A naphthylenone derivative and an electroluminescent device based thereon

Abstract

The invention discloses a rylene phenone derivative and an electroluminescent device based thereon, belonging to the technical field of organic light-emitting materials and semiconductors. The rylene phenone derivative is used as a bipolar host material in the light-emitting layer of an OLED device, and while effectively balancing holes and electrons, a wider carrier recombination region can be formed, thereby greatly improving the luminous efficiency of the electroluminescent device, reducing the starting voltage and energy consumption, and extending the working life of the electroluminescent device.

Description

Technical Field

[0001] The invention belongs to the technical field of organic light-emitting materials and semiconductors, and in particular relates to a rylenephenone derivative and an electroluminescent device based thereon. Background Art

[0002] Display technology is inseparable from people's daily life. As a new generation of information display technology, Organic Light-Emitting Diode (OLED) is becoming more and more familiar and recognized by people. OLED is revolutionizing the display industry with its many excellent characteristics such as self-luminescence, high brightness, high contrast, see-through, wearable, foldable, low energy consumption, wide viewing angle and low temperature resistance. Therefore, this technology is becoming a hot research direction in the field of lighting and display.

[0003] At present, OLED devices are mostly realized by multi-layer functional composite method. Its functional layers mainly include hole injection layer, hole transport layer, hole blocking layer, electron injection layer, electron transport layer, electron blocking layer and light-emitting layer. Among them, the light-emitting layer is the most important part reflecting the quality of the device. Generally, the light-emitting layer material is composed of the main light-emitting material (Host) and the guest light-emitting material (Dopant) in a certain proportion. Furthermore, a sensitizer can also be added to optimize the light-emitting layer. In order to obtain efficient and stable light-emitting devices, in addition to having high stability, the main light-emitting material generally needs to have a higher lowest unoccupied molecular orbital (Lowest Unoccupied Molecular Orbital; LUMO) energy level and a lower highest occupied molecular orbital (Highest Occupied Molecular Orbital; HOMO) energy level, so that the molecule has a larger energy system, and a more efficient energy transfer process can be achieved for the guest molecule, thereby achieving efficient light emission of the guest molecule and avoiding the exciton annihilation phenomenon of the guest molecule due to excessive concentration.

[0004] At present, host materials are generally divided into hole transport type, electron transport type and bipolar transport type host materials. When a hole transport type host material is used, a charge recombination region will be generated at the interface between the light-emitting layer and the electron transport layer; when an electron transport type host material is used, a charge recombination region will be generated at the interface between the light-emitting layer and the hole transport layer. However, the weak carrier mobility and the unbalanced charge in the light-emitting layer have an adverse effect on the luminescence efficiency of organic light-emitting devices. At the same time, the narrow charge recombination region of organic electrophosphorescent devices will accelerate the triplet-triplet annihilation process, thereby causing a decrease in luminescence efficiency, especially under high current density conditions. To avoid this effect, the commonly used strategies are: (1) using two light-emitting layers, one of which uses a hole transport type host material and the other uses an electron transport type host material; (2) mixing hole transport type and electron transport type host materials in a single light-emitting layer. However, these two strategies make the device preparation complicated, and the mixed host materials will lead to phase separation problems. Therefore, in order to achieve efficient electroluminescence, it is necessary to develop host materials with balanced carrier transport properties to broaden the charge recombination area.

[0005] In recent years, bipolar transport host materials have attracted people's attention in the field of organic electroluminescent devices because of their ability to balance holes and electrons, and this material can simplify the structure of the device, but the existing bipolar transport host materials still have the problem that the luminous efficiency, stability and life span are difficult to meet the market demand. Therefore, it is very necessary to develop bipolar host materials with a larger energy system, which also has a very broad application prospect. Summary of the invention

[0006] In order to overcome the shortcomings of the above-mentioned prior art, the purpose of the present invention is to provide a naphthylenediol derivative and an electroluminescent device based thereon, so as to solve the technical problem that the existing bipolar transmission host materials still have luminous efficiency, stability and life span that are difficult to meet market demand.

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

[0008] The first aspect of the present invention discloses a pyrrolidine derivative, the structure of which is shown in general formula 1:

[0009]

[0010] Where:

[0011] As the main structure;

[0012] B is C 6 ~C 30 The bonding mode of B to the main structure is single bond;

[0013] L 1 C 6 ~C 40 The aromatic group, or C 6 ~C 40 Heteroaryl, L 1 The bonding mode with B is single bond;

[0014] The ring structure corresponding to B is called ring B.

[0015] Preferably, C 6 ~C 30 The fused ring aromatic group is selected from any one of the following groups or their derivatives:

[0016]

[0017] Among them, the Ring B and the main structure, and Ring B and L 1 The bonding position between .

[0018] Preferably, C 6 ~C 40 The heteroaryl group is selected from any one of the following groups or their derivatives:

[0019]

[0020] Among them, the substituent To replace the position.

[0021] The second aspect of the present invention discloses the use of the above-mentioned rylenephenone derivatives in the preparation of electroluminescent devices.

[0022] In a third aspect of the present invention, an organic electroluminescent device is disclosed, comprising an anode layer 2, a cathode layer 10 and an organic layer located between the anode layer 2 and the cathode layer 10, wherein the organic layer comprises a hole transport layer 4, a light-emitting layer 6 and an electron transport layer 8, wherein the light-emitting layer 6 comprises a host light-emitting material and a guest light-emitting material, wherein the host light-emitting material comprises the above-mentioned pyrrolidine derivative.

[0023] Preferably, the guest luminescent material is selected from phosphorescent materials , and The mass of the guest luminescent material accounts for 0.1% to 3.0% of the mass fraction of the entire luminescent layer 6.

[0024] Preferably, the guest luminescent material is selected from fluorescent materials or , and the mass of the guest luminescent material accounts for 2.0%~10.0% of the mass fraction of the entire luminescent layer 6.

[0025] Preferably, the light-emitting layer 6 further includes a sensitizer.

[0026] Further preferably, the sensitizer is selected from , and The mass of the sensitizer accounts for 0.05% to 0.5% of the mass fraction of the entire light-emitting layer 6.

[0027] Compared with the prior art, the present invention has the following beneficial effects:

[0028] The invention provides a pyrrolidine derivative, which takes pyrrolidine as the main structure. The pyrrolidine itself belongs to an electron-withdrawing group (Aceppt) and has high structural stability. Then, a common fluorescent host material structure fragment (B) is introduced at the α position of the pyrrolidine, thereby increasing the spatial rigidity of the entire molecule, retaining the efficient fluorescent luminescence efficiency of the conventional fluorescent host structure, and further improving the stability of the traditional fluorescent host material in terms of spatial structure, thereby further extending the device life. Finally, an electron-donating group (Donat) L is introduced into the fragment B. 1 , forming an ADD-type bipolar host luminescent material, which can maintain the balance of electrons and holes in the luminescent layer and effectively improve the luminescent performance of the device. The present invention introduces pyrrolidine derivatives with high triplet energy levels. Experiments have shown that when this type of material is used as a host material, it can more efficiently transfer and transfer the energy of its triplet excitons to the matching guest material, thereby greatly improving the luminescent efficiency of the luminescent layer, reducing the starting voltage and energy consumption, and extending the stability and working life of the electroluminescent device. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 is a cross-sectional view of the electroluminescent device of the present invention;

[0030] Figure 2 is the H NMR spectrum of compound 5 of the present invention;

[0031] Figure 3 is the H NMR spectrum of compound 127 of the present invention;

[0032] Figure 4 is the H NMR spectrum of compound 169 of the present invention;

[0033] Figure 5 is the H NMR spectrum of compound 35 of the present invention;

[0034] Figure 6 is the H NMR spectrum of compound 189 of the present invention;

[0035] Attached Figure 1 Marking Description:

[0036] 1- polymer substrate, 2- anode layer, 3- hole injection layer, 4- hole transport layer, 5- electron blocking layer, 6- light emitting layer, 7- hole blocking layer, 8- electron transport layer, 9- electron injection layer, 10- cathode layer, 11- covering layer. DETAILED DESCRIPTION

[0037] In order to enable those skilled in the art to understand the characteristics and effects of the present invention, the following is a general description and definition of the terms and expressions mentioned in the specification and claims. Unless otherwise specified, all technical and scientific terms used in the text are the common meanings understood by those skilled in the art for the present invention. In the event of a conflict, the definition in this specification shall prevail.

[0038] The theories or mechanisms described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, that is, the present invention can be implemented without being limited by any specific theory or mechanism.

[0039] In this article, all features such as values, quantities, contents and concentrations defined in the form of numerical ranges or percentage ranges are for simplicity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to have included and specifically disclosed all possible secondary ranges and individual values ​​within the range (including integers and fractions).

[0040] In this document, unless otherwise specified, “includes,” “including,” “contains,” “has,” or similar terms cover the meanings of “consisting of” and “mainly consisting of,” for example, “A includes a” covers the meanings of “A includes a and other” and “A only includes a.”

[0041] In this article, "D" in the structural formula represents "deuterium" unless otherwise specified.

[0042] In this document, in order to make the description concise, not all possible combinations of various technical features in various embodiments or examples are described. Therefore, as long as there is no contradiction in the combination of these technical features, the various technical features in various embodiments or examples can be combined arbitrarily, and all possible combinations should be considered to be within the scope of this specification.

[0043] The present invention provides a pyrrolidine derivative, the structure of which is shown in general formula 1:

[0044]

[0045] Where:

[0046] As the main structure;

[0047] The ring structure corresponding to B is called ring B, and B is C 6 ~C 30 The bonding mode of B to the main structure is single bond; preferably, C 6 ~C 30 The fused aromatic group is selected from the following groups (Y1~Y7) or any one of their derivatives:

[0048]

[0049] The asterisks in the above groups ( ) is between ring B and the main structure, and between ring B and L 1 The bonding position between

[0050] L 1 C 6 ~C 40 Aryl or C 6 ~C 40 Heteroaryl, L 1 The bonding mode with B is single bond; preferably, C 6 ~C 40 The heteroaryl L 1 Any one selected from the following groups (R1~R19) or their derivatives:

[0051]

[0052] The asterisk ( ) is the replacement position.

[0053] The present invention provides a method for preparing the above-mentioned rylene phenone derivatives, and the reaction formula is as follows:

[0054] The present invention provides an organic electroluminescent device, such as Figure 1 As shown, from the anode to the cathode direction, it includes a polymer substrate 1, an anode layer 2, a hole injection layer 3 (HIL), a hole transport layer 4 (HTL), an electron blocking layer 5 (EBL5), a light emitting layer 6 (EML6), a hole blocking layer 7 (HBL), an electron transport layer 8 (ETL), an electron injection layer 9 (EIL), a cathode layer 10 and a high refractive index covering layer 11.

[0055] As the polymer substrate 1, it is necessary to have the characteristics of high mechanical strength, excellent thermal stability, excellent water resistance and excellent transparency;

[0056] As the anode layer 2, in order to enable holes to be smoothly injected into the organic layer, the anode material is preferably a material with a large work function. Specific examples of the anode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, and gold, or their alloys; oxides such as zinc oxide, aluminum oxide, or tin dioxide; conductive polymers such as polypyrrole and polyaniline;

[0057] As functional organic layers, the hole injection layer 3, the hole transport layer 4, the electron blocking layer 5, the light emitting layer 6, the hole blocking layer 7, the electron transport layer 8 and the electron injection layer 9 can be formed on the electrode by vacuum thermal evaporation, spin coating, printing and other means or methods. The compounds used for each organic layer except the light emitting layer 6 can be organic small molecules, organic macromolecules and polymers, and combinations thereof. The materials used for the hole injection layer 3, the hole transport layer 4, the electron blocking layer 5, the hole blocking layer 7, the electron transport layer 8 and the electron injection layer 9 are selected from the corresponding functional layer materials with excellent cost performance in the industry. The compatibility between the functional layers needs to be determined through a series of tests and screening processes;

[0058] The hole injection layer 3 is preferably MoO 3 ;

[0059] The hole transport layer 4 can be selected from one of the following materials:

[0060] ;

[0061] The electron blocking layer 5 is selected from One of;

[0062] The light-emitting layer 6 is co-evaporated by a composite form of a main light-emitting material and a guest light-emitting material; the main light-emitting material is selected from one of the naphthylenediphenone derivatives shown in general formula 1, and the guest light-emitting material is selected from a fluorescent material or The main luminescent material and the guest luminescent material (fluorescent material) are compounded at a ratio of 95:5, and the mass fraction of the guest luminescent material (fluorescent material) in the entire luminescent layer 6 is 2.0% to 10.0%; the guest luminescent material can also be selected from phosphorescent materials. , and The main luminescent material and the guest luminescent material (phosphorescent material) are compounded in a ratio of 98:2, and the mass fraction of the guest luminescent material (phosphorescent material) in the entire luminescent layer 6 is 0.1% to 3.0%. Similarly, a sensitizer material can be added between the main luminescent material and the guest luminescent material to further optimize the structure of the luminescent layer 6. In this case, the main luminescent material is selected from one of the naphthylenediol derivatives shown in general formula 1, and the sensitizer is selected from , and The guest luminescent material is one of the phosphorescent materials DP-1, DP-2 and DP-3. The host luminescent material, the sensitizer and the guest luminescent material are used in a mass ratio of 98:0.3:2. The mass fraction of the sensitizer in the entire luminescent layer 6 is between 0.05% and 0.5%.

[0063] The hole blocking layer 7 is selected from One of;

[0064] The electron transport layer 8 is made of one of the following materials:

[0065] ;

[0066] As the cathode layer 10, in order to facilitate the injection of electrons into the organic layer, the cathode material is preferably a material with a small work function. Specific examples of the cathode material that can be used in the present invention include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof: LiF-Al or LiO 2 -A1, Mg-Al, Mg-Ag and other multilayer structure materials;

[0067] As a high refractive index cover layer 11, it can improve the refractive index of the surface of the cathode layer 10 and increase the light extraction rate; preferably .

[0068] The present invention provides a method for preparing the above-mentioned organic electroluminescent device, comprising: adhering an anode layer 2 on a polymer substrate 1 after pretreatment and cleaning, and then sequentially evaporating a hole injection layer 3, a hole transport layer 4, an electron blocking layer 5, a light-emitting layer 6, a hole blocking layer 7, an electron transport layer 8 and an electron injection layer 9 with set thicknesses under low temperature conditions, and then sputtering a cathode layer 10 and a high refractive index covering layer 11 under low temperature, and finally packaging the test device using conventional device testing and packaging means to obtain an organic electroluminescent device.

[0069] The present invention is further described below in conjunction with specific examples. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the contents described in the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the claims attached to the present application. In addition, those skilled in the art can refer to the preparation method of the above-mentioned general formula one compound, the important reactants shown in Table 1, and the following specific examples, and prepare compounds 1 to compound 222 in combination with intermediates M3 to M8.

[0070] Table 1 Important reactants involved

[0071]

[0072] The following examples use conventional instruments and equipment in the art. The experimental methods in the following examples without specifying specific conditions are usually carried out under conventional conditions or under conditions recommended by the manufacturer. The various raw materials used in the following examples, unless otherwise specified, are conventional commercial products, and their specifications are conventional specifications in the art.

[0073] The structural formula of the representative compound of the pyrrolidine derivative provided by the present invention is as follows:

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095] Example 1 Synthesis of Compound 5

[0096] 1. Synthesize intermediate M1 according to the following reaction formula:

[0097]

[0098] Add 65% concentrated nitric acid (335 mL) to naphthylenediol (180 g, 1.0 mol), dissolve in 36% concentrated hydrochloric acid (5.0 L), stir at 20°C for 3 h, extract with water and dichloromethane, dry the organic phase with anhydrous magnesium sulfate, filter and concentrate, and pass the organic phase through a silica gel column with n-hexane / dichloromethane to obtain intermediate M 1 , yellow solid, 120 g, yield 56.0%, GC purity 98%, GC-MS molecular weight 214.0.

[0099] 2. Synthesize intermediate M2 according to the following reaction formula:

[0100]

[0101] Under an inert atmosphere, M1 (120 g, 0.56 mol), diboronic acid pinacol ester (171 g, 0.67 mol), potassium acetate (110 g, 1.12 mol) and 1.5 L 1,4-dioxane were added to a 3 L three-necked flask. The mixture was stirred and heated to 60-65 °C. Pd(dppf)Cl was then added. 2 (4.6 g, 5.6 mmol), continue to heat to 100 ° C, reflux reaction for 8 h until M1 reacts completely. The reaction solution is directly filtered, the filtrate is collected, concentrated under reduced pressure and dried, and then dissolved in 1000 mL of toluene, washed with water, the organic phase is dried over anhydrous magnesium sulfate, filtered and concentrated, and the organic phase is passed through a silica gel column, and the column liquid is again concentrated under reduced pressure until solids precipitate and then stopped, cooled to 10-15 ° C, and filtered after crystallization is completed, and dried to obtain a light yellow solid M2, 130.8 g, yield 76.3%, HPLC content 99%, LC-MS molecular weight 307.1.

[0102] 3. Synthesize intermediate M3 according to the following reaction formula:

[0103]

[0104] Under inert atmosphere, M2 (30.6 g, 0.1 mol), 9,10-dichloroanthracene (24.7 g, 0.1 mol), 400 mL 1,4-dioxane, potassium carbonate (27.6 g, 0.2 mol), 50 mL deionized water and dichlorodi-tert-butyl-(4-dimethylaminophenyl)phosphine palladium (II) (0.71 g, 1.0 mmol) were added to a 1000 mL three-necked flask, and the system was heated to 100°C and refluxed for 18 hours until the reaction was completed. The reaction solution was washed with water and separated, and the organic phase was passed through a diatomaceous earth funnel and the filtrate was collected and concentrated under reduced pressure to dryness to obtain a solid crude product, which was passed through a silica gel column to obtain an off-white solid M3, 27.5 g, with a yield of 70.5%, an HPLC content of 99%, and an LC-MS molecular weight of 391.0.

[0105] 4. Synthesize compound 5 according to the following reaction formula

[0106]

[0107] Under an inert atmosphere, M3 (3.9 g, 0.01 mol), perdeuterated carbazole (1.8 g, 0.01 mol) and 50 mL toluene were added to a 100 mL three-necked flask and stirred until the solution was clear. Pd 2 (dba) 3 (0.18 g, 0.2 mmol), Am-phos (0.13 g, 0.5 mmol) and sodium tert-butoxide (1.9 g, 0.02 mmol), the reaction solution was heated to 120 ° C, and the reaction was continued for 10 h. After the reaction was completed, diatomaceous earth was used for hot filtration, the filtrate was cooled to room temperature, purified water was added for washing, the organic phase was retained after separation, and the aqueous phase was extracted with ethyl acetate, the organic phases were combined, dried over anhydrous magnesium sulfate, concentrated, and passed through a column to obtain compound 5. 4.0 g, off-white solid, yield 76.3%, HPLC content 99%, LC-MS showed a molecular weight of 530.2. The nuclear magnetic hydrogen spectrum of compound 5 is as follows Figure 2 shown.

[0108] Example 2 Synthesis of Compound 127

[0109] 1. Synthesize intermediate M4 according to the following reaction formula:

[0110]

[0111] M2 was synthesized according to step 2 of Example 1. Under an inert atmosphere, M2 (30.6 g, 0.1 mol), 1,6-dichloropyrene (27.1 g, 0.1 mol), 400 mL of 1,4-dioxane, potassium carbonate (27.6 g, 0.2 mol), 50 mL of deionized water and Pd(PPh 3 ) 4 (1.2 g, 1.0 mmol), the system was heated to 100°C and refluxed for 18 h until the reaction was completed. The reaction solution was washed with water and separated, the organic phase was passed through a diatomaceous earth funnel and the filtrate was collected and concentrated under reduced pressure to dryness to obtain a solid crude product, which was passed through a silica gel column to obtain compound M4, 28.7 g, with a yield of 69.3%, HPLC content of 99%, and LC-MS showed a molecular weight of 415.1.

[0112] 2. Synthesize intermediate M7 according to the following reaction formula:

[0113]

[0114] Under inert atmosphere, M4 (16.6 g, 0.04 mol), diboronic acid pinacol ester (12.2 g, 0.05 mol), potassium acetate (7.9 g, 0.08 mol) and 250 mL 1,4-dioxane were added to a 500 mL three-necked flask. The mixture was stirred and heated to 60-65 °C. Pd(dppf)Cl was then added. 2 (0.33 g, 4.0 mmol), continue to heat to 100℃ and reflux for 8 h until M4 reacts completely. The reaction solution is directly filtered, the filtrate is collected, concentrated under reduced pressure and then dissolved in 200 mL toluene, then washed with water, the organic phase is dried over anhydrous magnesium sulfate, filtered and concentrated, the organic phase is passed through a silica gel column, the column liquid is again concentrated under reduced pressure until solids precipitate and then stopped, the temperature is lowered to 10~15℃, crystallization is completed, filtered and dried to obtain compound M7, 15.6 g, yield 76.9%, HPLC content 99%, LC-MS shows molecular weight 507.2.

[0115] 4. Synthesize compound 127 according to the following reaction formula

[0116]

[0117] Under inert atmosphere, M7 (5.7 g, 0.01 mol), (Z)-9-chloro-10-(1-propenyl)anthracene (2.5 g, 0.01 mol), 40 mL of 1,4-dioxane, potassium carbonate (2.8 g, 0.02 mol), 10 mL of deionized water and Pd(PPh 3 ) 4(0.12 g, 0.1 mmol), the system was heated to 100 ° C, and refluxed for 18 h until the reaction was completed. The reaction solution was washed with water and separated, and the organic phase was passed through a diatomaceous earth funnel and the filtrate was collected and concentrated under reduced pressure to dryness to obtain a solid crude product, which was passed through a silica gel column to obtain compound 127, 4.5 g, off-white solid, with a yield of 66.9%, HPLC content of 99%, and LC-MS molecular weight of 597.2. The H NMR spectrum of compound 127 is as follows Figure 3 shown.

[0118] Example 3 Synthesis of Compound 169

[0119] 1. Synthesize intermediate M5 according to the following reaction formula:

[0120]

[0121] M2 was synthesized according to step 2 of Example 1. Under an inert atmosphere, M2 (30.6 g, 0.1 mol), 1,5-dichloronaphthalene (19.7 g, 0.1 mol), 400 mL 1,4-dioxane, potassium carbonate (27.6 g, 0.2 mol), 50 mL deionized water and Pd(PPh 3 ) 4 (1.2 g, 1.0 mmol), the system was heated to 100°C and refluxed for 18 h until the reaction was completed. The reaction solution was washed with water and separated, the organic phase was passed through a diatomaceous earth funnel and the filtrate was collected and concentrated under reduced pressure to dryness to obtain a solid crude product, which was passed through a silica gel column to obtain compound M5, 23.9 g, with a yield of 70.2%, an HPLC content of 99%, and a molecular weight of 341.0 according to LC-MS.

[0122] 2. Compound 169 was synthesized according to the following reaction formula:

[0123]

[0124] Under an inert atmosphere, M5 (3.4 g, 0.01 mol), bis(4-(tert-butyl)phenyl)amine (2.8 g, 0.01 mol) and 50 mL of toluene were added to a 100 mL three-necked flask and stirred until the solution was clear. Pd 2 (dba) 3(0.18 g, 0.2 mmol), Am-phos (0.13 g, 0.5 mmol) and sodium tert-butoxide (1.9 g, 0.02 mmol), the reaction solution was heated to 120 ° C, and the reaction was continued for 10 h. After the reaction was completed, diatomaceous earth was used for hot filtration, the filtrate was cooled to room temperature, purified water was added for washing, the organic phase was retained after separation, and the aqueous phase was extracted with ethyl acetate, the organic phases were combined, dried over anhydrous magnesium sulfate, concentrated, and passed through a column to obtain compound 169, 4.5 g, off-white solid, with a yield of 75.4%, HPLC content of 99%, and LC-MS showing a molecular weight of 586.3. The nuclear magnetic hydrogen spectrum of compound 169 is as follows Figure 4 shown.

[0125] Example 4 Synthesis of Compound 35

[0126] 1. Synthesize intermediate M6 according to the following reaction formula:

[0127]

[0128] Operation process: Under inert atmosphere, add M3 (15.6 g, 0.04 mol), biboric acid pinacol ester (12.2 g, 0.05 mol), potassium acetate (7.9 g, 0.08 mol) and 200 mL 1,4-dioxane into a 500 mL three-necked flask, start stirring and heat to 60-65 °C, then add X-Phos (0.38 g, 0.8 mmol) and Pd 2 (dba) 3 (0.33 g, 0.4 mmol), then continue to heat to 100 ° C, reflux reaction for 8 h until M3 reacts completely. The reaction solution was directly filtered, the filtrate was collected, concentrated under reduced pressure, dissolved with 100 mL toluene and then washed with water. After the organic phase passed through the silica gel column, the column liquid was again concentrated under reduced pressure until solids precipitated and then stopped. The temperature was lowered to 10-15 ° C. After crystallization, it was filtered and dried to obtain a white solid 6, 14.9 g, with a yield of 77.4%, HPLC content of 99%, and LC-MS showing a molecular weight of 483.2.

[0129] 2. Compound 35 was synthesized according to the following reaction formula:

[0130]

[0131] Operation process: Under inert atmosphere, add M6 (4.8 g, 0.01 mol), 1-bromodibenzofuran (2.5 g, 0.01 mol), 40 mL 1,4-dioxane, potassium carbonate (2.8 g, 0.02 mol), 10 mL deionized water and Pd(PPh 3 ) 4(0.12 g, 0.1 mmol), the system was heated to 100 ° C, and refluxed for 18 h until the reaction was completed. The reaction solution was washed with water and separated, and the organic phase was passed through a diatomaceous earth funnel and the filtrate was collected and concentrated under reduced pressure to dryness to obtain a solid crude product, which was passed through a silica gel column to obtain compound 35, 3.5 g, off-white solid, with a yield of 67.3%, HPLC content of 99%, and LC-MS molecular weight of 523.1. The H NMR spectrum of compound 35 is as follows Figure 5 shown.

[0132] Example 5 Synthesis of Compound 189

[0133] 1. Synthesize intermediate M8 according to the following reaction formula:

[0134]

[0135] The synthesis process of M8 refers to the synthesis process of M2. M5 (13.6 g, 0.04 mol) and bipyralidone (12.2 g, 0.05 mol) were added to obtain compound M6, which was 13.2 g, with a yield of 76.3%, HPLC content of 99%, and LC-MS showed a molecular weight of 433.1.

[0136] 2. Compound 189 was synthesized according to the following reaction formula:

[0137]

[0138] Under inert atmosphere, M8 (4.3 g, 0.01 mol), 9-bromophenanthrene (2.6 g, 0.01 mol), 40 mL 1,4-dioxane, potassium carbonate (2.8 g, 0.02 mol), 10 mL deionized water and Pd(PPh 3 ) 4 (0.12 g, 0.1 mmol), the system was heated to 100 ° C, and refluxed for 18 h until the reaction was completed. The reaction solution was washed with water and separated, and the organic phase was passed through a diatomaceous earth funnel and the filtrate was collected and concentrated under reduced pressure to dryness to obtain a solid crude product, which was passed through a silica gel column to obtain compound 189, 3.2 g, off-white solid, with a yield of 66.1%, HPLC content of 99%, and LC-MS molecular weight of 483.2. The H NMR spectrum of compound 189 is as follows Figure 6 shown.

[0139] According to the structural information of the light-emitting layer 6 of the electroluminescent device given in Table 2, the electroluminescent devices of Examples 6 to 24 and Comparative Examples 1 to 4 were prepared.

[0140] Table 2 Light-emitting layer structure of electroluminescent device

[0141]

[0142] Example 6 Electroluminescent device containing compound 5

[0143] An electroluminescent device containing compound 5, which comprises polyethylene terephthalate (PET) plastic, indium tin oxide (ITO) conductive glass, MoO 3 , HT-2, EB-2, luminescent layer 6, HB-1, ET-2, LiF, Al-Mg (Al:Mg=9:1) and CPL;

[0144] The light-emitting layer 6 includes compound 5 and Rubrene in a mass ratio of 95:5.

[0145] The method for preparing the electroluminescent device containing compound 5 comprises the following steps:

[0146] 1. Using 1.5 mm PET plastic as the polymer substrate 1 and 0.15 mm ITO conductive glass as the anode layer 2, alkaline washing, pure water washing, drying, and then ultraviolet-ozone washing are used to remove organic residues on the surface of PET plastic and ITO conductive glass.

[0147] 2. Attach a layer of ITO conductive glass to the PET plastic, and use a vacuum evaporation device to evaporate a 20 nm thick MoO 3 As the hole injection layer 3, then 45 nm thick HT-2 is evaporated as the hole transport layer 4, followed by 30 nm thick EB-2 as the electron blocking layer 5, and 60 nm of the light-emitting layer 6 formed by compound 5 and Rubrene with a mass ratio of 95:5 is continuously evaporated on EB-2, and then 10 nm thick HB-1 is continuously evaporated on the light-emitting layer 6 as the hole blocking layer 7, followed by 30 nm thick ET-2 as the electron transport layer 8, and then 16 nm LiF is continuously evaporated on the electron transport layer 8 as the electron injection layer 9, after the electron injection layer 9 is evaporated, 10 nm thick Al-Mg (Al:Mg=9:1) alloy is sputtered as the cathode layer 10 by low-temperature sputtering, and finally 40 nm thick CPL is continuously evaporated on the cathode layer 10 as the high refractive index covering layer 11.

[0148] 3. To MoO 3 , HT-2, EB-2, the light-emitting layer 6, HB-1, ET-2 and the LiF layer are vacuum packaged to obtain an organic electroluminescent device.

[0149] Embodiment 7~embodiment 9

[0150] The difference from Example 6 is that in the light-emitting layer 6 , compounds 25, 55 and 60 are selected as the main light-emitting materials of the light-emitting layer 6 .

[0151] Embodiment 10~embodiment 21

[0152] The difference from Example 6 is that in the light-emitting layer 6, compounds 5, 25, 55, 60, 77, 97, 127, 132, 149, 169, 199 and 204 are selected as the main light-emitting materials, and the phosphorescent material DP-1 is used as the guest light-emitting material, and the mass ratio of the main light-emitting material to the guest light-emitting material is 98:2.

[0153] Embodiment 22 to Embodiment 24

[0154] The difference from Example 6 is that in the light-emitting layer 6, compounds 55, 127 and 199 are selected as the main light-emitting materials, S-7 is used as the sensitizer, and the phosphorescent material DP-1 is used as the guest light-emitting material. The mass ratio of the main light-emitting material, the sensitizer and the guest light-emitting material is 98:0.3:2.

[0155] Comparative Example 1

[0156] The difference from Example 6 is that in the light-emitting layer 6, As the main luminescent material. The structure of the electroluminescent device is: PET substrate / ITO / MoO 3 (20 nm) / HT-2(45 nm) / EB-2(30 nm) / PH-1: Rubrene =95:5(60 nm) / HB-1(10 nm) / ET-2(30 nm) / LiF(16 nm) / Al: Mg=9:1(10 nm) / CPL(40 nm).

[0157] Comparative Example 2

[0158] The difference from Example 6 is that in the light-emitting layer 6, PH-1 is used as the main light-emitting material and TBPE is used as the guest light-emitting material. The structure of the electroluminescent device is: PET substrate / ITO / MoO 3 (20 nm) / HT-2(45 nm) / EB-2(30nm) / PH-1:TBPE=95:5(60 nm) / HB-1(10 nm) / ET-2 (30 nm) / LiF(16 nm) / Al:Mg=9:1(10 nm) / CPL(40 nm).

[0159] Comparative Example 3

[0160] The difference from Example 6 is that in the light-emitting layer 6, PH-1 is used as the main light-emitting material, DP-1 is used as the guest light-emitting material, and the mass ratio of the main light-emitting material to the guest light-emitting material is 98:2. The structure of the electroluminescent device is: PET substrate / ITO / MoO 3 (20 nm) / HT-2(45 nm) / EB-2(30 nm) / PH-1:DP-1=98:2 (60 nm) / HB-1(10 nm) / ET-2 (30 nm) / LiF(16 nm) / Al: Mg=9:1 (10 nm) / CPL(40 nm).

[0161] Comparative Example 4

[0162] The difference from Example 22 is that PH-1 is used as the main luminescent material in the luminescent layer 6. The structure of the electroluminescent device is: PET substrate / ITO / MoO 3 (20 nm) / HT-2(45 nm) / EB-2(30 nm) / PH-5:S-7:PH-1=98:0.3:2 (60 nm) / HB-1(10 nm) / ET-2 (30 nm) / LiF(16 nm) / Al:Mg=9:1 (10 nm) / CPL(40 nm).

[0163] The electroluminescent devices in the above embodiments and comparative examples were prepared into samples of 30 mm×30 mm, and then the anode and cathode were connected using a driving circuit known in the industry under the same device manufacturing process conditions, and the OLED was characterized, and the life was calculated from the current / voltage / luminous density characteristic line showing Lambertian emission characteristics. The test results are shown in Table 3.

[0164] Table 3 Electroluminescent device performance test results

[0165]

[0166] (Note: The current density during the test is 10 mA / cm, and LT95 refers to the time it takes for the device brightness to decay to 95% of the initial brightness.)

[0167] It can be seen from the test data in Table 3 that 1) compared with the test devices prepared by the commonly used host luminescent materials (Comparative Examples 1-4), the test devices prepared by the preferred naphthylenone derivatives of the present invention have obvious advantages in comprehensive luminous efficiency. 2) The devices prepared after the host luminescent material-fluorescent material adaptation (Examples 6-9) are slightly inferior to the electroluminescent devices prepared after the host luminescent material-phosphorescent material adaptation (Examples 10-13) in comprehensive luminescent performance. 3) When the electroluminescent devices prepared after adding the sensitizer (Examples 22-24), compared with the electroluminescent devices without adding the sensitizer (Examples 12, 16 and 20), the roll-off efficiency is significantly reduced, the current efficiency is increased by more than 15%, the LT95 life of the device is increased by more than 10%, and the maximum external quantum efficiency is increased by more than 20%. These results show that the test devices prepared by using the preferred naphthylenone derivatives of the present invention as the bipolar host luminescent material and the sensitizer at the same time have significantly improved device life and comprehensive luminous efficiency.

[0168] The above contents are only for explaining the technical idea of ​​the present invention and cannot be used to limit the protection scope of the present invention. Any changes made on the basis of the technical solution in accordance with the technical idea proposed by the present invention shall fall within the protection scope of the claims of the present invention.

Claims

1. A rylenephenone derivative, characterized in that: The structure is shown in general formula 1: Where: As the main structure; The bonding mode between B and the main structure is single bond, and the cyclic structure corresponding to B is called ring B. B is selected from any one of the following groups: , in the group is the bonding position between ring B and the main structure, and between ring B and L1; L1 is C6~C 40 The aromatic group is C6~C 40 Heteroaryl, C6~C 40 The heteroaryl group is selected from the following groups: , in the substituent For the substitution position, the bonding mode between L1 and B is a single bond.

2. A rylenephenone derivative, characterized in that: The pyrrolidine derivatives are selected from the following compounds: 。 3. Use of the rylenephenone derivatives according to claim 1 or 2 in the preparation of electroluminescent devices.

4. An organic electroluminescent device, characterized in that: The invention comprises an anode layer (2), a cathode layer (10) and an organic layer located between the anode layer (2) and the cathode layer (10), wherein the organic layer comprises a hole transport layer (4), a light-emitting layer (6) and an electron transport layer (8), wherein the light-emitting layer (6) comprises a host light-emitting material and a guest light-emitting material, and the host light-emitting material comprises the naphthylene phenone derivative according to claim 1 or 2.

5. The electroluminescent device according to claim 4, characterized in that The guest luminescent material is selected from phosphorescent materials , and The mass of the guest luminescent material accounts for 0.1% to 3.0% of the mass fraction of the entire luminescent layer (6).

6. The electroluminescent device according to claim 4, characterized in that The guest luminescent material is selected from fluorescent materials or , and the mass of the guest luminescent material accounts for 2.0% to 10.0% of the mass fraction of the entire luminescent layer (6).

7. The electroluminescent device according to claim 5, characterized in that The light-emitting layer (6) further includes a sensitizer.

8. The electroluminescent device according to claim 7, characterized in that The sensitizer is selected from , and The mass of the sensitizer accounts for 0.05% to 0.5% of the mass fraction of the entire light-emitting layer (6).

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