An anthracene ketone compound, a preparation method and application thereof, and an organic electroluminescent device

Abstract

The application provides an anthracene ketone compound and a preparation method and application thereof, and an organic electroluminescent device, and belongs to the technical field of semiconductors.The anthracene ketone compound provided by the application has the characteristics of strong rigidity, difficulty in crystallization and aggregation between molecules, good film-forming property, high glass transition temperature and high thermal stability, so that the compound can keep the stability of a film layer after material film-forming when applied to an OLED device; the current efficiency of the device is greatly improved when the organic compound is applied to the OLED device as an organic electroluminescent functional layer material; and the service life of the device is obviously improved. The results of examples show that the anthracene ketone compound provided by the application is used as a light-emitting layer material, the current efficiency of the obtained organic electroluminescent device is 147.1-157.3, and the service life is 351.6-373.9h.

Description

Technical Field

[0001] This invention relates to the field of semiconductor technology, and in particular to an anthrone compound, its preparation method and application, and an organic electroluminescent device. Background Technology

[0002] Organic light emission diodes (OLED) technology can be used to manufacture new display products as well as new lighting products, and is expected to replace existing liquid crystal displays and fluorescent lighting, with a very wide range of applications.

[0003] OLED light-emitting devices have a sandwich-like structure, consisting of electrode material layers and an organic light-emitting functional layer sandwiched between different electrode layers. Various materials with different functions are stacked together according to their applications to form an OLED light-emitting device. As a current-emitting device, when a voltage is applied to its two electrodes and an electric field is applied to the positive and negative charges in the organic light-emitting functional layer, the positive and negative charges will recombine in the light-emitting layer, thus generating OLED electroluminescence.

[0004] Although OLED display technology has been widely used in smartphones, tablets and other fields, and will be further expanded to large-size applications such as televisions, the performance of OLED devices, such as luminous efficiency and lifespan, still needs to be improved compared with the actual product application requirements.

[0005] Current research on improving the performance of OLED light-emitting devices mainly includes reducing the driving voltage, improving the current efficiency, and extending the lifespan of the devices. To continuously improve the performance of OLED devices, it is necessary not only to improve the OLED device structure and manufacturing process, but also to develop new OLED functional materials with higher performance. Summary of the Invention

[0006] In view of this, the present invention aims to provide anthrone compounds, their preparation methods and applications, and an organic electroluminescent device. The anthrone compounds provided by the present invention can effectively improve the current efficiency and lifetime of OLED devices.

[0007] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0008] This invention provides an anthrone compound having the structure shown in formula (1):

[0009]

[0010] In equation (1), L1 and L2 are each independently a single bond, substituted or unsubstituted C6-C bond. 30aryl, substituted or unsubstituted C2-C 30 One of the heteroaryl groups;

[0011] R represents substituted or unsubstituted C6-C. 30 aryl, substituted or unsubstituted C2-C 30 Mixed aromatics;

[0012] X is -O-, -S-, or -N(R1)-; where R1 is substituted or unsubstituted C6-C. 30 aryl, substituted or unsubstituted C2-C 30 One of the heteroaryl groups;

[0013] Among the substituted groups mentioned above, each substituent is independently a halogen, cyano, or C1-C group. 20 Alkyl, C6-C 30 Aryl, C2-C 30 One or more of the heteroaryl groups;

[0014] The heteroatoms in the heteroaryl and heteroaryl groups are one or more of oxygen, sulfur, or nitrogen atoms.

[0015] Preferably, it has the structure shown in any one of equations (2-1) to (2-2):

[0016]

[0017] Preferably, it has the structure shown in any one of equations (3-1) to (3-2):

[0018]

[0019] Preferably, it has the structure shown in any one of equations (4-1) to (4-2):

[0020]

[0021] Preferably, L1 and L2 are each independently one of the following: substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted diphenylene, substituted or unsubstituted pyridylene, substituted or unsubstituted carbazolyl, substituted or unsubstituted furanylene, substituted or unsubstituted pyrimidinylene, substituted or unsubstituted pyrazinylene, substituted or unsubstituted pyridazinylene, substituted or unsubstituted dibenzofuranylene, substituted or unsubstituted 9,9-dimethylfluorenylene, substituted or unsubstituted N-phenylcarbazolyl, substituted or unsubstituted quinolinylene, substituted or unsubstituted isoquinolinylene, or substituted or unsubstituted naphthidylene.

[0022] R is one of methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted diphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted anthraquinyl, substituted or unsubstituted pyridyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted furanyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted thiophenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted 9,9-dimethylfluorenyl, substituted or unsubstituted N-phenylcarbazolyl, substituted or unsubstituted quinolinyl, substituted or unsubstituted isoquinolinyl, substituted or unsubstituted naphridinyl, substituted or unsubstituted oxazolyl, substituted or unsubstituted imidazolyl, substituted or unsubstituted benzoxazolyl, or substituted or unsubstituted benzimidazolyl.

[0023] R1 is one of the following: substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted diphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted anthraquinyl, substituted or unsubstituted pyridyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted furanyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted thiophenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted 9,9-dimethylfluorenyl, substituted or unsubstituted N-phenylcarbazolyl, substituted or unsubstituted quinolinyl, substituted or unsubstituted isoquinolinyl, substituted or unsubstituted naphridyl, substituted or unsubstituted oxazolyl, substituted or unsubstituted imidazolyl, substituted or unsubstituted benzoxazolyl, or substituted or unsubstituted benzimidazolyl.

[0024] In the above-mentioned substituted groups, each substituent is independently one or more of the following: fluorine atom, cyano, methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, phenyl, naphthyl, biphenyl, pyridyl, benzofuranyl, carbazoleyl, diphenylaminoyl, benzothiopheneyl or furanyl.

[0025] This invention provides a method for preparing the above-mentioned anthrone compounds, comprising the following steps:

[0026] (1) Prepare compounds having the structure shown in formula a;

[0027]

[0028] The method for preparing the compound having the structure shown in Formula a includes:

[0029] When X is -O-, the preparation method includes the following steps:

[0030] A compound having the structure shown in formula b undergoes a first cyclization reaction with a compound having the structure shown in formula c to obtain a compound having the structure shown in formula a.

[0031]

[0032] When X is -S-, the compound having the structure shown in formula d undergoes a second cyclization reaction with the compound having the structure shown in formula e to obtain the compound having the structure shown in formula a.

[0033]

[0034] When X is -N(R1)-, the compound having the structure shown in formula f undergoes a third cyclization reaction with the compound having the structure shown in formula g to obtain the compound having the structure shown in formula h.

[0035]

[0036] A compound having the structure shown in formula h undergoes a first substitution reaction with a compound having the structure shown in formula i to obtain a compound having the structure shown in formula a.

[0037] IR1 formula i;

[0038] (2) A compound having the structure shown in formula a undergoes a second substitution reaction with a compound having the structure shown in formula j to obtain a compound having the structure shown in formula k.

[0039]

[0040] (3) A compound having the structure shown in formula k undergoes a third substitution reaction with a compound having the structure shown in formula m to obtain anthrone compounds having the structure shown in formula (1);

[0041]

[0042] This invention provides the application of the above-mentioned anthrone compounds in the preparation of organic electroluminescent devices.

[0043] The present invention provides an organic electroluminescent device, comprising a cathode, an anode, and an organic functional layer, wherein the organic functional layer is located between the anode and the cathode, and the organic functional layer comprises the aforementioned anthrone compounds.

[0044] Preferably, the organic functional layer includes a light-emitting layer, which includes the above-mentioned anthrone compounds.

[0045] Preferably, the light-emitting layer comprises a host material and a dopant material, wherein the host material comprises the aforementioned anthrone compounds.

[0046] This invention provides an anthrone compound having the structure shown in formula (1). The anthrone compound provided by this invention has a rigid functional group, exhibiting characteristics such as low intermolecular crystallization and aggregation, good film-forming properties, avoiding aggregation-induced quenching (ACQ), and possessing high glass transition temperature and thermal stability. Therefore, when the compound of this invention is applied to OLED devices, it can maintain the stability of the film layer after material formation. When the organic compound of this invention is used as an organic electroluminescent functional layer material in OLED devices, the current efficiency of the device is greatly improved; at the same time, the device lifetime is significantly improved. The results of the examples show that, when the anthrone compound provided by this invention is used as the light-emitting layer material, the current efficiency of the resulting organic electroluminescent device is 147.1–157.3, and the lifetime is 351.6–373.9 h.

[0047] This invention provides a method for preparing the above-mentioned anthrone compounds. This method is simple to operate and suitable for industrial mass production.

[0048] This invention provides an organic electroluminescent device, comprising a cathode, an anode, and an organic functional layer, wherein the organic functional layer is located between the anode and the cathode, and the organic functional layer comprises the aforementioned anthrone compounds. The organic electroluminescent device provided by this invention exhibits good device efficiency and lifetime. Attached Figure Description

[0049] Figure 1 This is a schematic cross-sectional view of the organic electroluminescent device of the present invention. Detailed Implementation

[0050] This invention provides an anthrone compound having the structure shown in formula (1):

[0051]

[0052] In equation (1), L1 and L2 are each independently a single bond, substituted or unsubstituted C6-C bond. 30 aryl, substituted or unsubstituted C2-C 30 One of the heteroaryl groups;

[0053] R represents substituted or unsubstituted C6-C. 30 aryl, substituted or unsubstituted C2-C 30 Mixed aromatics;

[0054] X is -O-, -S-, or -N(R1)-; where R1 is substituted or unsubstituted C6-C. 30 aryl, substituted or unsubstituted C2-C 30 One of the heteroaryl groups;

[0055] Among the substituted groups mentioned above, each substituent is independently a halogen, cyano, or C1-C group.20 Alkyl, C6-C 30 Aryl, C2-C 30 One or more of the heteroaryl groups;

[0056] The heteroatoms in the heteroaryl and heteroaryl groups are one or more of oxygen, sulfur, or nitrogen atoms.

[0057] In this invention, L1 and L2 are each preferably, independently, one of the following: substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted diphenylene, substituted or unsubstituted pyridinylene, substituted or unsubstituted carbazolyl, substituted or unsubstituted furanylene, substituted or unsubstituted pyrimidinylene, substituted or unsubstituted pyrazinylene, substituted or unsubstituted pyridazinylene, substituted or unsubstituted dibenzofuranylene, substituted or unsubstituted 9,9-dimethylfluorenylene, substituted or unsubstituted N-phenylcarbazolyl, substituted or unsubstituted quinolinylene, substituted or unsubstituted isoquinolinylene, or substituted or unsubstituted naphthidylene.

[0058] In this invention, R is preferably one of methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted diphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted anthraquinyl, substituted or unsubstituted pyridyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted furanyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted thiophenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted 9,9-dimethylfluorenyl, substituted or unsubstituted N-phenylcarbazolyl, substituted or unsubstituted quinolinyl, substituted or unsubstituted isoquinolinyl, substituted or unsubstituted naphthidyl, substituted or unsubstituted oxazolyl, substituted or unsubstituted imidazolyl, substituted or unsubstituted benzoxazolyl, or substituted or unsubstituted benzimidazolyl.

[0059] In this invention, R1 is preferably one of the following: substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted diphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted anthraquinyl, substituted or unsubstituted pyridyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted furanyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted thiophenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted 9,9-dimethylfluorenyl, substituted or unsubstituted N-phenylcarbazolyl, substituted or unsubstituted quinolinyl, substituted or unsubstituted isoquinolinyl, substituted or unsubstituted naphridyl, substituted or unsubstituted oxazolyl, substituted or unsubstituted imidazolyl, substituted or unsubstituted benzoxazolyl, or substituted or unsubstituted benzimidazolyl.

[0060] In this invention, the substituents are each preferably one or more of the following: fluorine atom, cyano, methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, phenyl, naphthyl, biphenyl, pyridyl, benzofuranyl, carbazoleyl, diphenylaminoyl, benzothiopheneyl or furanyl.

[0061] In this invention, the anthrone compound preferably has the structure shown in any one of formulas (2-1) to (2-2):

[0062]

[0063] In this invention, the anthrone compound preferably has the structure shown in any one of formulas (3-1) to (3-2):

[0064]

[0065] In this invention, the anthrone compound preferably has the structure shown in any one of formulas (4-1) to (4-2):

[0066]

[0067]

[0068] In this invention, the anthrone compound preferably has the structure shown in any one of Formulas 1 to 60:

[0069]

[0070]

[0071]

[0072] This invention provides a method for preparing the above-mentioned anthrone compounds, comprising the following steps:

[0073] The method for preparing the anthrone compound includes the following steps:

[0074] (1) Prepare compounds having the structure shown in formula a;

[0075]

[0076] The method for preparing the compound having the structure shown in Formula a includes:

[0077] When X is -O-, the preparation method includes the following steps:

[0078] A compound having the structure shown in formula b undergoes a first cyclization reaction with a compound having the structure shown in formula c to obtain a compound having the structure shown in formula a.

[0079]

[0080] When X is -S-, the compound having the structure shown in formula d undergoes a second cyclization reaction with the compound having the structure shown in formula e to obtain the compound having the structure shown in formula a.

[0081]

[0082] When X is -N(R1)-, the compound having the structure shown in formula f undergoes a third cyclization reaction with the compound having the structure shown in formula g to obtain the compound having the structure shown in formula h.

[0083]

[0084] A compound having the structure shown in formula h undergoes a first substitution reaction with a compound having the structure shown in formula i to obtain a compound having the structure shown in formula a.

[0085] IR1 formula i;

[0086] (2) A compound having the structure shown in formula a undergoes a second substitution reaction with a compound having the structure shown in formula j to obtain a compound having the structure shown in formula k.

[0087]

[0088] (3) A compound having the structure shown in formula k undergoes a third substitution reaction with a compound having the structure shown in formula m to obtain anthrone compounds having the structure shown in formula (1);

[0089]

[0090] This invention prepares compounds having the structure shown in formula a. In this invention, when X is -O-, the preparation method includes the following steps:

[0091] A compound having the structure shown in formula b undergoes a first cyclization reaction with a compound having the structure shown in formula c to obtain a compound having the structure shown in formula a.

[0092] In this invention, the molar ratio of the compound having the structure shown in formula b to the compound having the structure shown in formula c is preferably 1:1.

[0093] In this invention, the solvent used in the first cyclization reaction is preferably polyphosphoric acid. The temperature of the first cyclization reaction is preferably reflux temperature, and the time is preferably 6–9 hours, more preferably 7–8 hours.

[0094] After the first cyclization reaction, the present invention preferably performs post-treatment on the obtained first cyclization reaction solution, the post-treatment preferably including the following steps:

[0095] The first cyclization reaction solution was mixed with a mixed solvent, stirred, allowed to stand, filtered, the filter cake was dried, and recrystallized to obtain a pure compound with the structure shown in formula a.

[0096] In this invention, the mixed solvent is preferably a mixture of water and n-hexane; the volume ratio of water to n-hexane is preferably 5:3.

[0097] In this invention, the solvent used for recrystallization is preferably water and petroleum ether, and the volume ratio of water to petroleum ether is preferably 5:3.

[0098] In this invention, when X is -S-, the compound having the structure shown in formula d undergoes a second cyclization reaction with the compound having the structure shown in formula e to obtain the compound having the structure shown in formula a.

[0099] In this invention, the molar ratio of the compound having the structure shown in Formula d to the compound having the structure shown in Formula e is preferably 1:1.

[0100] In this invention, the solvent used in the second cyclization reaction is preferably polyphosphoric acid. The temperature of the second cyclization reaction is preferably reflux temperature, and the time is preferably 6–9 h, more preferably 7–8 h.

[0101] Following the second cyclization reaction, the present invention preferably performs post-treatment on the obtained second cyclization reaction solution, the post-treatment preferably including the following steps:

[0102] The second cyclization reaction solution was mixed with a mixed solvent, stirred, allowed to stand, filtered, the filter cake was dried, and recrystallized to obtain a pure compound with the structure shown in formula a.

[0103] In this invention, the mixed solvent is preferably a mixture of water and n-hexane; the volume ratio of water to n-hexane is preferably 5:3.

[0104] In this invention, the solvent used for recrystallization is preferably water and petroleum ether, and the volume ratio of water to petroleum ether is preferably 5:3.

[0105] In this invention, when X is -N(R1)-, the compound having the structure shown in formula f undergoes a third cyclization reaction with the compound having the structure shown in formula g to obtain the compound having the structure shown in formula h.

[0106] In this invention, the molar ratio of the compound having the structure shown in formula f to the compound having the structure shown in formula g is preferably 4:5.

[0107] In this invention, the third cyclization reaction is preferably carried out in the presence of Cs2CO3, Cu powder and 18-crown 6; the molar ratio of Cs2CO3, Cu powder and 18-crown 6 is preferably 50:4:4, and the molar ratio of the compound having the structure shown in formula f to Cs2CO3 is preferably 4:5.

[0108] In this invention, the temperature of the third cyclization reaction is preferably a reflux temperature, and the time is preferably 12 hours.

[0109] Following the third cyclization reaction, the present invention preferably performs post-treatment on the resulting third cyclization reaction solution, the post-treatment preferably including the following steps:

[0110] The third cyclization reaction solution was filtered, and the resulting filtrate was rotary evaporated under reduced pressure until no fractions remained. The filtrate was then passed through a neutral silica gel column to obtain a pure compound having the structure shown in formula h.

[0111] In this invention, a compound having the structure shown in formula h undergoes a first substitution reaction with a compound having the structure shown in formula i to obtain a compound having the structure shown in formula a.

[0112] In this invention, the molar ratio of the compound having the structure shown in formula h to the compound having the structure shown in formula i is preferably 1:1.

[0113] In this invention, the first substitution reaction is preferably carried out in the presence of sodium tert-butoxide, and the molar ratio of the compound having the structure shown in formula h to sodium tert-butoxide is preferably 1:2.

[0114] In this invention, the first substitution reaction is preferably carried out in the presence of a catalyst, preferably Pd2(dba)3 and tri-tert-butylphosphine, and the molar ratio of Pd2(dba)3 to tri-tert-butylphosphine is preferably 1:1.

[0115] In this invention, the organic solvent used in the first substitution reaction is preferably toluene.

[0116] In this invention, the temperature of the first substitution reaction is preferably a reflux temperature, and the time is preferably 12 hours.

[0117] Following the first substitution reaction, the present invention preferably performs post-treatment on the obtained first substitution reaction solution, the post-treatment preferably including the following steps:

[0118] The first substitution reaction solution was filtered, and the resulting filtrate was rotary evaporated under reduced pressure until no fraction was obtained. The filtrate was then passed through a neutral silica gel column to obtain a pure compound having the structure shown in formula a.

[0119] In this invention, a compound having the structure shown in formula a undergoes a second substitution reaction with a compound having the structure shown in formula j to obtain a compound having the structure shown in formula k.

[0120] In this invention, the molar ratio of the compound having the structure shown in Formula a to the compound having the structure shown in Formula j is preferably 1:1.2.

[0121] In this invention, the second substitution reaction is preferably carried out in the presence of sodium tert-butoxide, and the molar ratio of the compound having the structure shown in Formula j to sodium tert-butoxide is preferably 1:3.

[0122] In this invention, the second substitution reaction is preferably carried out in the presence of a catalyst, preferably Pd2(dba)3 and tri-tert-butylphosphine, wherein the molar ratio of Pd2(dba)3 to tri-tert-butylphosphine is preferably 1:1.

[0123] In this invention, the organic solvent used in the second substitution reaction is preferably toluene.

[0124] In this invention, the temperature of the second substitution reaction is preferably a reflux temperature, and the time is preferably 24 hours.

[0125] Following the second substitution reaction, the present invention preferably performs post-treatment on the obtained second substitution reaction solution, the post-treatment preferably including the following steps:

[0126] The second substitution reaction solution was filtered, and the resulting filtrate was rotary evaporated under reduced pressure until no fraction was obtained. The filtrate was then passed through a neutral silica gel column to obtain a pure compound having the structure shown in formula k.

[0127] In this invention, a compound having the structure shown in formula k undergoes a third substitution reaction with a compound having the structure shown in formula m to obtain anthrone compounds having the structure shown in formula (1).

[0128] In this invention, the molar ratio of the compound having the structure shown in formula k to the compound having the structure shown in formula m is preferably 1:1.

[0129] In this invention, the third substitution reaction is preferably carried out in the presence of K2CO3.

[0130] In this invention, the third substitution reaction is preferably carried out in the presence of a catalyst, preferably Pd(PPh3)4.

[0131] In this invention, the organic solvent used in the third substitution reaction is preferably toluene and ethanol, and the volume ratio of toluene to ethanol is preferably 3:1.

[0132] In this invention, the temperature of the third substitution reaction is preferably 95-110°C, and the time is preferably 18 hours.

[0133] Following the third substitution reaction, the present invention preferably performs post-treatment on the resulting third substitution reaction solution, the post-treatment preferably including the following steps:

[0134] The third substitution reaction solution was filtered, and the resulting filtrate was rotary evaporated under reduced pressure until no fractions were obtained. The solvent was removed by rotary evaporation of the filtrate, and the crude product was passed through a silica gel column to obtain a pure anthrone compound with the structure shown in formula (1).

[0135] This invention provides the application of the above-mentioned anthrone compounds in the preparation of organic electroluminescent devices. In this invention, the application is preferably as a light-emitting layer.

[0136] The present invention provides an organic electroluminescent device, comprising a cathode, an anode, and an organic functional layer, wherein the organic functional layer is located between the anode and the cathode, and the organic functional layer comprises the aforementioned anthrone compounds.

[0137] In this invention, the organic functional layer preferably includes a light-emitting layer, which comprises the aforementioned anthrone compounds. In this invention, the organic functional layer preferably comprises a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, an electron transport layer, and an electron injection layer stacked sequentially, wherein the hole injection layer is in contact with the anode, and the electron injection layer is in contact with the cathode.

[0138] In this invention, the surface of the cathode layer is preferably provided with a light extraction layer.

[0139] The present invention does not have any special requirements for the materials of the anode, hole injection layer, hole transport layer, electron blocking layer, electron transport layer, electron injection layer, and cathode; materials well known in the art can be used.

[0140] In this invention, the light-emitting layer preferably comprises a host material and a dopant material, wherein the host material comprises the above-mentioned anthrone compounds.

[0141] In this invention, the mass percentage of the host material in the light-emitting layer is preferably 80-95%, more preferably 85-90%, and the mass percentage of the dopant material in the light-emitting layer is preferably 5-20%, more preferably 10-15%. This invention does not have any special requirements regarding the specific type of the dopant material; conventional guest light-emitting materials in the art can be used.

[0142] As a specific embodiment of the present invention, the cross-sectional structural schematic diagram of the organic electroluminescent device is shown below. Figure 1 As shown. Figure 1 In the diagram, 1-substrate layer, 2-anode layer, 3-hole injection layer, 4-hole transport layer, 5-electron blocking layer, 6-light emitting layer, 7-electron transport layer, 8-electron injection layer, 9-cathode layer, and 10-light extraction layer.

[0143] Each organic layer in the organic electroluminescent device provided by the present invention is preferably prepared by vacuum evaporation, molecular beam evaporation, solvent-based dip coating, spin coating, rod coating, or inkjet printing. Metal electrodes are preferably prepared by evaporation or sputtering.

[0144] The following detailed description, in conjunction with embodiments, provides an anthrone compound, its preparation method and application, and an organic electroluminescent device provided by the present invention. However, these descriptions should not be construed as limiting the scope of protection of the present invention.

[0145] Example 1: Synthesis of intermediates

[0146] (1) Synthesis of intermediate A-1

[0147]

[0148] Synthesis of intermediate D-1: 0.015 mol of starting material H-1, 0.015 mol of intermediate G-1 and 120 ml of polyphosphoric acid were added to a 250 ml flask. The mixture was heated under reflux at 180 °C for 8 hours until the reaction was complete. After cooling to room temperature, 50 ml of a mixture of water and n-hexane (volume ratio 5:3) was added, the mixture was stirred, allowed to stand, filtered, and the filter cake was dried. The mixture was then recrystallized from the filter cake with water and petroleum ether (volume ratio 5:3) to obtain intermediate D-1.

[0149] Synthesis of intermediate A-1: ​​In a 250 ml three-necked flask under nitrogen protection, add 0.01 mol of starting material B-1, 0.012 mol of intermediate D-1, and 150 ml of toluene and stir to mix. Then add 5 × 10⁻⁶ ml of toluene. -5 molPd2(dba)3, 5×10 -5 0.03 mol P(t-Bu)3 and 0.03 mol sodium tert-butoxide were heated to 105 °C and refluxed for 24 hours. The reaction was observed on a TLC plate and found to be complete. After natural cooling to room temperature, the mixture was filtered, and the filtrate was rotary evaporated until no fraction remained. The filtrate was then passed through a neutral silica gel column to obtain intermediate A-1. Elemental analysis revealed the structure (molecular formula C). 34 H 22 ClNO4): Theoretical values: C, 75.07; H, 4.08; N, 2.57; O, 11.76; Measured values: C, 75.13; H, 4.02; N, 2.48; O, 11.53. LC-MS (m / z) (M + The theoretical value is 543.12, and the measured value is 543.07.

[0150] (2) Synthesis of intermediate A-2

[0151]

[0152]

[0153] Synthesis of intermediate D-2: The synthesis steps of intermediate D-2 are the same as those of intermediate D-1, except that intermediate G-1 is replaced with G-2 and raw material H-1 is replaced with raw material H-2 to obtain intermediate D-2.

[0154] Synthesis of Intermediate A-2: The synthesis steps of intermediate A-2 are the same as those of intermediate A-1, except that intermediate D-2 replaces D-1 and starting material B-2 replaces B-1; thus, intermediate A-2 is obtained; elemental analysis structure (molecular formula C). 34 H 22 ClNO2S2): Theoretical values: C, 70.88; H, 3.85; N, 2.43; S, 11.13; Measured values: C, 70.91; H, 3.83; N, 2.39; S, 11.17. LC-MS (m / z) (M + The theoretical value is 575.08, and the measured value is 575.05.

[0155] (3) Synthesis of intermediate A-3

[0156]

[0157] Synthesis of intermediate J-1: In a 500 ml three-necked flask under nitrogen protection, 0.04 mol of starting material M-1, 0.05 mol of intermediate I-1, 0.05 mol of Cs₂CO₃, 0.004 mol of Cu powder, 0.004 mol of 18-crown 6, and 200 ml of o-dichlorobenzene were added sequentially. The mixture was stirred and heated to reflux for 12 hours. A sample was spotted onto a TLC plate to indicate complete reaction. The mixture was then allowed to cool naturally to room temperature, filtered, and the filtrate was rotary evaporated under reduced pressure until no fraction remained. The filtrate was then passed through a neutral silica gel column to obtain intermediate J-1.

[0158] Synthesis of intermediate D-3: In a 250 ml three-necked flask under nitrogen protection, 0.03 mol of intermediate J-1, 0.032 mol of iodobenzene, and 150 ml of toluene were added and stirred. Then, 0.06 mol of sodium tert-butoxide, 0.0015 mol of Pd2(dba)3, and 0.0015 mol of tri-tert-butylphosphine were added. The mixture was stirred and heated to 115 °C and refluxed for 12 hours. Samples were taken and spotted onto a TLC plate to indicate complete reaction. The mixture was allowed to cool naturally to room temperature, filtered, and the filtrate was rotary evaporated under reduced pressure until no fraction was obtained. The filtrate was then passed through a neutral silica gel column to obtain intermediate D-3.

[0159] Synthesis of Intermediate A-3: The synthesis steps of intermediate A-3 are the same as those of intermediate A-1, except that intermediate D-3 replaces D-1 and starting material B-2 replaces B-1, yielding intermediate A-3; elemental analysis structure (molecular formula C). 46 H32 ClN3O2): Theoretical values: C, 79.59; H, 4.65; N, 6.05; Measured values: C, 79.63; H, 4.62; N, 6.01. LC-MS (m / z) (M + The theoretical value is 693.22, and the measured value is 693.20.

[0160] Example 2 Synthesis of Compound 11

[0161]

[0162] 20 mmol of intermediate A-1 and 20 mmol of starting material C-1 were dissolved in a mixed solution of 30 mL toluene and 10 mL ethanol. After deoxygenation, 0.1 mmol of Pd(PPh3)4 and 15 mL of 3 mol / L K2CO3 aqueous solution were added. The mixture was reacted at 100 °C for 18 hours under an inert atmosphere. After the starting material had reacted completely, the mixture was cooled and filtered. The solvent was removed by rotary evaporation of the filtrate. The crude product was passed through a silica gel column to obtain the target product compound 11.

[0163] Elemental analysis of the structure (molecular formula C) 46 H 29 NO5): Theoretical values: C, 81.76; H, 4.33; N, 2.07; Measured values: C, 81.78; H, 4.32; N, 2.03. LC-MS: Material molecular weight is 675.20, measured molecular weight is 675.24.

[0164] 1 H NMR(400MHz,Chloroform-d)δ8.07-7.92(m,2H),7.79(d,1H),7.67-7.58(m,2H),7.56-7.43(m,4H),7.41-7 .20(m,5H),7.17(m,2H),7.11(td,1H),7.06(m,2H),6.97(dd,1H),6.78(dd,1H),6.70(d,2H),1.58(s,6H).

[0165] Example 3 Synthesis of Compound 12

[0166]

[0167] Compound 11 was prepared according to the synthesis method of Compound 11 in Example 1, using starting material C-2 instead of starting material C-1; elemental analysis structure (molecular formula C 46 H 29NO5): Theoretical values: C, 81.76; H, 4.33; N, 2.07; Measured values: C, 81.73; H, 4.37; N, 2.04. LC-MS: Material molecular weight is 675.20, measured molecular weight is 675.25.

[0168] 1 H NMR(400MHz,Chloroform-d)δ8.09-7.93(m,2H),7.86(d,1H),7.61(m,2H),7.58-7.52(m,2H),7.52-7.41(m,3H), 7.41-7.22(m,4H),7.17(m,2H),7.11(m,1H),7.06(m,2H),6.97(dd,1H),6.78(dd,1H),6.70(d,2H),1.58(s,6H).

[0169] Example 4 Synthesis of Compound 33

[0170]

[0171] Compound 11 was prepared according to the synthesis method of Example 1, except that intermediate A-2 was used instead of intermediate A-1; and starting material C-3 was used instead of starting material C-1; elemental analysis structure (molecular formula C 44 H 29 N3O2S2): Theoretical values: C, 75.95; H, 4.20; N, 6.04; S, 9.21; Measured values: C, 75.96; H, 4.23; N, 6.06; S, 9.27. LC-MS: Material molecular weight is 695.17, measured molecular weight is 695.13.

[0172] 1 H NMR(400MHz,Chloroform-d)δ8.71(d,2H),8.01(d,1H),7.78(d,1H),7.76-7.70(m,2H),7.67(dd,1H),7.6 4-7.56(m,2H),7.44-7.26(m,4H),7.24-7.04(m,7H),7.03(d,1H),6.91(s,1H),6.73(s,1H),1.59(s,6H).

[0173] Example 5 Synthesis of Compound 34

[0174]

[0175] Compound 11 was prepared according to the synthesis method of Example 1, except that intermediate A-2 was used instead of intermediate A-1; and starting material C-4 was used instead of starting material C-1; elemental analysis structure (molecular formula C 44 H 29 N3O2S2): Theoretical values: C, 75.95; H, 4.20; N, 6.04; S, 9.21; Measured values: C, 75.93; H, 4.27; N, 6.03; S, 9.23. LC-MS: Material molecular weight is 695.17, measured molecular weight is 695.15.

[0176] 1 H NMR(400MHz,Chloroform-d)δ8.72(d,2H),8.62(t,1H),8.39(m,1H),8.03(d,1H),7.86-7.69(m,2H),7.64(dd,1H), 7.55(m,1H),7.42(d,1H),7.38-7.26(m,3H),7.24-7.04(m,7H),7.03(d,1H),6.91(s,1H),6.73(s,1H),1.59(s,6H).

[0177] Example 6 Synthesis of Compound 55

[0178]

[0179] Compound 11 was prepared according to the synthesis method of Example 1, except that intermediate A-3 was used instead of intermediate A-1; and starting material C-5 was used instead of starting material C-1; elemental analysis structure (molecular formula C 56 H 39 N3O2): Theoretical values: C, 85.58; H, 5.00; N, 5.35; Measured values: C, 85.54; H, 5.07; N, 5.37. LC-MS: Material molecular weight is 785.30, measured molecular weight is 785.33.

[0180] 1 H NMR(400MHz,Chloroform-d)δ8.02(d,1H),8.00-7.92(m,2H),7.89-7.83(m,1H),7.78(d,1H),7.73(t,1H),7. 61(dd,1H),7.58-7.46(m,3H),7.43(d,1H),7.36-7.24(m,4H),7.21-6.96(m,17H),6.90(s,1H),1.56(s,6H).

[0181] Example 7 Synthesis of Compound 56

[0182]

[0183] Compound 1 was prepared according to the synthesis method of Example 2, except that intermediate A-3 was used instead of intermediate A-1; and starting material C-6 was used instead of starting material C-1; elemental analysis showed the structure (molecular formula C). 58 H 41 N3O2): Theoretical values: C, 85.79; H, 5.09; N, 5.18; Measured values: C, 85.77; H, 5.04; N, 5.14. LC-MS: Material molecular weight is 811.32, measured molecular weight is 811.33.

[0184] 1 H NMR(400MHz,Chloroform-d)δ8.01(d,1H),7.78(d,1H),7.69-7.53(m,7H),7.48-7.37(m,3H),7.37-7.32(m,1H),7.32-7.25(m,4H),7.25-

[0185] 6.98(m,17H),6.90(s,1H),1.56(s,6H).

[0186] The following examples 1-6 and comparative examples 1-2 illustrate in detail the application effects of the OLED materials synthesized in this invention in devices. The fabrication processes of the devices in examples 1-6 and comparative example 2 are completely identical to those in comparative example 1, and the same substrate and electrode materials are used. The electrode film thickness is also consistent. The difference lies in the main material of the light-emitting layer. The structures of the devices in each example are shown in Table 1, and the device performance test results are shown in Table 2.

[0187] Fabrication process of device comparative example 1:

[0188] a) The substrate layer 1 is transparent glass, and an anode layer 2 (Ag, with a thickness of 100nm) is deposited on the surface of the substrate layer 1 by vacuum evaporation.

[0189] b) HAT-CN with a thickness of 10 nm is deposited on the anode layer 2 by vacuum evaporation to serve as the hole injection layer 3;

[0190] c) HT-1 with a thickness of 140 nm is deposited on hole injection layer 3 by vacuum evaporation to serve as hole transport layer 4.

[0191] d) EB-1 with a thickness of 30 nm is deposited on top of hole transport layer 4 by vacuum evaporation to serve as electron blocking layer 5.

[0192] e) A light-emitting layer 6 is deposited on top of the electron blocking layer 5, with Ref-1 and GH-2 as the host materials and GD-1 as the dopant material. The mass ratio of Ref-1, GH-2 and GD-1 is 45:45:10, and the thickness is 40nm.

[0193] f) On the light-emitting layer 6, ET-1 and Liq with a mass ratio of 1:1 are vapor-deposited by vacuum evaporation, with a thickness of 40 nm, to serve as the electron transport layer 7.

[0194] g) On top of the electron transport layer 7, LiF with a thickness of 1 nm is vacuum-deposited as the electron injection layer 8;

[0195] h) Above the electron injection layer 8, a Mg:Ag layer with a mass ratio of 1:9 and a thickness of 15 nm is vacuum-deposited as the cathode layer 9.

[0196] i) On the cathode layer 9, Alq3 with a thickness of 70 nm is deposited by vacuum evaporation and used as the light extraction layer 10.

[0197] After completing the fabrication of the electroluminescent device according to the above steps, the current efficiency of the device was measured, and the results are shown in Table 2. The molecular structural formulas of the relevant materials are shown below:

[0198]

[0199] Table 1. Structure of Application Examples Devices

[0200]

[0201]

[0202]

[0203] Table 2 shows the test data of the electroluminescent devices.

[0204]

[0205]

[0206] Note: Current efficiency was tested using an IVL (current-voltage-luminance) testing system at a current density of 10 mA / cm². 2 .

[0207] As can be seen from the results in Table 2, when the organic compounds of the present invention are applied to the fabrication of OLED light-emitting devices, the device efficiency is improved and the service life is extended compared with comparative examples 1 to 2.

[0208] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. An anthrone compound having the structure shown in formula (3-1) or formula (3-2): Equation (3-1); Equation (3-2); In equation (3-1) or equation (3-2), L1 is a single bond, substituted or unsubstituted C6-C 30 Alpha-aryl; The R is one of the following: substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted diphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted anthraquinyl, substituted or unsubstituted pyridyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted furanyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted thiophenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted 9,9-dimethylfluorenyl, substituted or unsubstituted N-phenylcarbazolyl, substituted or unsubstituted quinolinyl, substituted or unsubstituted isoquinolinyl, substituted or unsubstituted naphridyl, substituted or unsubstituted oxazolyl, substituted or unsubstituted imidazolyl, substituted or unsubstituted benzoxazolyl, or substituted or unsubstituted benzimidazolyl. X is -O-, -S-, or -N(R1)-; where R1 is substituted or unsubstituted C6-C. 30 aryl; Among the substituted groups mentioned above, each substituent is independently a halogen, cyano, or C1-C group. 20 Alkyl, C6-C 30 One or more of the aryl groups.

2. The anthrone compound according to claim 1, characterized in that, It has the structure shown in any one of equations (4-1) to (4-2): Equation (4-1); Equation (4-2).

3. The anthrone compound according to claim 1, characterized in that, L1 is one of substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, or substituted or unsubstituted diphenylene; R1 is one of substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted diphenyl, substituted or unsubstituted triphenyl, or substituted or unsubstituted anthraquinone. In the above-mentioned substituted groups, each substituent is independently one or more of the following: fluorine atom, cyano, methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, phenyl, naphthyl, biphenyl, pyridyl, benzofuranyl, carbazoleyl, diphenylaminoyl, benzothiopheneyl or furanyl.

4. A method for preparing the anthrone compound according to any one of claims 1 to 3, comprising the following steps: (1) Prepare compounds having the structure shown in formula a; Formula a; The method for preparing the compound having the structure shown in Formula a includes: When X is -O-, the preparation method includes the following steps: A compound having the structure shown in formula b undergoes a first cyclization reaction with a compound having the structure shown in formula c to obtain a compound having the structure shown in formula a. Formula b; Formula c; When X is -S-, the compound having the structure shown in formula d undergoes a second cyclization reaction with the compound having the structure shown in formula e to obtain the compound having the structure shown in formula a. Formula d; Formula e; When X is -N(R1)-, the compound having the structure shown in formula f undergoes a third cyclization reaction with the compound having the structure shown in formula g to obtain the compound having the structure shown in formula h. Formula f; Formula g; Formula h; A compound having the structure shown in formula h undergoes a first substitution reaction with a compound having the structure shown in formula i to obtain a compound having the structure shown in formula a. IR1 formula i; (2) A compound having the structure shown in formula a undergoes a second substitution reaction with a compound having the structure shown in formula j to obtain a compound having the structure shown in formula k. Formula j; Formula k; (3) A compound having the structure shown in formula k undergoes a third substitution reaction with a compound having the structure shown in formula m to obtain anthrone compounds having the structure shown in formula (3-1) or formula (3-2); Formula m.

5. The application of the anthrone compound according to any one of claims 1 to 3 or the anthrone compound prepared by the preparation method according to claim 4 in the preparation of organic electroluminescent devices.

6. An organic electroluminescent device, comprising a cathode, an anode, and an organic functional layer, wherein the organic functional layer is located between the anode and the cathode, characterized in that, The organic functional layer comprises anthrone compounds as described in any one of claims 1 to 3 or anthrone compounds prepared by the preparation method described in claim 4.

7. The organic electroluminescent device according to claim 6, characterized in that, The organic functional layer includes a light-emitting layer, which comprises an anthrone compound as described in any one of claims 1 to 3 or an anthrone compound prepared by the preparation method described in claim 4.

8. The organic electroluminescent device according to claim 7, characterized in that, The light-emitting layer comprises a host material and a dopant material, wherein the host material comprises anthrone compound as described in any one of claims 1 to 3 or anthrone compound prepared by the preparation method described in claim 4.

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