Anthracene-containing organic compound as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of semiconductor materials, and particularly relates to an anthracene-containing organic compound and a preparation method and application thereof. The LUMO electron cloud distribution of the anthracene-containing organic compound provided by the invention is further delocalized, so that the anti-electron characteristic of the material can be improved, and the electron stability of the material is effectively improved. According to the anthracene-containing organic compound, anthracene serves as a core, aromatic fused ring groups are connected through specific connecting sites to form a parent nucleus, the parent nucleus can increase weak interaction in molecules, the evaporation temperature of the molecules is effectively reduced, and the thermal durability of a material is improved; furthermore, the parent nucleus can inhibit pi-pi accumulation among molecules, the electron mobility of the molecules is remarkably improved, and the driving voltage of the device is reduced; moreover, due to the existence of the electricity absorption conjugation effect of the parent nucleus, the glass transition temperature of the material is improved, and the film stability of the material is effectively improved. As an electron transport material, the compound provided by the invention can effectively improve device efficiency and prolong the service life.

Description

Technical Field

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

[0002] At present, organic light emitting diodes (OLED) have been used in products such as smart phones and tablets, and will be used in large-size products such as TVs in the future. The structure of OLED devices 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 doping materials.

[0003] For OLED devices, electrons are injected from the cathode and then transferred to the main material through the electron transport layer, where they recombine with holes to generate excitons. Therefore, improving the injection and transmission capabilities of the electron transport layer is conducive to reducing the device driving voltage while obtaining efficient electron-hole recombination efficiency. Therefore, the electron transport layer is very important and needs to have efficient electron injection and transmission capabilities and high electron durability.

[0004] With the continuous development of OLED devices, the performance requirements for materials are also increasing. Not only are materials required to have good material stability, but also good efficiency and life at low driving voltages. However, existing electron transport materials have insufficient thermal stability and defects in electron tolerance, which leads to phase separation or decomposition of materials when the device is working. 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, Ar 1 C 6 ~C 60 Aryl or C 5 ~C 60 Heteroaryl; n is 0 or 1, R1 is phenyl, biphenyl, naphthyl or pyridyl (R 1 The connection site 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 CH or N atom.

[0012] Preferably, Ar 1 In the C 6 ~C 60 Aryl includes one or more of phenyl, biphenyl, terphenyl, naphthyl and phenanthryl; the C 5 ~C 60 The heteroaryl group 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.

[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, Ar 1 ,n,R 1 , 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, Ar 1 , R 1 , 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, Ar 1 , R 1 , L and X have the same meanings as in formula M.

[0022] Preferably, the anthracene-containing organic compound is any one of Formula 1 to Formula 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) The raw material D, bipyraclostrobin, potassium acetate, [1,1-bis(diphenylphosphino)ferrocene] palladium dichloride, dichloromethane and dioxane are mixed to carry out a Suzuki cross-coupling reaction to obtain an 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 materials A, Pd(PPh 3 ) 4 , sodium carbonate, toluene, ethanol and water are mixed for a first reflux reaction to obtain an intermediate Z, the structure of which is shown in Formula Z:

[0031] HLR style Z;

[0032] In formula Z, H is 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 type A;

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

[0036] (3) The intermediate Z, raw material C, Pd(PPh 3 ) 4 , sodium carbonate, toluene, ethanol and water are mixed for 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, Ar 1 , n and R 1 The meaning is the same as Ar in formula M 1 , n and R 1 Consistent.

[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 more than one; 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 aromatic condensed ring groups through specific connection sites 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 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 large-scale prospects.

[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 high glass transition temperature (above 120°C), high heat resistance, high electron tolerance and molecular thermal stability, high electron mobility (greater than 4.0×10 -4 cm 2 / Vs), low evaporation temperature (below 350°C) and appropriate HOMO / LUMO energy levels. The anthracene-containing organic compound provided by the present invention is used as an electron transport material for OLED devices, has excellent electron transport ability and good electron injection property, can effectively reduce the device driving voltage, and improve the device efficiency and working 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 electrode and the second electrode; the number of layers of the organic thin film layer is more than one; 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. The organic electroluminescent device provided by the present invention has high efficiency, long service life and excellent comprehensive performance.

[0047] The present invention also provides a display element, comprising the organic electroluminescent device described in the above solution. The display element provided by the present invention adopts the high-performance organic electroluminescent device of the present invention, has a longer service life and better comprehensive 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 drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0049] Figure 1 It is a schematic structural diagram of an OLED device used in the anthracene-containing organic compound of the present invention;

[0050] Figure 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, Ar 1 C 6 ~C 60 Aryl or C 5 ~C 60 Heteroaryl; n is 0 or 1, R 1 is phenyl, biphenyl, naphthyl or pyridyl (R 1 The connection site 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, Ar 1 In the C 6 ~C 60 The aryl group preferably includes one or more of phenyl, biphenyl, terphenyl, naphthyl and phenanthryl, and more preferably phenyl, biphenyl or naphthyl.

[0057] In the present invention, Ar 1 In the C 5 ~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 naphthylbenzofuranyl group, an N-phenylbenzimidazolyl group and a benzoxazolyl group, and more preferably a pyridyl group or a dibenzofuranyl group.

[0058] In the present invention, Ar 1 More preferably:

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

[0060]

[0061] In Formula S or Formula T, Ar 1 ,n,R 1 , 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, Ar 1 , R 1 , 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, Ar 1 The meanings of and X are consistent with those 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, Ar 1 , R 1 The meanings of and X are consistent with those 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, Ar 1 The meaning is consistent with that of 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, Ar 1 and R 1 The meaning is consistent with that of formula M.

[0078] In a specific embodiment of the present invention, the anthracene-containing organic compound is preferably any one of Formula 1 to Formula 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) The raw material D, bipyraclostrobin, potassium acetate, [1,1-bis(diphenylphosphino)ferrocene] palladium dichloride, dichloromethane and dioxane are mixed to carry out a Suzuki cross-coupling reaction to obtain an 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 materials A, Pd(PPh 3 ) 4 , sodium carbonate, toluene, ethanol and water are mixed for a first reflux reaction to obtain an intermediate Z, the structure of which is shown in Formula Z:

[0096] HLR style Z;

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

[0098] (3) The intermediate Z, raw material C, Pd(PPh 3 ) 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, bipyraclostrobin, potassium acetate, [1,1-bis(diphenylphosphino)ferrocene] palladium dichloride, dichloromethane and dioxane are mixed to carry out a Suzuki cross-coupling reaction to obtain an 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 further 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 further preferably 1:3.

[0105] In the present invention, the molar ratio of the raw material D to [1,1-bis(diphenylphosphino)ferrocene]palladium dichloride dichloromethane is preferably 10-50:1-10, more preferably 20-40:6-10, and further 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., and further preferably 125° C., and the insulation time is preferably 3-24 h, more preferably 3-8 h, and 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 the intermediate B, the present invention further comprises reacting the intermediate B with the raw material A, Pd(PPh 3 ) 4 , sodium carbonate, toluene, ethanol and water are mixed for a first reflux reaction to obtain an intermediate Z. In the present invention, the structure of the raw material A is shown in formula A:

[0110] HLG type 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 further preferably 22:20.

[0114] In the present invention, the intermediate B and Pd(PPh 3 ) 4 The molar ratio of is preferably 20 to 25:1 to 1.5, more preferably 20 to 23:1 to 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 further 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 further preferably 1:1.

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

[0120] In the present invention, the intermediate B and the raw material A, Pd(PPh 3 ) 4 The mixing of 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 further preferably 100°C, and the insulation time is preferably 3-24h, more preferably 10-15h, and further preferably 12h. In a specific embodiment of the present invention, it is preferred to confirm whether the raw materials have reacted completely by using a sampling point plate.

[0122] In the present invention, after the first reflux reaction, the first post-treatment of the obtained product is preferably further included; the first post-treatment preferably includes first cooling, first filtration, filtrate distillation and second purification in sequence.

[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 70-100°C, more preferably 85°C, and the pressure is preferably -0.07-0.10MPa, more preferably -0.09MPa, 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 the intermediate Z, the raw material C, Pd(PPh 3 ) 4 , sodium carbonate, toluene, ethanol and water are mixed for 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, Ar 1 , n and R 1 The meaning is the same as Ar in formula M 1 , n and R 1 Consistent.

[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 further 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 further preferably 20:60.

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

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

[0137] In the present invention, the intermediate Z, the raw material C, Pd(PPh 3 ) 4 The mixing of 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 further preferably 90°C, and the insulation time is preferably 3-48h, more preferably 12-24h, and further preferably 16h. In a specific embodiment of the present invention, it is preferred to confirm whether the raw materials have reacted completely by using a sampling point plate.

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

[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 temperature of the vacuum rotary evaporation 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 of 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, 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, including 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 / Vs), low evaporation temperature (below 350°C) and appropriate HOMO / LUMO energy levels. The anthracene-containing organic compound provided by the present invention is used as an electron transport material for OLED devices, has excellent electron transport ability and good electron injection property, can effectively reduce the device driving voltage, and improve the device efficiency and working 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 more than one; 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 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 the 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 comprehensive performance.

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

[0152] In the specific embodiments of the present invention, unless otherwise specified, all raw materials and reactants are 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 bipyralidin, 0.09 mol of potassium acetate, and 0.007 mol of [1,1-bis(diphenylphosphino)ferrocene]palladium dichloride dichloromethane were dissolved in 60 mL of dioxane, reacted at 125 °C for 5 h, and 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 the protection of nitrogen. Then, 1×10 -3 mol of Pd(PPh 3 ) 4 , heated to reflux reaction for 12 hours, sampling point plate, showing that the raw material reaction was complete, naturally cooled to room temperature, filtered, the filtrate was subjected to vacuum rotary evaporation (-0.09MPa, 85°C) until there was no fraction, and 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 the protection of nitrogen, and then 1×10 -4 mol of Pd(PPh 3 ) 4 , heated to reflux reaction for 16 hours, sampling point plate, showing that the raw material reaction was complete, naturally cooled to room temperature, filtered, and 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, and then the light yellow solid powder was 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 raw material A, raw material / intermediate B and raw material C corresponding to 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 to replace raw material D-1.

[0163]

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

[0165]

[0166]

[0167]

[0168]

[0169] The anthracene-containing organic compounds prepared in Examples 1 to 25 of the present invention were subjected to nuclear magnetic resonance hydrogen spectrum testing, and 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 synthesizes 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 Application Comparative Examples 1 to 6, and the differences are marked in brackets:

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

[0178] (b) HAT-CN is 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 deposited by vacuum evaporation with a thickness of 140 nm as the hole transport layer 4;

[0180] (d) On the hole transport layer 4, EB-1 is deposited by vacuum evaporation with 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, with BH-1 as the main material and BD-1 as the doping material, the mass ratio of BH-1 to BD-1 being 90:10, and the thickness being 40 nm;

[0182] (f) On the light-emitting layer 6, the compound of the present invention (the comparative examples are ET-1 to ET-6) and Liq are evaporated in a mass ratio of 1:1 by vacuum evaporation to a thickness of 40 nm to serve as the electron transport layer 7;

[0183] (g) On the electron transport layer 7, LiF is vacuum evaporated to a thickness of 1 nm to serve as the electron injection layer 8;

[0184] (h) On 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;

[0185] (i) On the cathode layer 9, CP-1 is deposited by vacuum evaporation to a thickness of 70 nm as a light extraction layer 10 to obtain an organic electroluminescent device having a structure as shown in FIG. 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 of application examples 2 to 25 and application comparative examples 1 to 6 are the same as those of application example 1, and the same substrate materials and electrode materials are used, and the film thickness of the electrode materials remains the same. The materials used for each layer of the organic electroluminescent devices prepared in application examples 1 to 25 and application comparative examples 1 to 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 were performed on the devices prepared by using Examples 1 to 25 and Comparative Examples 1 to 6, 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 the IVL (current-voltage-luminance) test system, and the current density during the test is 10mA / cm 2 .

[0200] It can be seen from Table 4 that when the anthracene-containing organic compound of the present invention is used as an 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, and 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 describes the present invention in detail, 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 protection scope of the present invention.

Claims

1. An anthracene-containing organic compound, characterized in that: The structure is shown in 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; In formula P, X is CH or N atom.

2. The anthracene-containing organic compound according to claim 1, characterized in that In Ar1, the C6~C 60 Aryl includes one or more of phenyl, biphenyl, terphenyl, naphthyl and phenanthryl; C5~C 60 The heteroaryl group 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.

3. The anthracene-containing organic compound according to claim 1 or 2, 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: In Formula S or Formula T, Ar1, n, R1, L and X have the same meanings as in Formula M.

4. The anthracene-containing organic compound according to claim 3, 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: In Formula U or Formula V, Ar1, R1, L and X have the same meanings as in Formula M.

5. The anthracene-containing organic compound according to claim 3, 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: In Formula W or Formula Y, Ar1, R1, L and X have the same meanings as in Formula M.

6. The anthracene-containing organic compound according to claim 1 or 2, characterized in that: The anthracene-containing organic compound is any one of Formula 1 to Formula 348:

7. The method for preparing anthracene-containing organic compounds according to any one of claims 1 to 6, characterized in that: The following steps are involved: (1) The raw material D, bipyraclostrobin, potassium acetate, [1,1-bis(diphenylphosphino)ferrocene] palladium dichloride, dichloromethane and dioxane are mixed to carry out a Suzuki cross-coupling reaction to obtain an 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 an intermediate Z, the structure of which is shown in Formula Z: HLR style Z; In formula Z, H is 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 type 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 for a second reflux reaction to obtain an anthracene-containing organic compound; The structure of the raw material C is shown in Formula C: In formula C, Ar1, n and R1 have the same meanings as Ar1, n and R1 in formula M.

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

9. An organic electroluminescent device, characterized in that: It comprises 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 more than one; at least one layer of the organic thin film layer contains the anthracene-containing organic compound according to any one of claims 1 to 6 or the anthracene-containing organic compound obtained by the preparation method according to claim 7.

10. A display element, characterized in that: Comprising the organic electroluminescent device as claimed in claim 9.

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