAILED DESCRIPTION

[0040] 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.

[0041] Preparation Example

[0042] When X in the general formula (I) is N, the relevant intermediate synthesis route is as follows:

[0043]

[0044] Synthesis of intermediate 1-3: Under nitrogen protection, intermediate 1-1 and intermediate 1-2, Pd(PPh3)4 (tetrakis(triphenylphosphine)palladium, K2CO3, TBAB (tetrabutylammonium bromide), and a solvent in a ratio of toluene / ethanol / water = 4:2:1 were added to a three-necked flask, reacted at 80°C for 6 hours, cooled to room temperature, washed with water until neutral, dried, and purified by a silica gel column to obtain intermediate 1-3.

[0045] Synthesis of intermediate 1-4: Under nitrogen protection, add intermediate 1-3, Pd(PPh3)2Cl2 (bis(triphenylphosphine)palladium dichloride), K2CO3, DBU (1,8-diazabicyclo[5.4.0]undec-7-ene), and DMF solvent into a three-necked flask, and stir to react at 150°C. When TLC detects that the raw material reaction is complete, cool to room temperature, add dichloroethane, wash with water until neutral, dry, and purify through a silica gel column to obtain intermediate 1-4.

[0046] Synthesis of intermediate 1-5: Under nitrogen protection, add intermediate 1-4, NBS (N-bromosuccinimide), and chloroform solvent into a three-necked flask, stir and react at room temperature for 3 hours, wash with water, dry, and purify through a silica gel column to obtain intermediate 1-5.

[0047] Synthesis of intermediate 1-6: Under nitrogen protection, add intermediate 1-5 and tetrahydrofuran solvent to a three-necked flask, cool the liquid nitrogen to -78°C, then drop butyl lithium and keep warm for 1 hour, then drop trimethyl borate, keep warm for 1 hour, then naturally warm to room temperature 24°C and continue to react for 2 hours. After the reaction is completed, quench the reaction with an aqueous ammonium chloride solution, add dilute hydrochloric acid to adjust the pH to 3, then wash with water, dry, concentrate, add ethanol to precipitate the product, and filter to obtain intermediate 1-6.

[0048] Synthesis of intermediate 1-7: Add intermediate 1-6, amidine intermediate with L1 and R1 groups, Cu(OAc)2 (copper acetate), NaOPiv (sodium pivalate), and DMF solvent into a three-necked flask, stir and react at 60°C for 30h, then introduce O2, heat to 120°C and continue to react for 20h, then naturally cool to room temperature, add ammonium hydroxide aqueous solution to quench, then wash with water, dry, and purify through a silica gel column to obtain intermediate 1-7.

[0049] The synthetic routes and methods of intermediates with the same core structure as intermediate 1-7 but with different numbers of nitrogen atoms on the fluoranthene ring are similar. The substituents and yields of each intermediate are shown in the following table:

[0050]

[0051]

[0052] When Y2 is C, the synthetic routes of intermediates and compounds are as follows:

[0053]

[0054] The synthesis of intermediate 1-9 was carried out by referring to the synthesis method of intermediate 1-5, except that intermediate 1-4 was replaced by intermediate 1-8.

[0055] Synthesis of intermediate 1-10: Under nitrogen protection, add intermediate 1-9, Pd(PPh3)4(tetrakis(triphenylphosphine)palladium, Cy2PF-PtBu2((S)-1-[(S)-2-(dicyclohexylphosphino)ferrocenyl]ethyl di-tert-butylphosphine), ammonium sulfate, sodium tert-butoxide, and toluene into a three-necked flask, stir and react at 105°C for 6 hours, then cool to room temperature, wash with water until neutral, dry, and purify through a silica gel column to obtain intermediate 1-10.

[0056] The synthesis of intermediate 1-11 was carried out by referring to the synthesis method of intermediate 1-5, except that intermediate 1-4 was replaced by intermediate 1-10.

[0057] Synthesis of intermediate 1-12: Under nitrogen protection, add intermediate 1-11 and ethanol solvent to a three-necked flask, slowly add sulfuric acid at 0°C, and then continue to add sodium nitrite aqueous solution, stir and react for 1 hour, then add copper powder, add sulfuric acid, heat to reflux after the addition is complete, cool to room temperature after TLC detection of the complete reaction of the raw materials, add toluene extraction, wash with water until neutral, dry, and purify through a silica gel column to obtain intermediate 1-12.

[0058] The synthetic routes and methods of intermediates with the same core structure as intermediates 1-12 but with different numbers of N on the fluoranthene ring are similar. The substituents and yields of each intermediate are shown in the following table:

[0059]

[0060]

[0061] When X in the general formula (I) is O, the corresponding intermediate synthesis route is as follows:

[0062]

[0063] The synthesis method of intermediate 2-2 refers to the synthesis method of intermediate 1-4, except that intermediate 1-3 is replaced by 2-1.

[0064] Synthesis of intermediate 2-3: Under nitrogen protection, add intermediate 2-2 and acetic acid to a three-necked flask, and slowly add two equivalents of a mixed acid of nitric acid / concentrated sulfuric acid while stirring at room temperature. After the addition is complete, continue to react for 2 hours. When TLC detects that the raw material has reacted completely, add ice water, stir, cool to 10°C, filter, add the filtered solid into ice water again, slurry for 1 hour, and filter to obtain intermediate 2-3.

[0065] Synthesis of intermediate 2-4: Under nitrogen protection, add intermediate 2-3, BBr3 (boron tribromide), and dichloroethane solvent into a three-necked flask, react at 78°C for 3h, cool to room temperature, wash with water, dry, and purify through a silica gel column to obtain intermediate 2-4.

[0066] Synthesis of intermediate 2-6: Under nitrogen protection, add intermediate 2-4, intermediate 2-5, DPPF (1,1'-bis(diphenylphosphino)ferrocene), and o-dichlorobenzene solvent into a three-necked flask, heat to 178°C and reflux for 2h, reflux and separate water under normal pressure throughout the process, reduce pressure and concentrate, cool to room temperature, add 4 times n-heptane, reflux for 30min and filter quickly, pass the filtrate through a silica gel column and concentrate, add ethanol to precipitate the product, and filter to obtain intermediate 2-6.

[0067] The intermediates with the same core structure as intermediate 2-6 but with different numbers of N on the fluoranthene ring have similar synthetic routes and methods. The substituents and yields of each intermediate are shown in the following table:

[0068]

[0069] When X in the general formula (I) is S, the corresponding intermediate synthesis route is as follows:

[0070]

[0071]

[0072] Synthesis of intermediate 3-1: Under nitrogen protection, add intermediate 1-5, Pd(OAc)2 (palladium acetate), sodium tert-butoxide, 1,4-dioxane solvent, and 5 mol / L ammonia solution into a three-necked flask, reflux at 100°C for 5 hours, then cool to room temperature, add toluene to extract and wash with water until neutral, dry and pass through a silica gel column, and concentrate the column liquid to obtain intermediate 3-1.

[0073] Synthesis of intermediate 3-3: Under nitrogen protection, add intermediate 3-1, NEt3 (triethylamine), and dichloroethane solvent into a three-necked flask, heat to 80°C and reflux, slowly add intermediate 3-2 in batches, reflux for 16 hours, cool to room temperature, add dichloroethane and wash with water until neutral, dry and concentrate to obtain intermediate 3-3.

[0074] Synthesis of intermediate 3-4: Under nitrogen protection, add intermediate 3-3, Lawesson's reagent, and toluene solvent into a three-necked flask, heat to 110°C and reflux for 4 hours, then cool to room temperature, add n-heptane to precipitate solid, filter and recrystallize with toluene / ethanol mixed solvent to obtain intermediate 3-4.

[0075] Synthesis of intermediate 3-5: Under nitrogen protection, add intermediate 3-4, sodium glycine, acetonitrile solvent, Ru(bpy)3(PF6)2(tris(2,2'-bipyridine)ruthenium di(hexafluorophosphate)), Co(dmgH)2(4-NMe2Py)Cl(chlorobis(dimethylglyoxime)[4-(dimethylamino)pyridine]cobalt(III)), DMAP (4-dimethylaminopyridine) into a three-necked flask, stir and reflux at 80°C and react under blue light irradiation for 15h, add dichloroethane to extract and wash with water until neutral, dry and pass through a silica gel column, and concentrate the column liquid to obtain intermediate 3-5.

[0076] The intermediates with the same core structure as intermediate 3-5 but different numbers of N on the fluoranthene ring have similar synthetic routes and methods. The substituents and yields of each intermediate are shown in the following table:

[0077]

[0078]

[0079] When Y2 is C, referring to the synthesis method of intermediate 1-12, the intermediate shown below can be obtained:

[0080]

[0081]

[0082] Synthesis of compound 1:

[0083]

[0084] Under nitrogen protection, intermediate 1 (10.0 g, 21 mmol) and pyridine-3-boric acid (3.1 g, 24 mmol), Pd(PPh3)4 (tetrakis(triphenylphosphine)palladium, 0.3 g, 0.2 mmol), K2CO3 (potassium carbonate, 11.6 g, 84 mmol), TBAB (tetrabutylammonium bromide, 0.6 g, 2 mmol), toluene (100 mL), ethanol (50 mL), water (25 mL) were added to a three-necked flask, stirred at 76 ° C for 6 h, cooled to room temperature, washed with water until pH = 7, the organic phase was dried over anhydrous magnesium sulfate and passed through a silica gel column, concentrated and squeezed out with 30 ml of ethanol to obtain 7.7 g of compound 1, with a yield of 78%. The results of mass spectrometry of the obtained sample are: HR-MS (APCI): m / z 472.1688 [M+H] + ; C 33 H 20 N4 calculated value: C, 83.8773; N, 11.8565; H, 4.2662; measured value: C, 83.8768; N, 11.8572; H, 4.2660;

[0085] Synthesis of compound 26:

[0086]

[0087] Under nitrogen protection, intermediate 1 (10.0 g, 21 mmol) and dibenzofuran-4-boric acid (4.6 g, 22 mmol), Pd(PPh3)4 (tetrakis(triphenylphosphine)palladium, 0.3 g, 0.2 mmol), K2CO3 (potassium carbonate, 11.6 g, 84 mmol), TBAB (tetrabutylammonium bromide, 0.6 g, 2 mmol), toluene (100 mL), ethanol (50 mL), water (25 mL) were added to a three-necked flask, stirred at 76°C for 7.5 h, cooled to room temperature, washed with water until pH = 7, the organic phase was dried over anhydrous magnesium sulfate and passed through a silica gel column, concentrated and recrystallized from toluene to obtain 9.4 g of compound 26, with a yield of 80%. The mass spectrometry results of the obtained sample are: HR-MS (APCI): m / z 561.1841 [M+H] + ; C 40 H 23 ON3 calculated value: C, 85.5471; N, 7.4818; O, 2.8486; H, 4.1279; measured value: C, 85.5437; N, 7.4849; O, 2.8481; H, 4.1233;

[0088] Synthesis of compound 58:

[0089]

[0090] Under nitrogen protection, intermediate 5 (10.0 g, 21 mmol) and 2,4,6-triphenylphenylboronic acid (7.4 g, 21 mmol), Pd(PPh3)4 (tetrakis(triphenylphosphine)palladium, 0.3 g, 0.2 mmol), K2CO3 (potassium carbonate, 11.6 g, 84 mmol), TBAB (tetrabutylammonium bromide, 0.6 g, 2 mmol), toluene (100 mL), ethanol (50 mL), water (25 mL) were added to a three-necked flask, stirred at 76°C for 7 hours, cooled to room temperature, washed with water until pH = 7, the organic phase was dried over anhydrous magnesium sulfate and passed through a silica gel column, concentrated and squeezed out with 50 ml of ethanol to obtain 11 g of compound 58, with a yield of 75%. The mass spectrometry results of the obtained sample are: HR-MS (APCI): m / z 700.2627 [M+H] + ; C 51 H 32 N4 calculated value: C, 87.4032; N, 7.9943; H, 4.6024; measured value: C, 87.4135; N, 7.9901; H, 4.5964;

[0091] Synthesis of compound 70:

[0092]

[0093] Under nitrogen protection, intermediate 3 (10.1 g, 21 mmol), diphenyl-4-ylamine (6.8 g, 21 mmol), Pd2(dba)3 (tri(dibenzylideneacetone)dipalladium, 0.4 g, 0.4 mmol), P(t-Bu)3 (tri-tert-butylphosphine, 0.2 g, 1 mmol), DBU (1,8-diazabicyclo[5.4.0]undec-7-ene, 0.7 g, 5 mmol), sodium tert-butoxide (8 g, 83 mmol), toluene (100 mL) were added to a three-necked flask, and the mixture was stirred and refluxed at 110°C for 2 h. After the reaction was complete, the reaction solution was cooled to room temperature, washed with water until neutral, the organic phase was dried over anhydrous 10 g magnesium sulfate for 2 h and filtered, and the filtrate was purified by silica gel column to obtain 12.1 g of compound 70 with a yield of 81%. The results of mass spectrometry of the obtained sample are: HR-MS (APCI): m / z 715.2736 [M+H] + ; C 51 H 33 N5 calculated value: C, 85.5699; N, 9.7833; H, 4.6467; measured value: C, 85.5721; N, 9.7880; H, 4.6399;

[0094] Synthesis of compound 80:

[0095]

[0096] Under nitrogen protection, intermediate 4 (10.0 g, 21 mmol) and 10-phenylanthracene-9-ylboronic acid (6.3 g, 21 mmol), Pd(PPh3)4 (tetrakis(triphenylphosphine)palladium, 0.3 g, 0.2 mmol), K2CO3 (potassium carbonate, 11.6 g, 84 mmol), TBAB (tetrabutylammonium bromide, 0.6 g, 2 mmol), toluene (100 mL), ethanol (50 mL), water (25 mL) were added to a three-necked flask, heated to 76 ° C and stirred for 6 h, then cooled to room temperature, washed with water until pH = 7, the organic phase was dried over anhydrous magnesium sulfate and passed through a silica gel column, concentrated and recrystallized with 60 ml of toluene to obtain 11 g of compound 80, with a yield of 81%. The mass spectrometry results of the obtained sample are: HR-MS (APCI): m / z 647.2361 [M+H] + ; C 48 H 29 N3 calculated value: C, 89.0004; N, 6.4869; H, 4.5126; measured value: C, 89.0052; N, 6.4835; H, 4.5113;

[0097] Synthesis of compound 100:

[0098]

[0099] Under nitrogen protection, intermediate 14 (10.0 g, 21 mmol) and 100 ml of THF solvent were added to a three-necked flask. The liquid nitrogen was cooled to -78°C, and then butyl lithium (20 ml, 2.5 M) was slowly added dropwise with stirring. After the addition was completed, the temperature was maintained and the reaction was continued with stirring for 1 h. Then diphenylphosphine chloride (5.1 g, 23 mmol) was added, and the temperature was maintained and the reaction was continued for 3 h. After that, 20 ml of saturated ammonium chloride solution was added to quench the reaction. After warming to room temperature, THF was evaporated under reduced pressure, 100 ml of dichloroethane was added, and the mixture was washed with water until neutral. After concentration, 50 ml of hydrogen peroxide was added, and the mixture was stirred at 40°C for 3 h. After the solid was precipitated, 200 ml of dichloroethane was added and the mixture was washed with water until neutral, and dried over anhydrous magnesium sulfate. After filtration, the filtrate was completely concentrated, and 45 ml of toluene was added for recrystallization to obtain 9.9 g of compound 100 with a yield of 70%. The mass spectrometry results of the obtained samples were: HR-MS (APCI): m / z 672.6079 [M+H] + ; C 45 H 29 ON4P calculated value: C, 80.3438; N, 8.3285; H, 4.3453; O, 2.3782; P, 4.6042; measured value: C, 80.3468; N, 8.3291; H, 4.3434; O, 2.3746; P, 4.6061;

[0100] Synthesis of compound 106:

[0101]

[0102] Synthesis of intermediate 9-3: Under nitrogen protection, add intermediate 9-2, phosphorus oxychloride (POCl3), and acetonitrile solvent into a three-necked flask, heat to 80°C and reflux for 1 hour, add intermediate 9-1 in batches, continue to react for 3 hours, then cool to room temperature, add toluene for extraction and wash with water until neutral, dry the organic phase with anhydrous magnesium sulfate, concentrate the filtrate and squeeze out the solid with n-heptane, then recrystallize with toluene to obtain intermediate 9-3.

[0103] The synthesis method of intermediate 9-4 refers to the synthesis of intermediate 1-6, except that intermediate 1-5 is replaced by intermediate 9-3.

[0104] Under nitrogen protection, intermediate 9 (10.0 g, 21 mmol) and intermediate 9-4 (7.7 g, 21 mmol), Pd(PPh3)4 (tetrakis(triphenylphosphine)palladium, 0.3 g, 0.2 mmol), K2CO3 (9.4 g, 68 mmol), TBAB (tetrabutylammonium bromide, 0.6 g, 2 mmol), toluene (100 mL), ethanol (50 mL), water (25 mL) were added to a three-necked flask, stirred at 76°C for 6 h, cooled to room temperature, and washed with 100 ml of toluene water until pH = 7. The organic phase was dried over anhydrous magnesium sulfate, and the filtrate was passed through a silica gel column. When the column liquid was concentrated to about 40 ml, 40 ml of ethanol was added to precipitate the solid, and 10.2 g of compound 106 was obtained by filtration, with a yield of 68%. The mass spectrometry results of the obtained sample are: HR-MS (APCI): m / z 719.2182 [M+H] + ; C 46 H 25 ON9 calculated value: C, 76.7617; N, 17.5144; O, 2.2228; H, 3.5011; measured value: C, 76.7629; N, 17.5135; O, 2.2212; H, 3.5024;

[0105] Synthesis of compound 119:

[0106]

[0107] The synthesis method of intermediate 42-2 refers to the synthesis of intermediate 1-3, except that intermediate 1-1 and intermediate 1-2 are replaced by intermediate 42 and intermediate 42-1.

[0108] Under nitrogen protection, intermediate 42-2 (10.0 g, 17 mmol) and 1,3,5-triazine, 2-bromo-4,6-diphenyl (5.9 g, 19 mmol), Pd(PPh3)4 (tetrakis(triphenylphosphine)palladium, 0.3 g, 0.2 mmol), K2CO3 (9.4 g, 68 mmol), TBAB (tetrabutylammonium bromide, 0.6 g, 2 mmol), toluene (100 mL), ethanol (50 mL), water (25 mL) were added to a three-necked flask, and the reaction was stirred at 76 ° C for 8 h, then cooled to room temperature, 100 ml of dichloroethane was added and washed to pH = 7, the organic phase was dried over anhydrous magnesium sulfate and concentrated completely, 120 ml of toluene was added, heated to 60 ° C until completely dissolved, and passed through a 60 ° C insulated silica gel column. When the column liquid was concentrated to about 50 ml, 50 ml of ethanol was added to precipitate the solid, and 9.3 g of compound 119 was obtained by filtration, with a yield of 71%. The mass spectrometry results of the obtained samples were as follows: HR-MS (APCI): m / z 768.1944 [M+H] + ; C 48 H 28O3N6S calculated values: C, 74.9857; N, 10.9309; O, 6.2427; H, 3.6709; S, 4.1699; Found values: C, 74.9891; N, 10.9313; O, 6.2379; H, 3.6726; S, 4.1691;

[0109] The following compounds were prepared by referring to the synthesis method of compound 1 or compound 70. The only difference was that different intermediates were used to replace the reactant intermediates in the synthesis of compound 1 or compound 70 according to different products, and the mass amount of the compound was changed according to the different molar amounts.

[0110] Among them, reactants B are all intermediate compounds that can be directly purchased or easily prepared.

[0111]

[0112]

[0113] The above method can achieve a better preparation of the compound involved in the present invention, and the remaining compounds can be prepared by referring to the above preparation method.

[0114] Test Case

[0115] This test example provides parameter measurements of some compounds, as well as the performance of organic electroluminescent device embodiments made from these compounds.

[0116] The compounds provided by the present invention can be used as the main material of the light-emitting layer and the electron transport layer material of the OLED device. The performance parameters (including Tg temperature, HOMO energy level and LUMO energy level, triplet energy T1) of Examples 1-45 and the existing OLED materials ET1 (comparative example) and CBP (comparative example) are measured as shown in Table 1 below, wherein:

[0117] The Tg temperature was measured on a DSC-60 differential thermal scanning analyzer (Shimadzu Corporation, Japan) with a nitrogen flow rate of 10 ml / min;

[0118] The HOMO / LUMO energy levels and triplet energy T1 are obtained by simulation calculation using Gaussian 09 software. The calculation method adopts B3LYP hybrid functional and basis set 6-31g(d).

[0119] Table 1: Comparison of performance parameters of the compounds in each example and the comparative example

[0120]

[0121]

[0122] 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; the compounds of the present invention also have suitable HOMO / LUMO energy levels and higher triplet energy, and can be used as light-emitting host materials or electron transport materials.

[0123] The 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.

[0124] 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 GD01 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.

[0125] The basic material structure used in each functional layer of the device is as follows:

[0126]

[0127] The specific preparation steps of the above organic electroluminescent device are as follows:

[0128] 1) Clean the ITO anode 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;

[0129] 2) On the ITO anode layer, a hole injection layer material HAT-CN is deposited by vacuum evaporation with a thickness of 5 nm, which serves as a hole injection layer;

[0130] 3) Vacuum evaporation of a hole transport material HT1 with a thickness of 60 nm was performed on the hole injection layer, and this layer was used as the first hole transport layer;

[0131] 4) A hole transport material HT2 is deposited on the first hole transport layer HT1 by vacuum evaporation with a thickness of 10 nm, and this layer serves as the second hole transport layer;

[0132] 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 GD01 as the light-emitting material, with a doping mass ratio of 6% and a thickness of 30 nm;

[0133] 6) On the light-emitting layer, a hole blocking material HB1 is deposited by vacuum evaporation with a thickness of 10 nm, and this layer serves as a hole blocking layer;

[0134] 7) On the hole blocking layer, an electron transport material ET1 is deposited by vacuum evaporation with a thickness of 35 nm, and this layer serves as an electron transport layer;

[0135] 8) On the electron transport layer, the electron injection material Liq is evaporated by vacuum evaporation with a thickness of 2 nm, and this layer serves as the electron injection layer;

[0136] 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.

[0137] Device Example 2 to Device Example 20

[0138] The implementation process is the same as that of device embodiment 1, except that the main material of the light-emitting layer is replaced by other developed compounds instead of compound 1.

[0139] Device Comparison

[0140] The implementation process is the same as that of device embodiment 1, except that conventional material CBP is used as the main material of the light-emitting layer instead of compound 1.

[0141] Device Example 21 to Device Example 45

[0142] The implementation process is the same as that of device embodiment 1, except that the electron transport material is replaced by other developed compounds instead of ET1, and CBP is used as the main material of the light-emitting layer instead of compound 1.

[0143] The components of different devices prepared in device embodiments 1 to 45 of the present invention and comparative examples are shown in Table 2.

[0144] Table 2: Comparison of organic electroluminescent device components of various device examples

[0145]

[0146]

[0147] 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 test brightness to decay to 90% of the initial brightness is the device LT90 life.

[0148] Taking the test data of the starting voltage V, brightness efficiency and life LT90 of the device comparison as 1, the starting voltage V, brightness efficiency and life LT90 of device embodiments 1-45 are the relative values ​​of their respective test data and the test data of the device comparison, as shown in Table 3.

[0149] Table 3: Comparison of performance results of organic electroluminescent devices in each group

[0150]

[0151]

[0152] As can be seen from Table 3, the compounds provided by the present invention are applied to OLED devices as the main materials of the light-emitting layer, and the performance is improved. For example, the compound 26 in device embodiment 5 is used as the main material, compared with CBP in the comparative example, the luminous efficiency and service life are significantly improved, the brightness efficiency is increased by 52%, and the service life is increased by 14%; the compound 106 in device embodiment 33 is used as the electron transport material, compared with ET1 in the comparative example, the luminous efficiency and service life are significantly improved. It can be seen that the optoelectronic properties such as 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.

[0153] The present invention uses the strong electron-pulling property of the azafluoranthene-azapentacyclic core skeleton to connect different electronegative groups at fixed substitution positions to obtain a specific compound with balanced carrier transport performance. This type of compound has a suitable frontier orbital energy level and a relatively high triplet energy, and exhibits excellent performance as a light-emitting layer host and electron transport in an organic electroluminescent (OLED) device. Although there are contradictions such as the difficulty of having high triplet energy levels and high mobility, and the difficulty of reconciling wide band gaps and stability, it is expected that ideal materials with both high mobility and high stability will be further developed in the future to promote the further development of the OLED industry.

[0154] Obviously, those skilled in the art can make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if these modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, they are also intended to be included.

[0155] 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 (I), Wherein, X is selected from one of NR1, O, and S; Y1-Y5 are independently selected from one of C or N; At least one of Y1 or Y2 is N; The L1 or L2 is independently a bridging group; Ar1, Ar2, and R1 are each independently selected from a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl group having 6 to 30 carbon atoms and containing a heteroatom of N, O, S, Si, or P.

2. The compound according to claim 1, characterized in that The bridging group is a combination of one or more of a single bond, an arylene group, a heteroaryl group, a phosphorus oxide group, and a sulfoxide group.

3. The compound according to claim 2, characterized in that The L1 or L2 contains an arylene group and / or a heteroaryl group; The arylene group and / or heteroaryl group has no more than 30 carbon atoms.

4. The compound according to claim 1, characterized in that Having structures shown in Formula 1 to Formula 12, 5. The compound according to claim 4, characterized in that Having structures as shown in Formula 13 to Formula 48, 6. The compound according to claim 1, characterized in that The bridging group is selected from a single bond, a phenyl group, a pyridyl group, a triazine group, a fluoranthenyl group, and a spirobifluorenyl group.

7. The compound according to claim 1, characterized in that The Ar1, Ar2, and R2 are independently selected from the following substituted or unsubstituted groups: phenyl, pyridyl, pyrrolyl, pyrazinyl, pyrimidinyl, azanaphthyl, quinolyl, azadiphenyl, terphenyl, azaterphenyl, anthracenyl, benzophenanthryl, fluoranthene, dicyanobenzene, fluorophenyl, tert-butylbenzene, benzofuranyl, benzocarbazolyl, benzothiophenyl, dimethylfluorenyl, benzimidazolyl, phenanthroimidazolyl, naphthioimidazolyl, azophenyl-3-ylcarbazolyl, triazolyl, benzoxazolyl, indolyl, naphthoxazolyl, naphthiothiazolyl, 3,5-diphenyltriazine, 3,5-dipyridyltriazine, and one of the amino derivatives.

8. The compound according to claim 1, characterized in that Having a structure as shown in any one of Compound 1 to Compound 156, 9. An intermediate for synthesizing a compound according to any one of claims 1 to 8, characterized in that: Selected from Intermediate 1 to Intermediate 48, 10. Use of the compound according to any one of claims 1 to 8 in an organic electroluminescent device or an organic electroluminescent apparatus.

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