Anthracene-containing organic compound and its preparation method and application

Abstract

The present invention belongs to the field of semiconductor material technology, and in particular to a kind of anthracene-containing organic compound and its preparation method and application. The LUMO electron cloud distribution of the anthracene-containing organic compound provided by the present invention is further delocalized, which can improve the anti-electronic properties of the material and effectively improve the electronic stability of the material. The anthracene-containing organic compound provided by the present invention is based on anthracene as the core, and an aromatic fused ring group is connected to form a parent nucleus through a specific connection site. The parent nucleus can increase the weak interaction within the molecule, effectively reduce the evaporation temperature of the molecule, and improve the thermal durability of the material; further, the parent nucleus can suppress the π-π stacking between molecules, significantly improve the electron mobility of the molecule, and reduce the driving voltage of the device; and, due to the presence of the electron-withdrawing conjugation effect of the parent nucleus, the glass transition temperature of the material is increased, and the thin film stability of the material is effectively improved. As an electron transport material, the compound of the present invention can effectively improve device efficiency and service life.

Description

Technical Field

[0001] The present invention belongs to the technical field of semiconductor materials, and in particular relates to an anthracene-containing organic compound and a preparation method and application thereof. Background Art

[0002] Currently, organic light emitting diodes (OLEDs) have been used in products such as smartphones and tablets, and will be used in large-size products such as televisions in the future. The structure of an OLED device is similar to a sandwich, including electrode film layers and organic functional materials sandwiched between different electrode film layers. Among them, the optoelectronic functional materials of OLED devices are divided into two categories: charge injection transport materials and luminescent materials. Charge injection transport materials are further divided into electron injection transport materials, electron blocking materials, hole injection transport materials and hole blocking materials. Luminescent materials are further divided into main luminescent materials and dopant materials.

[0003] In OLED devices, electrons are injected from the cathode and then transferred to the host material through the electron transport layer, where they recombine with holes to generate excitons. Therefore, improving the injection and transport capabilities of the electron transport layer can help reduce the device's driving voltage while achieving high electron-hole recombination efficiency. Therefore, the electron transport layer is very important and needs to have efficient electron injection and transport capabilities and high electron durability.

[0004] As OLED devices continue to develop, material performance requirements are also increasing. They require not only good material stability but also high efficiency and lifespan at low driving voltages. However, existing electron transport materials lack thermal stability and exhibit poor electron tolerance, leading to phase separation or decomposition during device operation. Summary of the Invention

[0005] The purpose of the present invention is to provide an anthracene-containing organic compound and a preparation method and application thereof. The anthracene-containing organic compound provided by the present invention has excellent thermal durability and electronic stability.

[0006] In order to achieve the above object, the present invention provides the following technical solutions:

[0007] The present invention provides an anthracene-containing organic compound, the structure of which is shown in Formula M:

[0008]

[0009] In formula M, Ar1 is C6~C 60 Aryl or C5~C 60Heteroaryl; n is 0 or 1, R1 is phenyl, biphenyl, naphthyl or pyridyl (the attachment site of R1 is any substitutable site on the anthracene ring); L is a single bond, phenyl, biphenyl or naphthyl; R is a structure represented by formula P or a structure represented by formula Q;

[0010]

[0011] In formula P, X is a CH or N atom.

[0012] Preferably, in Ar1, the C6 to C 60 Aryl includes one or more of phenyl, biphenyl, terphenyl, naphthyl and phenanthrenyl; the C5~C 60 The heteroaryl group includes one or more of pyridyl, phenyl-substituted pyridyl, quinolyl, isoquinolyl, carbazolyl, N-phenylcarbazolyl, dibenzofuranyl, phenyl-substituted dibenzofuranyl, naphthobenzofuranyl, N-phenylbenzimidazolyl and benzoxazolyl.

[0013] Preferably, the anthracene-containing organic compound includes one or more of the compound represented by formula S and the compound represented by formula T:

[0014]

[0015] In Formula S or Formula T, Ar1, n, R1, L and X have the same meanings as in Formula M.

[0016] Preferably, the compound represented by formula S includes one or more of the compound represented by formula U and the compound represented by formula V:

[0017]

[0018] In Formula U or Formula V, Ar1, R1, L and X have the same meanings as in Formula M.

[0019] Preferably, the compound represented by formula T includes one or more of the compound represented by formula W and the compound represented by formula Y:

[0020]

[0021] In formula W or formula Y, Ar1, R1, L and X have the same meanings as in formula M.

[0022] Preferably, the anthracene-containing organic compound is any one of Formulas 1 to 348.

[0023] The present invention also provides a method for preparing the anthracene-containing organic compound described in the above scheme, comprising the following steps:

[0024] (1) Raw material D, pinacol diboronate, potassium acetate, [1,1-bis(diphenylphosphino)ferrocene] palladium dichloride, dichloromethane, and dioxane were mixed to undergo a Suzuki cross-coupling reaction to obtain intermediate B, the structure of which is shown in Formula B:

[0025] RB(OH)2 formula B;

[0026] In formula B, R has the same meaning as R in formula M;

[0027] The structure of the raw material D is shown in Formula D:

[0028] RK type D;

[0029] In formula D, K is a halogen, and R has the same meaning as R in formula M;

[0030] (2) The intermediate B is mixed with raw material A, Pd(PPh3)4, sodium carbonate, toluene, ethanol and water to carry out a first reflux reaction to obtain intermediate Z, the structure of which is shown in Formula Z:

[0031] HLR type Z;

[0032] In formula Z, H is a halogen, and R has the same meaning as R in formula M;

[0033] The structure of the raw material A is shown in formula A:

[0034] HLG formula A;

[0035] In formula A, H is halogen, G is halogen, and L has the same meaning as L in formula M;

[0036] (3) mixing the intermediate Z, the raw material C, Pd(PPh3)4, sodium carbonate, toluene, ethanol and water to perform a second reflux reaction to obtain an anthracene-containing organic compound;

[0037] The structure of the raw material C is shown in Formula C:

[0038]

[0039] In formula C, Ar1, n and R1 have the same meanings as Ar1, n and R1 in formula M.

[0040] The present invention also provides the use of the anthracene-containing organic compound described in the above scheme or the anthracene-containing organic compound obtained by the preparation method described in the above scheme in an organic electroluminescent device.

[0041] The present invention also provides an organic electroluminescent device, comprising a first electrode, a second electrode, and an organic thin film layer located between the first electrode and the second electrode; the number of layers of the organic thin film layer is one or more; at least one layer of the organic thin film layer contains the anthracene-containing organic compound described in the above scheme or the anthracene-containing organic compound obtained by the preparation method described in the above scheme.

[0042] The present invention also provides a display element, comprising the organic electroluminescent device described in the above solution.

[0043] The present invention provides an anthracene-containing organic compound. The LUMO electron cloud distribution of the anthracene-containing organic compound provided by the present invention is further delocalized, which can improve the anti-electronic properties of the material and effectively improve the electronic stability of the material. The anthracene-containing organic compound provided by the present invention takes anthracene as the core, and connects an aromatic fused ring group through a specific connection site to form a parent nucleus. The parent nucleus can increase the weak interaction within the molecule, effectively reduce the evaporation temperature of the molecule, and improve the thermal durability of the material; further, the parent nucleus can inhibit the π-π stacking between molecules, significantly improve the electron mobility of the molecule, and reduce the driving voltage of the device; and, due to the existence of the electron-withdrawing conjugation effect of the parent nucleus, the glass transition temperature of the material is increased, and the thin film stability of the material is effectively improved. Therefore, the compound of the present invention, as an electron transport material, can effectively reduce the device driving voltage, improve the device efficiency and service life.

[0044] The present invention also provides a method for preparing the anthracene-containing organic compound described in the above scheme. The preparation method provided by the present invention has simple steps, convenient operation, high feasibility, and has the prospect of large-scale production.

[0045] The present invention also provides the use of the anthracene-containing organic compound described in the above scheme or the anthracene-containing organic compound obtained by the preparation method described in the above scheme in an organic electroluminescent device. The anthracene-containing organic compound provided by the present invention has excellent properties, including a high glass transition temperature (above 120°C), high heat resistance, high electron tolerance and molecular thermal stability, and high electron mobility (greater than 4.0×10 -4 cm 2 The anthracene-containing organic compound provided by the present invention has the following characteristics: a low evaporation temperature (below 350°C) and suitable HOMO / LUMO energy levels. As an electron transport material for OLED devices, it has excellent electron transport ability and good electron injection properties, which can effectively reduce the device driving voltage and improve the device efficiency and operating life.

[0046] The present invention also provides an organic electroluminescent device comprising a first electrode, a second electrode, and an organic thin film layer located between the first and second electrodes; the number of the organic thin film layers is one or more; at least one of the organic thin film layers comprises the anthracene-containing organic compound described in the above embodiment or the anthracene-containing organic compound prepared by the above embodiment. The organic electroluminescent device provided by the present invention has high efficiency, a long operating life, and excellent overall performance.

[0047] The present invention also provides a display element comprising the organic electroluminescent device of the above solution. The display element provided by the present invention uses the high-performance organic electroluminescent device of the present invention, has a longer service life and better overall performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0048] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments. 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 any creative work.

[0049] Figure 1 Schematic diagram of the structure of an OLED device in which the anthracene-containing organic compound of the present invention is used;

[0050] Reference numerals: 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, 10-light extraction layer. DETAILED DESCRIPTION

[0051] The present invention provides an anthracene-containing organic compound, the structure of which is shown in Formula M:

[0052]

[0053] In formula M, Ar1 is C6~C 60 Aryl or C5~C 60 Heteroaryl; n is 0 or 1, R1 is phenyl, biphenyl, naphthyl or pyridyl (the attachment site of R1 is any substitutable site on the anthracene ring); L is a single bond, phenyl, biphenyl or naphthyl; R is a structure represented by formula P or a structure represented by formula Q;

[0054]

[0055] In formula P, X is CH or N atom.

[0056] In the present invention, in Ar1, the C6 to C 60The aryl group preferably includes one or more of phenyl, biphenyl, terphenyl, naphthyl and phenanthrenyl, and more preferably phenyl, biphenyl or naphthyl.

[0057] In the present invention, in Ar1, the C5 to C 60 The heteroaryl group preferably includes one or more of a pyridyl group, a phenyl-substituted pyridyl group, a quinolyl group, an isoquinolyl group, a carbazolyl group, an N-phenylcarbazolyl group, a dibenzofuranyl group, a phenyl-substituted dibenzofuranyl group, a naphthobenzofuranyl group, an N-phenylbenzimidazolyl group and a benzoxazolyl group, more preferably a pyridyl group or a dibenzofuranyl group.

[0058] In the present invention, Ar1 is more preferably:

[0059] In the present invention, the anthracene-containing organic compound preferably includes one or more of the compound represented by formula S and the compound represented by formula T:

[0060]

[0061] In Formula S or Formula T, Ar1, n, R1, L and X have the same meanings as in Formula M.

[0062] In the present invention, the compound represented by formula S preferably includes one or more of the compound represented by formula U and the compound represented by formula V; the compound represented by formula T preferably includes one or more of the compound represented by formula W and the compound represented by formula Y:

[0063]

[0064] In Formula U, Formula V, Formula W or Formula Y, Ar1, R1, L and X have the same meanings as in Formula M.

[0065] In the present invention, the compound represented by formula U preferably includes one or more of the compound represented by formula U-1, the compound represented by formula U-2, the compound represented by formula U-3 and the compound represented by formula U-4:

[0066]

[0067] In formula U-1, formula U-2, formula U-3 or formula U-4, Ar1 and X have the same meanings as in formula M.

[0068] In the present invention, the compound represented by formula V preferably includes one or more of the compound represented by formula V-1, the compound represented by formula V-2, the compound represented by formula V-3 and the compound represented by formula V-4:

[0069]

[0070]

[0071] In Formula V-1, Formula V-2, Formula V-3 or Formula V-4, Ar1, R1 and X have the same meanings as in Formula M.

[0072] In the present invention, the compound represented by formula W preferably includes one or more of the compound represented by formula W-1, the compound represented by formula W-2, the compound represented by formula W-3 and the compound represented by formula W-4:

[0073]

[0074] In Formula W-1, Formula W-2, Formula W-3 or Formula W-4, Ar1 has the same meaning as in Formula M.

[0075] In the present invention, the compound represented by formula Y preferably includes one or more of the compound represented by formula Y-1, the compound represented by formula Y-2, the compound represented by formula Y-3 and the compound represented by formula Y-4:

[0076]

[0077] In Formula Y-1, Formula Y-2, Formula Y-3 or Formula Y-4, Ar1 and R1 have the same meanings as in Formula M.

[0078] In a specific embodiment of the present invention, the anthracene-containing organic compound is preferably any one of Formulas 1 to 348:

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091] The present invention also provides a method for preparing the anthracene-containing organic compound described in the above scheme, comprising the following steps:

[0092] (1) Raw material D, pinacol diboronate, potassium acetate, [1,1-bis(diphenylphosphino)ferrocene] palladium dichloride, dichloromethane, and dioxane were mixed to undergo a Suzuki cross-coupling reaction to obtain intermediate B, the structure of which is shown in Formula B:

[0093] RB(OH)2 formula B;

[0094] In formula B, R has the same meaning as R in formula M;

[0095] (2) The intermediate B is mixed with raw material A, Pd(PPh3)4, sodium carbonate, toluene, ethanol and water to carry out a first reflux reaction to obtain intermediate Z, the structure of which is shown in Formula Z:

[0096] HLR type Z;

[0097] In formula Z, H is a halogen, and R has the same meaning as R in formula M;

[0098] (3) The intermediate Z, raw material C, Pd(PPh3)4, sodium carbonate, toluene, ethanol and water are mixed to carry out a second reflux reaction to obtain an anthracene-containing organic compound.

[0099] In the present invention, raw material D, pinacol diboronate, potassium acetate, [1,1-bis(diphenylphosphino)ferrocene] palladium dichloride, dichloromethane and dioxane are mixed to perform a Suzuki cross-coupling reaction to obtain intermediate B. In the present invention, the structure of the raw material D is shown in Formula D:

[0100] RK type D;

[0101] In formula D, K is a halogen, and R has the same meaning as R in formula M.

[0102] In the present invention, the halogen in formula D is preferably Cl, Br or I.

[0103] In the present invention, the molar ratio of the raw material D to the diboric acid pinacol ester is preferably 1-5:1-10, more preferably 2-4:4-8, and even more preferably 3:6.

[0104] In the present invention, the molar ratio of the raw material D to potassium acetate is preferably 1-5:2-10, more preferably 1-2:3-8, and even more preferably 1:3.

[0105] In the present invention, the molar ratio of the raw material D to [1,1-bis(diphenylphosphino)ferrocene]dichloropalladium dichloromethane is preferably 10-50:1-10, more preferably 20-40:6-10, and even more preferably 30:7.

[0106] In the present invention, the mass ratio of the raw material D to dioxane is preferably 300 mg:1 mL.

[0107] In the present invention, the temperature of the Suzuki cross-coupling reaction is preferably 80-150° C., more preferably 100-130° C., further preferably 125° C., and the holding time is preferably 3-24 h, more preferably 3-8 h, further preferably 5 h.

[0108] In the present invention, the Suzuki cross-coupling reaction preferably further comprises a first purification of the obtained reaction product; the first purification method is preferably column chromatography.

[0109] After obtaining intermediate B, the present invention mixes the intermediate B with raw material A, Pd(PPh3)4, sodium carbonate, toluene, ethanol and water to perform a first reflux reaction to obtain intermediate Z. In the present invention, the structure of the raw material A is shown in formula A:

[0110] HLG formula A;

[0111] In formula A, H is halogen, G is halogen, and L has the same meaning as L in formula M;

[0112] In the present invention, in formula A, H is preferably Cl, and G is preferably Br.

[0113] In the present invention, the molar ratio of the intermediate B to the raw material A is preferably 30-20:30-20, more preferably 24-20:24-20, and even more preferably 22:20.

[0114] In the present invention, the molar ratio of the intermediate B to Pd(PPh3)4 is preferably 20-25:1-1.5, more preferably 20-23:1-1.2, and further preferably 22:1.

[0115] In the present invention, the molar ratio of the intermediate B to sodium carbonate is preferably 10-30:20-60, more preferably 20-25:40-60, and further preferably 22:60.

[0116] In the present invention, the mass ratio of the intermediate B to toluene is preferably (100-600) mg:1 mL, more preferably (200-400) mg:1 mL, and even more preferably 300 mg:1 mL.

[0117] In the present invention, the mass ratio of sodium carbonate to water is preferably 1-1.2:2-5, more preferably 1-1.1:3-4, and further preferably 1:3.

[0118] In the present invention, the volume ratio of ethanol to water is preferably 1.0-1.5:1.0-1.5, more preferably 1.0-1.2:1.0-1.2, and even more preferably 1:1.

[0119] In the present invention, the water is preferably distilled water.

[0120] In the present invention, the mixing of the intermediate B with the raw material A, Pd(PPh3)4, sodium carbonate, toluene, ethanol and water is preferably carried out in a protective atmosphere; the protective atmosphere is preferably nitrogen.

[0121] In the present invention, the first reflux reaction is preferably carried out in a protective atmosphere; the protective atmosphere is preferably nitrogen; the temperature of the first reflux reaction is preferably 80-110°C, more preferably 90-100°C, and even more preferably 100°C, and the holding time is preferably 3-24 hours, more preferably 10-15 hours, and even more preferably 12 hours. In a specific embodiment of the present invention, it is preferred to confirm whether the raw materials have reacted completely using a sampling point plate.

[0122] In the present invention, after the first reflux reaction, the obtained product is preferably subjected to a first post-treatment; the first post-treatment preferably includes sequentially performing a first cooling, a first filtration, a filtrate distillation, and a second purification.

[0123] In the present invention, the first cooling is preferably natural cooling; and the final temperature of the first cooling is preferably room temperature.

[0124] In the present invention, the filtrate is preferably distilled by vacuum rotary evaporation; the temperature of the vacuum rotary evaporation is preferably 70 to 100°C, more preferably 85°C, and the pressure is preferably -0.07 to -0.10 MPa, more preferably -0.09 MPa, until no fraction is distilled out.

[0125] In the present invention, the second purification is preferably performed over a neutral silica gel column; the mobile phase of the neutral silica gel column is preferably ethyl acetate and petroleum ether; the volume ratio of ethyl acetate to petroleum ether is preferably 0.5-2:1-5, more preferably 1-2:2-4, and further preferably 1:3.

[0126] After obtaining the intermediate Z, the present invention further comprises mixing the intermediate Z, the raw material C, Pd(PPh3)4, sodium carbonate, toluene, ethanol and water to perform a second reflux reaction to obtain an anthracene-containing organic compound. In the present invention, in formula Z, the halogen is preferably Cl.

[0127] In the present invention, the structure of the raw material C is shown in Formula C:

[0128]

[0129] In formula C, Ar1, n and R1 have the same meanings as Ar1, n and R1 in formula M.

[0130] In the present invention, the molar ratio of the intermediate Z to the raw material C is preferably 10-30:10-30, more preferably 15-25:17-27, and even more preferably 20:22.

[0131] In the present invention, the molar ratio of the intermediate Z to sodium carbonate is preferably 10-50:20-100, more preferably 15-30:50-80, and even more preferably 20:60.

[0132] In the present invention, the molar ratio of the intermediate Z to Pd(PPh3)4 is preferably 100-500:0.1-5, more preferably 100-200:1-3, and further preferably 200:1.

[0133] In the present invention, the mass ratio of the intermediate Z to toluene is preferably (100-1000) mg:1 mL, more preferably (200-800) mg:1 mL, and even more preferably (200-600) mg:1 mL.

[0134] In the present invention, the mass ratio of sodium carbonate to water is preferably 1-1.2:2-5, more preferably 1-1.1:2-4, and further preferably 1:3.

[0135] In the present invention, the volume ratio of ethanol to water is preferably 1-5:1-5, more preferably 1-2:1-2, and even more preferably 1:1.

[0136] In the present invention, the water is preferably distilled water.

[0137] In the present invention, the mixing of the intermediate Z, raw material C, Pd(PPh3)4, sodium carbonate, toluene, ethanol and water is preferably carried out in a protective atmosphere; the protective atmosphere is preferably nitrogen.

[0138] In the present invention, the second reflux reaction is preferably carried out in a protective atmosphere; the protective atmosphere is preferably nitrogen; the temperature of the second reflux reaction is preferably 80-100°C, more preferably 90-100°C, and even more preferably 90°C, and the holding time is preferably 3-48 hours, more preferably 12-24 hours, and even more preferably 16 hours. In a specific embodiment of the present invention, it is preferred to confirm whether the raw materials have reacted completely using a sampling point plate.

[0139] In the present invention, the second reflux reaction preferably further includes a second post-treatment of the obtained product; the second post-treatment preferably includes a second cooling, a second filtration, a filtrate distillation and a third purification in sequence.

[0140] In the present invention, the second cooling is preferably natural cooling; and the final temperature of the second cooling is preferably room temperature.

[0141] In the present invention, the filtrate is preferably distilled by vacuum rotary evaporation; the vacuum rotary evaporation temperature is preferably 60 to 100°C, more preferably 85°C, and the pressure is preferably -0.08 to -0.10 MPa, more preferably -0.09 MPa, until no fraction is distilled out. The present invention obtains a light yellow solid by distilling the filtrate.

[0142] In the present invention, the third purification is preferably purification by silica gel column; the eluent for the silica gel column purification is preferably ethyl acetate and petroleum ether; the volume ratio of ethyl acetate to petroleum ether is preferably 0.1-10:1-20, more preferably 0.1-1:1-5, and further preferably 1:4.

[0143] The present invention also provides the use of the anthracene-containing organic compound described in the above scheme or the anthracene-containing organic compound obtained by the preparation method described in the above scheme in an organic electroluminescent device.

[0144] The anthracene-containing organic compound provided by the present invention has excellent properties, such as high glass transition temperature (above 120°C), high heat resistance, high electron tolerance and molecular thermal stability, and high electron mobility (greater than 4.0×10 -4 cm 2 The anthracene-containing organic compound provided by the present invention has the following characteristics: a low evaporation temperature (below 350°C) and suitable HOMO / LUMO energy levels. As an electron transport material for OLED devices, it has excellent electron transport ability and good electron injection properties, which can effectively reduce the device driving voltage and improve the device efficiency and operating life.

[0145] The present invention also provides an organic electroluminescent device, comprising a first electrode, a second electrode, and an organic thin film layer located between the first electrode and the second electrode; the number of layers of the organic thin film layer is one or more; at least one layer of the organic thin film layer contains the anthracene-containing organic compound described in the above scheme or the anthracene-containing organic compound obtained by the preparation method described in the above scheme.

[0146] In the present invention, the organic thin film layer preferably includes one or more layers selected from the group consisting of a light-emitting layer, a hole injection layer, a hole transport layer, an electron blocking layer, an electron transport layer, and an electron injection layer, and more preferably includes an electron transport layer.

[0147] In the present invention, the organic thin film layer preferably contains the anthracene-containing organic compound described in the above scheme or the anthracene-containing organic compound obtained by the preparation method described in the above scheme in the electron transport layer, and the type of anthracene-containing organic compound in the organic thin film layer is preferably one or more.

[0148] In the present invention, the electron transport layer preferably further contains an auxiliary electron transport material; the auxiliary electron transport material preferably includes lithium octahydroxyquinoline.

[0149] The present invention also provides a display element, comprising the organic electroluminescent device described in the above solution.

[0150] The display element provided by the present invention adopts the high-performance organic electroluminescent device of the present invention, and has a longer service life and better overall performance.

[0151] In order to further illustrate the present invention, the scheme of the present invention is described in detail below with reference to the accompanying drawings and embodiments, but they should not be understood as limiting the scope of protection of the present invention.

[0152] In the specific embodiments of the present invention, unless otherwise specified, all raw materials and reactants were purchased from CECEP Wanrun Co., Ltd.

[0153] Synthesis of Example Compound 1

[0154]

[0155] (1) Intermediate B-1:

[0156] 0.03 mol of raw material D-1, 0.06 mol of pinacol diboronate, 0.09 mol of potassium acetate, and 0.007 mol of [1,1-bis(diphenylphosphino)ferrocene]dichloropalladium in dichloromethane were dissolved in 60 mL of dioxane, and the mixture was reacted at 125 °C for 5 h. The remaining product was purified by column chromatography to obtain intermediate B-1.

[0157] (2) Intermediate Z-1:

[0158] In a 500 mL three-necked flask, 0.02 mol of raw material A-1, 0.022 mol of intermediate B-1, 33.3 g of sodium carbonate, 100 mL of toluene, 100 mL of ethanol, and 100 mL of distilled water were added under nitrogen. Then, 1×10 -3 mol of Pd(PPh3)4, heated to reflux for 12 h, sampled on a plate, and showed that the raw material had reacted completely. The mixture was naturally cooled to room temperature, filtered, and the filtrate was subjected to vacuum rotary evaporation (-0.09 MPa, 85 ° C) until there was no fraction. The mixture was passed through a neutral silica gel column (the mobile phase was ethyl acetate: petroleum ether in a volume ratio of 1:3) to obtain intermediate Z-1.

[0159] (3) Compound 1:

[0160] In a 500 mL three-necked flask, 0.02 mol of intermediate Z-1, 0.022 mol of raw material C-1, 0.06 mol of sodium carbonate, 100 mL of toluene, 100 mL of ethanol and 100 mL of distilled water were added under nitrogen, and then 1×10 -4 mol of Pd(PPh3)4, heated to reflux for 16 h, a sampling point plate was taken, and the reaction of the raw materials was complete. The mixture was naturally cooled to room temperature and filtered. The filtrate was subjected to reduced pressure rotary evaporation (-0.09 MPa, 85°C) until there was no fraction to obtain a light yellow solid. The light yellow solid powder was then purified by silica gel column with an eluent of ethyl acetate: petroleum ether = 1:4 (volume ratio) to obtain compound 1.

[0161] The preparation methods of the compounds of Examples 2 to 25 are the same as those of Example 1, except that each example uses the corresponding raw material A, raw material / intermediate B, and raw material C in Table 1;

[0162] Among them, intermediate B includes intermediate B-1 and intermediate B-2. The preparation method of intermediate B-2 is the same as that of intermediate B-1, except that raw material D-2 is used instead of raw material D-1.

[0163]

[0164] Table 1 Raw materials and intermediates and elemental analysis of Examples 1 to 25

[0165]

[0166]

[0167]

[0168]

[0169] The anthracene-containing organic compounds prepared in Examples 1 to 25 of the present invention were subjected to H NMR spectroscopy testing. The results are shown in Table 2:

[0170] Table 2 H NMR spectrum data of anthracene-containing organic compounds of Examples 1 to 25

[0171]

[0172]

[0173]

[0174] It can be seen from Table 2 that the present invention successfully synthesized anthracene-containing organic compounds.

[0175] Application Examples

[0176] The following device is prepared as Application Example 1. The preparation method of Application Example 1 is the same as that of Application Examples 2 to 25 and Comparative Application Examples 1 to 6. The differences are marked in brackets:

[0177] (a) The substrate layer 1 is transparent glass. Ag is deposited on the surface of the substrate layer 1 by vacuum evaporation to a thickness of 100 nm to serve as the anode layer 2.

[0178] (b) HAT-CN was deposited on the anode layer 2 by vacuum evaporation to a thickness of 10 nm as the hole injection layer 3;

[0179] (c) On the hole injection layer 3, HT-1 was vacuum-deposited to a thickness of 140 nm to serve as the hole transport layer 4;

[0180] (d) On the hole transport layer 4, EB-1 was deposited by vacuum evaporation to a thickness of 30 nm as the electron blocking layer 5;

[0181] (e) Evaporating a light-emitting layer 6 on the electron blocking layer 5, using BH-1 as the host material and BD-1 as the dopant material, with a mass ratio of BH-1 to BD-1 of 90:10 and a thickness of 40 nm;

[0182] (f) On the light-emitting layer 6, a compound of the present invention (comparative examples ET-1 to ET-6) and Liq were vacuum-deposited in a mass ratio of 1:1 to a thickness of 40 nm to form an electron transport layer 7;

[0183] (g) LiF was vacuum-deposited on the electron transport layer 7 to a thickness of 1 nm as the electron injection layer 8;

[0184] (h) On the electron injection layer 8, a 15 nm thick Mg-Ag layer with a mass ratio of 1:9 was vacuum-deposited as the cathode layer 9;

[0185] (i) On the cathode layer 9, CP-1 is deposited by vacuum evaporation to a thickness of 70 nm as the light extraction layer 10 to obtain an organic electroluminescent device with the following structure: Figure 1 As shown;

[0186] The structural formulas of the materials used in the application examples and comparative examples are as follows:

[0187]

[0188]

[0189] The preparation methods for Application Examples 2-25 and Comparative Application Examples 1-6 were the same as for Application Example 1, using the same substrate and electrode materials, with the same electrode thickness. The materials used for each layer of the organic electroluminescent devices prepared in Application Examples 1-25 and Comparative Application Examples 1-6 are shown in Table 3.

[0190] Table 3 Organic electroluminescent devices prepared in Application Examples 1 to 25 and Comparative Examples 1 to 6

[0191]

[0192]

[0193]

[0194] Test Case

[0195] The performance tests of the devices prepared in Example 1 to Example 25 and Comparative Example 1 to Comparative Example 6 were performed, and the results are shown in Table 4.

[0196] Table 4 Performance data of devices prepared in Application Examples 1 to 25 and Comparative Examples 1 to 6

[0197]

[0198]

[0199] Note: The current efficiency is tested using an IVL (current-voltage-luminance) test system at a current density of 10 mA / cm 2 .

[0200] It can be seen from Table 4 that when the anthracene-containing organic compound of the present invention is used as the electron transport layer, the device efficiency and device life are significantly improved compared with the application of Comparative Examples 1 to 6.

[0201] It can be seen from the above examples that the anthracene-containing organic compound provided by the present invention has excellent thermal durability and electronic stability. As an electron transport material, it can effectively reduce the device driving voltage and improve the device efficiency and service life.

[0202] Although the above embodiment provides a detailed description of the present invention, it is only a part of the embodiments of the present invention, not all of the embodiments. Other embodiments can be obtained based on this embodiment without creativity, and these embodiments all fall within the scope of protection of the present invention.

Claims

1. An anthracene-containing organic compound, characterized in that The structure is shown in Formula M: Formula M; In formula M, Ar1 is C6~C 60 Aryl or C5~C 60 Heteroaryl; n is 0 or 1, R1 is phenyl, biphenyl, naphthyl or pyridyl; L is a single bond, phenyl, biphenyl or naphthyl; R is a structure represented by formula P or a structure represented by formula Q; Formula P; Formula Q; In formula P, X is a CH or N atom; In Ar1, the C6~C 60 The aryl group is selected from one of phenyl, biphenyl, terphenyl, naphthyl and phenanthrenyl; The C5~C 60 The heteroaryl group is selected from one of pyridyl, phenyl-substituted pyridyl, quinolyl, isoquinolyl, carbazolyl, N-phenylcarbazolyl, dibenzofuranyl, phenyl-substituted dibenzofuranyl, naphthobenzofuranyl, N-phenylbenzimidazolyl and benzoxazolyl.

2. The anthracene-containing organic compound according to claim 1, characterized in that The anthracene-containing organic compound includes one or more of the compounds represented by formula S and the compounds represented by formula T: Formula S; Formula T; In Formula S or Formula T, Ar1, n, R1, L and X have the same meanings as in Formula M.

3. The anthracene-containing organic compound according to claim 2, characterized in that The compound represented by formula S includes one or more of the compound represented by formula U and the compound represented by formula V: Formula U; Formula V; In Formula U or Formula V, Ar1, R1, L and X have the same meanings as in Formula M.

4. The anthracene-containing organic compound according to claim 2, characterized in that The compound represented by formula T includes one or more of the compound represented by formula W and the compound represented by formula Y: Formula W; Formula Y; In formula W or formula Y, Ar1, R1, L and X have the same meanings as in formula M.

5. The anthracene-containing organic compound according to claim 1, characterized in that The anthracene-containing organic compound is any one of Formula 1 to Formula 348: Formula 1 Formula 2 Formula 3 Formula 4 Formula 5 Formula 6 Formula 7 Formula 8 Formula 9 Formula 10 Formula 11 Formula 12 Formula 13 Formula 14 Formula 15 Formula 16 Formula 17 Formula 18 Formula 19 Formula 20 Formula 21 Formula 22 Formula 23 Formula 24 Formula 25 Formula 26 Formula 27 Formula 28 Formula 29 Formula 30 Formula 31 Formula 32 Formula 33 Formula 34 Formula 35 Formula 36 Formula 37 Formula 38 Formula 39 Formula 40 Formula 41 Formula 42 Formula 43 Formula 44 Formula 45 Formula 46 Formula 47 Formula 48 Formula 49 Formula 50 Formula 51 Formula 52 Formula 53 Formula 54 Formula 55 Formula 56 Formula 57 Formula 58 Formula 59 Formula 60 Formula 61 Formula 62 Formula 63 Formula 64 Formula 65 Formula 66 Formula 67 Formula 68 Formula 69 Formula 70 Formula 71 Formula 72 Formula 73 Formula 74 Formula 75 Formula 76 Formula 77 Formula 78 Formula 79 Formula 80 Formula 81 Formula 82 Formula 83 Formula 84 Formula 85 Formula 86 Formula 87 Formula 88 Formula 89 Formula 90 Formula 91 Formula 92 Formula 93 Formula 94 Formula 95 Formula 96 Formula 97 Formula 98 Formula 99 Formula 100 Formula 101 Formula 102 Formula 103 Formula 104 Formula 105 Formula 106 Formula 107 Formula 108 Formula 109 Formula 110 Formula 111 Formula 112 Formula 113 Formula 114 Formula 115 Formula 116 Formula 117 Formula 118 Formula 119 Formula 120 Formula 121 Formula 122 Formula 123 Formula 124 Formula 125 Formula 126 Formula 127 Formula 128 Formula 129 Formula 130 Formula 131 Formula 132 Formula 133 Formula 134 Formula 135 Formula 136 Formula 137 Formula 138 Formula 139 Formula 140 Formula 141 Formula 142 Formula 143 Formula 144 Formula 145 Formula 146 Formula 147 Formula 148 Formula 149 Formula 150 Formula 151 Formula 152 Formula 153 Formula 154 Formula 155 Formula 156 Formula 157 Formula 158 Formula 159 Formula 160 Formula 161 Formula 162 Formula 163 Formula 164 Formula 165 Formula 166 Formula 167 Formula 168 Formula 169 Formula 170 Formula 171 Formula 172 Formula 173 Formula 174 Formula 175 Formula 176 Formula 177 Formula 178 Formula 179 Formula 180 Formula 181 Formula 182 Formula 183 Formula 184 Formula 185 Formula 186 Formula 187 Formula 188 Formula 189 Formula 190 Formula 191 Formula 192 Formula 193 Formula 194 Formula 195 Formula 196 Formula 197 Formula 198 Formula 199 Formula 200 Formula 201 Formula 202 Formula 203 Formula 204 Formula 205 Formula 206 Formula 207 Formula 208 Formula 209 Formula 210 Formula 211 Formula 212 Formula 213 Formula 214 Formula 215 Formula 216 Formula 217 Formula 218 Formula 219 Formula 220 Formula 221 Formula 222 Formula 223 Formula 224 Formula 225 Formula 226 Formula 227 Formula 228 Formula 229 Formula 230 Formula 231 Formula 232 Formula 233 Formula 234 Formula 235 Formula 236 Formula 237 Formula 238 Formula 239 Formula 240 Formula 241 Formula 242 Formula 243 Formula 244 Formula 245 Formula 246 Formula 247 Formula 248 Formula 249 Formula 250 Formula 251 Formula 252 Formula 253 Formula 254 Formula 255 Formula 256 Formula 257 Formula 258 Formula 259 Formula 260 Formula 261 Formula 262 Formula 263 Formula 264 Formula 265 Formula 266 Formula 267 Formula 268 Formula 269 Formula 270 Formula 271 Formula 272 Formula 273 Formula 274 Formula 275 Formula 276 Formula 277 Formula 278 Formula 279 Formula 280 Formula 281 Formula 282 Formula 283 Formula 284 Formula 285 Formula 286 Formula 287 Formula 288 Formula 289 Formula 290 Formula 291 Formula 292 Formula 293 Formula 294 Formula 295 Formula 296 Formula 297 Formula 298 Formula 299 Formula 300 Formula 301 Formula 302 Formula 303 Formula 304 Formula 305 Formula 306 Formula 307 Formula 308 Formula 309 Formula 310 Formula 311 Formula 312 Formula 313 Formula 314 Formula 315 Formula 316 Formula 317 Formula 318 Formula 319 Formula 320 Formula 321 Formula 322 Formula 323 Formula 324 Formula 325 Formula 326 Formula 327 Formula 328 Formula 329 Formula 330 Formula 331 Formula 332 Formula 333 Formula 334 Formula 335 Formula 336 Formula 337 Formula 338 Formula 339 Formula 340 Formula 341 Formula 342 Formula 343 Formula 344 Formula 345, Formula 346, Formula 347, Formula 348.

6. The method for preparing anthracene-containing organic compound according to any one of claims 1 to 5, characterized in that: The following steps are involved: (1) Raw material D, pinacol diboronate, potassium acetate, [1,1-bis(diphenylphosphino)ferrocene] palladium dichloride, dichloromethane and dioxane were mixed to undergo a Suzuki cross-coupling reaction to obtain intermediate B, the structure of which is shown in Formula B: RB(OH)2 formula B; In formula B, R has the same meaning as R in formula M; The structure of the raw material D is shown in Formula D: RK type D; In formula D, K is a halogen, and R has the same meaning as R in formula M; (2) The intermediate B is mixed with raw material A, Pd(PPh3)4, sodium carbonate, toluene, ethanol and water to carry out a first reflux reaction to obtain intermediate Z, the structure of which is shown in Formula Z: HLR type Z; In formula Z, H is a halogen, and R has the same meaning as R in formula M; The structure of the raw material A is shown in formula A: HLG formula A; In formula A, H is halogen, G is halogen, and L has the same meaning as L in formula M; (3) mixing the intermediate Z, the raw material C, Pd(PPh3)4, sodium carbonate, toluene, ethanol and water to carry out a second reflux reaction to obtain an anthracene-containing organic compound; The structure of the raw material C is shown in Formula C: Formula C; In formula C, Ar1, n and R1 have the same meanings as Ar1, n and R1 in formula M.

7. Use of the anthracene-containing organic compound according to any one of claims 1 to 5 or the anthracene-containing organic compound obtained by the preparation method according to claim 6 in an electron transport layer in an organic electroluminescent device.

8. An organic electroluminescent device, characterized in that: The invention comprises a first electrode, a second electrode and an organic thin film layer located between the first electrode and the second electrode; the organic thin film layer is an electron transport layer; the number of layers of the organic thin film layer is one or more; at least one layer of the organic thin film layer contains the anthracene-containing organic compound according to any one of claims 1 to 5 or the anthracene-containing organic compound obtained by the preparation method according to claim 6.

9. A display element, characterized in that: The organic electroluminescent device according to claim 8 is included.

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