An organic electroluminescent multi-host material, light-emitting device and application

Abstract

The present invention discloses a plurality of host materials for organic electroluminescence, a light-emitting device and an application. Among them, a plurality of host materials for organic electroluminescence includes a compound N having a structure shown in formula (1) and a compound M having a structure shown in formula (2); Formula (1): Formula (2): When the compound M in the present invention and the compound N in the present invention are used in combination as the host material for organic electroluminescence of an organic light-emitting device, the turn-on voltage of the organic light-emitting device can be significantly reduced, the luminous efficiency can be significantly improved, and the lifespan can be significantly extended.

Description

Technical Field

[0001] The present invention relates to the field of organic electroluminescence, and particularly to a variety of host materials, light-emitting devices and applications for organic electroluminescence. Background Art

[0002] An organic electroluminescent device (OLED) converts electrical energy into light by applying electricity to an organic electroluminescent material, and generally includes an anode, a cathode, and an organic layer formed between the two electrodes. The organic layer of the organic electroluminescent device may include a hole injection layer, a hole transport layer, a hole auxiliary layer, a light-emitting auxiliary layer, an electron blocking layer, a light-emitting layer (containing a host material and a dopant material), an electron buffer layer, a hole blocking layer, an electron transport layer, an electron injection layer, etc. Various materials used in the organic layer are classified into hole injection materials, hole transport materials, hole auxiliary materials, light-emitting auxiliary materials, electron blocking materials, light-emitting materials, electron buffer materials, hole blocking materials, electron transport materials, electron injection materials, etc. based on the functions achieved by each layer. In the organic electroluminescent device, holes from the anode and electrons from the cathode are injected into the light-emitting layer by applying a voltage, and excitons with high energy are generated by the recombination of holes and electrons. The organic light-emitting compound emits light by moving energy to the excited state and by the energy when the organic light-emitting compound returns from the excited state to the ground state.

[0003] Existing disclosed organic light-emitting compounds include amine derivatives of indeno[1,2,3-cd]pyrene, triazine-based electron transport materials, etc. For example, an amine derivative of indeno[1,2,3-cd]pyrene disclosed in US Patent Application US20200115369A1, and triazine-based electron transport materials, their preparation methods and applications disclosed in Chinese Patent Application CN113004295A. Existing disclosed amine derivatives of indeno[1,2,3-cd]pyrene and triazine-based electron transport materials can both be used as organic light-emitting functional materials in organic electroluminescent devices.

[0004] However, currently existing functional materials composed of organic light-emitting compounds all have problems such as low stability and unbalanced carrier mobility, and therefore, cause problems such as a high turn-on voltage, low luminous efficiency, and short lifespan of organic electroluminescent diodes, severely limiting the application of organic electroluminescent diodes. Summary of the Invention

[0005] Therefore, the technical problem to be solved by the present invention is to overcome the problems of high turn-on voltage, low luminous efficiency, and short lifespan existing in the application of organic electroluminescent materials in light-emitting devices in the prior art, and thus provide a variety of host materials, light-emitting devices and applications for organic electroluminescence to solve the above problems.

[0006] An organic electroluminescent multi-host material, including a compound N with the structure shown in formula (1) and a compound M with the structure shown in formula (2).

[0007] Formula (1):

[0008] In the said formula (1), X is selected from O, S, Se, NAr or CR 6 R 7 ; wherein, Ar is selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C5-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl; R 6 -R 7 are each independently selected from a hydrogen atom, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl;

[0009] R 1 is -L 1 Ar 1 R 2 is -L 2 Ar 2 R 3 is -L 3 Ar 3 ; L 1 -L 3 are each independently selected from a linking bond, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C3-C30 heteroarylene; Ar 1 -Ar 3 at least one of them is indicating a linking bond, the said R 4 is -L 4 Ar 4 R 5 is -L 5 Ar 5 ; L 4 -L 5 are each independently selected from a linking bond, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C3-C30 heteroarylene, Ar 4 -Ar 5 are each independently selected from hydrogen, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl; the remaining Ar 1 -Ar 3Each independently selected from hydrogen, deuterium, protium, tritium, halogen, cyano, substituted or unsubstituted C6-C60 arylamino, substituted or unsubstituted C3-C60 heteroarylamino, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl;

[0010] Formula (2):

[0011] In the said formula (2), X 1 -X 12 Selected from N or CR, R is selected from hydrogen or deuterium; L is selected from a linking bond, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C3-C30 heteroarylene; Ar 8 -Ar 9 Each independently selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl;

[0012] The above-mentioned substituted groups are selected from one or a combination of two of deuterium, halogen, cyano, C1-C6 alkyl, C3-C30 cycloalkyl, C6-C30 aryl, C3-C30 heteroaryl.

[0013] In formula (1), It can be understood that in the present invention, R 1 Can be substituted on ring B, can also be substituted on ring C, R 2 Can be substituted on ring D, R 3 Can be substituted on ring E.

[0014] In the said formula (2), X 1 -X 8 All are CR; or any one is N and the rest are CR;

[0015] In the said formula (2), X 9 -X 12 All are CR; or any one is N and the rest are CR.

[0016] Or, Ar 8 -Ar 9 Each independently selected from substituted or unsubstituted groups as follows: phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, triphenylene, Group, dimethylfluorenyl, spirobifluorenyl, fluoranthenyl, diphenylfluorenyl, benzyldimethylfluorenyl, benzylbiphenylfluorenyl, benzospirobifluorenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, phenylcarbazolyl, dipyridyl, pyrimidinyl, triazinyl. The structure of the compound M is as shown in any one of M-1 to M-224.

[0017] Among them, the structures of M-1 to M-224 are as follows:

[0018]

[0019]

[0020]

[0021]

[0022]

[0023]

[0024]

[0025] The structure of the compound N is shown in formula (1);

[0026] Said Ar 4 -Ar 5 are each independently selected from substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted dibenzoselenophenyl.

[0027] Said Ar 4 -Ar 5 are each independently selected from substituted or unsubstituted groups as follows: phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, triphenylene, group, dibenzofuranyl, benzonaphthofuranyl, dibenzothiophenyl, dibenzoselenophenyl, triphenylene, dimethylfluorenyl, spirobifluorenyl, fluoranthenyl, carbazolyl, phenylcarbazolyl, diphenylfluorenyl, benzyldimethylfluorenyl, benzyldiphenylfluorenyl, benzospirobifluorenyl, pyridyl, pyrimidinyl, triazinyl.

[0028] Said Ar 4 -Ar 5 are each independently selected from

[0029] wherein, R T1 -R T6 are each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C4-C30 heteroaralkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 heterocycloalkyl, substituted or unsubstituted C3-C30 cycloalkenyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryloxy, and any two adjacent ones substituted by the same phenyl group can be fused into a C6-C30 ring A; Y is selected from O, S, NAr, CR6 R 7 ; wherein Ar, R 6 , R 7 are as defined in claim 1;

[0030] When there are multiple R T1 -R T6 s, R T1 -R T6 are each independently of the others and may be the same or different;

[0031] Preferably, ring A is selected from a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, and a substituted or unsubstituted phenanthrene ring.

[0032] Said Ar is selected from a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group; preferably, selected from the following substituted or unsubstituted groups: phenyl, naphthyl, biphenyl, terphenyl, triphenylene, anthryl, dibenzofuranyl, dibenzothiophenyl;

[0033] and / or, R 6 , R 7 are each independently selected from a substituted or unsubstituted C1-C5 alkyl group, a substituted or unsubstituted C6-C30 aryl group.

[0034] L 1 -L 3 are each independently selected from a linking bond, a C6-C30 arylene group; preferably, L 1 -L 3 are each independently selected from a linking bond, phenylene, naphthylene, triphenylene, biphenylene; further optionally, L 1 is selected from a linking bond, L 2 is selected from phenylene, naphthylene, triphenylene, biphenylene, L 3 is a linking bond; preferably, L 1 -L 3 are each independently selected from single bonds;

[0035] and / or, L 4 -L 5 are each independently selected from single bonds, a substituted or unsubstituted C6-C30 arylene group; optionally, L 4 -L 5 are each independently selected from single bonds, phenylene, naphthylene; further optionally, L 4 -L 5 are each independently selected from single bonds;

[0036] and / or, the remaining Ar 1 -Ar 3Selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl.

[0037] The structure of the compound N is as shown in any one of Formula 1-1 to Formula 1-17;

[0038]

[0039]

[0040] wherein R 1 -R 7 、L 1 -L 3 、Ar are as defined in any one of Claims 1-7.

[0041] The structure of the compound N shown in Formula (1) is as shown in any one of N-1 to N-929.

[0042] The structures of N-1 to N-929 are as follows:

[0043]

[0044]

[0045]

[0046]

[0047]

[0048]

[0049]

[0050]

[0051]

[0052]

[0053]

[0054]

[0055]

[0056]

[0057]

[0058]

[0059]

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078] The mass ratio of the compound N to the compound M is 9:1 - 1:9; preferably 2:8 - 8:2; more preferably 3:7 - 7:3, and still more preferably 4:6 - 6:4.

[0079] The application of the above-mentioned organic electroluminescent multi-host material in a light-emitting device.

[0080] Preferably, the optical device includes any one of an organic light-emitting device, an organic field-effect transistor, an organic thin-film transistor, an organic light-emitting transistor, an organic integrated circuit, an organic solar cell, an organic field quenching device, a light-emitting electrochemical cell, an organic laser diode, or an organic photoreceptor.

[0081] An organic light-emitting material includes one of the above-mentioned organic light-emitting host materials. Preferably, the organic light-emitting material further contains a dopant material. Preferably, the dopant material includes a phosphorescent dopant, and the phosphorescent dopant includes a transition metal-containing complex.

[0082] An organic light-emitting device includes an anode and a cathode, and an organic layer disposed between the anode and the cathode; the organic layer includes one of the above-mentioned organic light-emitting host materials.

[0083] Preferably, the organic layer includes a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer (electron buffer layer), an electron transport layer, and an electron injection layer sequentially stacked from the anode side to the cathode side;

[0084] An organic light-emitting device includes one of the above-mentioned organic light-emitting devices.

[0085] The term "organic light-emitting material" disclosed in the present invention means a material that can be used in an organic light-emitting device and can contain at least one compound. If necessary, the organic light-emitting material can be contained in any layer constituting the organic light-emitting device. For example, the organic light-emitting material can be a hole injection material, a hole transport material, a hole auxiliary material, a light-emitting auxiliary material, an electron blocking material, a light-emitting material (including an organic light-emitting host material and a dopant material), an electron buffer material, a hole blocking material, an electron transport material, an electron injection material, etc.

[0086] An organic electroluminescent material disclosed in the present invention may include one organic electroluminescent material or may include a plurality of organic electroluminescent materials, wherein the plurality of organic electroluminescent materials means a material comprising a combination of at least two organic electroluminescent materials, and the material may be included in any layer constituting the organic electroluminescent device. It may mean both a material before the organic electroluminescent device (e.g., before vapor deposition) and a material after the organic electroluminescent device (e.g., after vapor deposition). For example, the material may be a combination of at least two compositions, and the compositions may be included in at least one of the following: a hole injection layer, a hole transport layer, a hole auxiliary layer, a light emission auxiliary layer, an electron blocking layer, a light emitting layer, an electron buffer layer, a hole blocking layer, an electron transport layer, and an electron injection layer. Two compositions in the plurality of organic electroluminescent materials may be included in the same layer or different layers, and may be mixed-evaporated or co-evaporated, or may be evaporated individually.

[0087] The term "organic electroluminescent host material plurality" disclosed in the present invention means an organic electroluminescent material comprising a combination of at least two host materials. It may mean both a material before the organic electroluminescent device (e.g., before vapor deposition) and a material after the organic electroluminescent device (e.g., after vapor deposition). The plurality of host materials disclosed in the present invention may be included in any light emitting layer constituting the organic electroluminescent device. Two or more compounds included in the plurality of host materials disclosed in the present invention may be included in one light emitting layer or may be included in different light emitting layers separately. For example: when two or more host materials are included in one layer, the layer may be formed by mixed evaporation or may be formed simultaneously by separate co-evaporation.

[0088] "Halogen" in the present invention may include fluorine, chlorine, bromine or iodine.

[0089] "C1-C30 alkyl" in the present invention refers to a monovalent substituent derived from a straight-chain or branched-chain saturated hydrocarbon having 1 to 30 carbon atoms, and examples thereof include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, and hexyl.

[0090] "C3-C30 cycloalkyl" in the present invention refers to a monocyclic hydrocarbon or polycyclic hydrocarbon derived from a hydrocarbon having 1 to 30 ring backbone carbon atoms, and the cycloalkane may include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclohexylmethyl, adamantyl, etc.

[0091] The aryl and arylene groups in the present invention include monocyclic, polycyclic or fused-ring aryl groups, the rings of which can be interrupted by short non-aromatic units and can include spiro structures, including but not limited to phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, phenylphenanthryl, binaphthyl, phenylnaphthyl, naphthylphenyl, anthryl, indenyl, triphenylenyl, tetraphenylenyl, pyrenyl, perylenyl, fluorenyl, phenylfluorenyl, diphenylfluorenyl, benzofluorenyl, spirobifluorenyl, fluorenyl, naphthacenyl, fluoranthenyl, etc.

[0092] The heteroaryl and heteroarylene groups in the present invention include monocyclic, polycyclic or fused-ring heteroaryl groups, the rings of which can be interrupted by short non-aromatic units, and the heteroatoms include nitrogen, oxygen and sulfur. Including but not limited to furyl, phenylthio, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuryl, benzothienyl, isobenzofuryl, dibenzofuryl, dibenzothienyl, benzimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolinyl, isoquinolinyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenothiazinyl, phenanthridinyl, benzodioxolyl, dihydroacridinyl, and their derivatives, etc.

[0093] "Substituted" in the present invention means that a hydrogen atom in a compound is replaced by another substituent. The position is not limited to a specific position as long as the hydrogen at that position can be replaced by a substituent. And it also includes the replacement of a hydrogen atom by a group formed by the connection of two or more substituents. When there are two or more substituents, the two or more substituents can be the same or different. For example, the group formed by the connection of two or more substituents can be pyridine-triazine. That is, pyridine-triazine can be interpreted as a heteroaryl substituent or a substituent in which two heteroaryl substituents are connected.

[0094] Unless otherwise specified in the present invention, the hydrogen atom includes protium, deuterium and tritium.

[0095] The groups in the present invention define the range of the number of carbon atoms, and the number of carbon atoms should be any integer within the defined range. For example, C6-C30 aryl means that the number of carbon atoms of the aryl can be any integer within the range of 6-60, such as 6, 8, 10, 13, 15, 17, 20, 22, 25 or 30, etc.

[0096] When the groups in the present invention have substituents, the substituents are each independently selected from deuterium, halogen, cyano, nitro, unsubstituted or R'-substituted C1-C4 straight-chain or branched alkyl, unsubstituted or R'-substituted C6-C20 aryl, unsubstituted or R'-substituted C3-C20 heteroaryl, and unsubstituted or R'-substituted C6-C20 arylamino; R' is selected from deuterium, halogen, cyano and nitro.

[0097] By including a specific combination of the compounds of the present invention as various host materials for organic electroluminescence, an organic electroluminescent device having improved luminous efficiency and lifetime characteristics compared to a conventional organic electroluminescent device can be provided, and a display system or a lighting system using the organic electroluminescent device is manufactured.

[0098] The technical solution of the present invention has the following advantages:

[0099] 1. A variety of host materials for organic electroluminescence provided by the present invention include a compound N having the structure shown in formula (1) and a compound M having the structure shown in formula (2). Specifically, the compound M having the structure shown in formula (2) of the present invention can cooperate with the compound N having the structure shown in formula (1) of the present invention as a variety of host materials for organic electroluminescence of an organic light-emitting device, which can significantly reduce the turn-on voltage of the organic light-emitting device, significantly improve the luminous efficiency, and significantly extend the lifetime; therefore, the compound M having the structure shown in formula (2) of the present invention can achieve the advantage of significantly improving the performance of the host material by cooperating with the compound N, and can be used to produce an organic electroluminescent device having high luminous efficiency and long lifetime characteristics.

[0100] 2. A variety of host materials for organic electroluminescence provided by the present invention, in which the compound M and the compound N can synergistically enhance the effect and cooperate with each other to significantly reduce the turn-on voltage of the light-emitting device, significantly improve the luminous efficiency, and significantly extend the lifetime, so that the driving voltage of the light-emitting device can be reduced to below 3.44 V, the current efficiency is increased to above 23 Cd / A, and the lifetime is increased to above 240 h; achieving the effect of significantly improving the luminous efficiency of the light-emitting device and significantly extending the lifetime of the light-emitting device. Detailed implementation mode

[0101] The following embodiments are provided to better further understand the present invention, which is not limited to the best implementation mode, and does not limit the content and protection scope of the present invention. Any product identical or similar to the present invention obtained by anyone under the inspiration of the present invention or by combining the features of the present invention with other prior art features falls within the protection scope of the present invention.

[0102] For those without specific experimental procedures or conditions noted in the examples, the operations or conditions of the conventional experimental procedures described in the literature in this field can be followed. For reagents or instruments without the manufacturer noted, they are all conventional reagent products that can be obtained through commercial purchase.

[0103] Example 1

[0104] An organic electroluminescent multi-host material, including compound N and compound M, wherein the compound M is compound M-17, and its synthesis process is as follows:

[0105]

[0106] Take a 50-milliliter two-necked round-bottom flask, place a magnetic stir bar and connect a reflux condenser. After drying, fill it with nitrogen. Add compound M17-A (14.1 mmol), M17-B (18.3 mmol), tetrakis(triphenylphosphine)palladium (0.7 mmol), potassium carbonate (28.2 mmol), 42 milliliters of toluene, 10 milliliters of ethanol, and 14 milliliters of distilled water respectively, and stir the mixture at 140 °C for 8 hours. After the reaction is completed, add the mixture dropwise to methanol and filter the resulting solid. Purify the resulting solid by column chromatography to obtain compound M-17 (5.8 g, yield: 75%).

[0107] Elemental analysis: C39H23N3O Theoretical values: C, 85.23; H, 4.22; N, 7.65; O, 2.91; Measured values: C, 85.24; H, 4.22; N, 7.63; HRMS(ESI) m / z (M+): Theoretical value: 549.18; Measured value: 550.60.

[0108] Example 2

[0109] An organic electroluminescent multi-host material, including compound N and compound M, wherein the compound M is compound M-127, and its synthesis process is as follows:

[0110] (I) Synthesis of intermediate M127-A, and the synthesis route is as follows:

[0111]

[0112] Add intermediate M127-1 (20 g, CAS: 91182-50-2) and 200 mL of anhydrous tetrahydrofuran to a 250 mL three-necked flask equipped with a thermometer and magnetic stirring. Under nitrogen protection, cool the temperature to -78 °C, and dropwise add n-butyllithium (1.6 M, 45.2 mL) while controlling the temperature. After the addition, stir for 1 h, then dropwise add triisopropyl borate (19.52 g) while controlling the temperature at -78 °C. After the addition, transfer the reaction mixture to room temperature and react for 12 h. Dropwise add hydrochloric acid solution (6.5 mL of 36% concentrated hydrochloric acid + 24 mL of water). Add 50 mL of ethyl acetate and 25 mL of water to the reaction solution for extraction and liquid separation. Rotate the organic phase to dryness, add 50 mL of n-hexane, reflux and stir for 1 h, filter at room temperature, and dry to obtain intermediate M127-2, 15 g.

[0113] Add intermediate M127-2 (15 g), intermediate 2,5-dibromonitrobenzene (11.2 g), potassium carbonate (16.6 g) and tetrakis(triphenylphosphine)palladium (2.0 g) to a 250 mL three-necked flask equipped with a thermometer and magnetic stirring. Add toluene (80 mL), ethanol (35 mL) and water (35 mL). Under nitrogen protection, heat to 85 °C and react for 6 h. Add 50 mL of ethyl acetate and 25 mL of water to the reaction solution for extraction and liquid separation. Stir the organic phase and pass it through a column to obtain intermediate M127-3, 15.2 g.

[0114] Add intermediate M127-3 (15.2 g) and iron powder (23.5 g) to a 250 mL three-necked flask equipped with a thermometer and magnetic stirring. Add ethanol (75 mL). Under nitrogen protection, dropwise add ammonium chloride solution (10.2 g, 76 mL), heat to reflux, and react for 1 h. Add 50 mL of ethyl acetate and 50 mL of water to the reaction solution for extraction and liquid separation. Rotate the organic phase to dryness to obtain intermediate M127-4, 14 g.

[0115] Add intermediate M127-4 (14 g) to a 250 mL three-necked flask equipped with a thermometer and magnetic stirring. Under nitrogen protection, dropwise add isoamyl nitrite (11 mL), heat to 85 °C, and react for 3 h. Add 30 mL of ethyl acetate and 25 mL of water to the reaction solution for extraction and liquid separation. Stir the organic phase and pass it through a column to obtain intermediate M127-5, 11 g.

[0116] Add intermediate 127-5 (11 g), bis(pinacolato)diboron (10.9 g), potassium acetate (8.8 g), and Pd(dppf)Cl2 (0.56 g) to a 250 mL three-necked flask equipped with a thermometer and magnetic stirring. Add 1,4-dioxane (110 mL). Under nitrogen protection, heat to 110 °C and react for 4 h. Add 100 mL of toluene and 100 mL of water to the reaction solution for extraction and liquid separation. Stir the organic phase and pass it through a column to obtain intermediate M127-A, 11 g.

[0117] (2) Synthesis of compound M-127. The synthesis route is as follows:

[0118]

[0119] Add intermediate M127-A (11 g), intermediate M127-B (10 g), potassium carbonate (9.9 g) and tetrakis(triphenylphosphine)palladium (1.2 g) to a 250 mL three-necked flask equipped with a thermometer and magnetic stirring. Add toluene (60 mL), ethanol (20 mL) and water (20 mL). Under nitrogen protection, heat to 85 °C and react for 6 h. Add water and ethanol to the reaction solution at room temperature, filter, and dry to obtain product M-127, 12 g (yield 86.7%).

[0120] Elemental analysis: C 32 H 20 N 4 Theoretical values: C, 83.46; H, 4.38; N, 12.17; Measured values: C, 83.44; H, 4.38; N, 12.18; HRMS(ESI) m / z (M+): Theoretical value: 460.17; Measured value: 460.57.

[0121] Example 3

[0122] An organic electroluminescent host material, comprising compound N and compound M, wherein the compound M is compound M-M174, and its synthesis process is as follows:

[0123] (I). Synthesis of intermediate M174-A, the synthesis route is as follows:

[0124]

[0125] Add intermediate M174-1 (20 g) and 200 mL of anhydrous tetrahydrofuran to a 250 mL three-necked flask equipped with a thermometer and magnetic stirring. Under nitrogen protection, cool to -78 °C, control the temperature and dropwise add n-butyllithium (1.6 M, 45.2 mL). After dropping, stir for 1 h, then control the temperature at -78 °C and dropwise add triisopropyl borate (19.52 g). After dropping, transfer to room temperature and react for 12 h. Dropwise add hydrochloric acid solution (6.5 mL of 36% concentrated hydrochloric acid + 24 mL of water). Add 50 mL of ethyl acetate and 25 mL of water to the reaction solution for extraction and liquid separation. Rotate the organic phase to dryness, add 50 mL of n-hexane, reflux and slurry for 1 h, filter at room temperature, and dry to obtain intermediate M174-2, 15 g.

[0126] Add intermediate M174-2 (15 g), intermediate 2,5-dibromo-6-nitropyridine (11.2 g), potassium carbonate (16.6 g) and tetrakis(triphenylphosphine)palladium(0) (2.0 g) to a 250 mL three-necked flask equipped with a thermometer and magnetic stirrer. Add toluene (80 mL), ethanol (35 mL) and water (35 mL). Under nitrogen protection, heat to 85 °C and react for 6 h. Add 50 mL of ethyl acetate and 25 mL of water to the reaction solution for extraction and liquid separation. The organic phase is stirred and passed through a column to obtain intermediate M174-3, 15.2 g.

[0127] Add intermediate M174-3 (15.2 g) and iron powder (23.5 g) to a 250 mL three-necked flask equipped with a thermometer and magnetic stirrer. Add ethanol (75 mL). Under nitrogen protection, dropwise add ammonium chloride solution (10.2 g, 76 mL). Heat to reflux and react for 1 h. Add 50 mL of ethyl acetate and 50 mL of water to the reaction solution for extraction and liquid separation. The organic phase is rotary evaporated to obtain intermediate M174-4, 14 g.

[0128] Add intermediate M174-4 (14 g) to a 250 mL three-necked flask equipped with a thermometer and magnetic stirrer. Under nitrogen protection, dropwise add isoamyl nitrite (11 mL). Heat to 85 °C and react for 3 h. Add 30 mL of ethyl acetate and 25 mL of water to the reaction solution for extraction and liquid separation. The organic phase is stirred and passed through a column to obtain intermediate M174-5, 11 g.

[0129] Add intermediate 174-5 (11 g), bis(pinacolato)diboron (10.9 g), potassium acetate (8.8 g) and Pd(dppf)Cl 2 (0.56 g) to a 250 mL three-necked flask equipped with a thermometer and magnetic stirrer. Add 1,4-dioxane (110 mL). Under nitrogen protection, heat to 110 °C and react for 4 h. Add 100 mL of toluene and 100 mL of water to the reaction solution for extraction and liquid separation. The organic phase is stirred and passed through a column to obtain intermediate M174-A 11 g.

[0130] (II) Synthesis of compound M-174. The synthesis route is as follows:

[0131]

[0132] Add intermediate M174-B (i.e., M17-B, 10 g), raw material M174-A (11 g), potassium carbonate (9.9 g) and tetrakis(triphenylphosphine)palladium(0) (1.2 g) to a 250 mL three-necked flask equipped with a thermometer and magnetic stirrer. Add toluene (60 mL), ethanol (20 mL) and water (20 mL). Under nitrogen protection, heat to 85 °C and react for 6 h. Add water and ethanol to the reaction solution at room temperature for extraction and filtration. After drying, the final product M-174, 12 g (yield 86.7%) is obtained.

[0133] Elemental analysis: C 37 H 21 N 5 Theoretical values: C, 80.57; H, 3.84; N, 12.70; O, 2.90; Measured values: C, 80.59; H, 3.83; N, 12.68; HRMS(ESI) m / z (M+): Theoretical value: 551.17; Measured value: 551.61.

[0134] Example 4

[0135] An organic electroluminescent multi-host material, including compound N and compound M, wherein compound M is any one of compound M-24, M-94, M-113, M-131, M-139 and M-173. The synthesis process of each compound M is as follows:

[0136] Raw material Mn-B (10 g), raw material Mn-A (11 g), potassium carbonate (9.9 g) and tetrakis(triphenylphosphine)palladium (1.2 g) were added to toluene (60 mL), ethanol (20 mL) and water (20 mL). Under nitrogen protection, the temperature was raised to 85 °C and the reaction was carried out for 6 h. The reaction solution was extracted and filtered with water and ethanol at room temperature, and the final product was obtained after drying.

[0137] The structures and yields of raw material Mn-B, raw material Mn-A and the final product are shown in Table 1 below. The elemental analysis results of the final product obtained are shown in Table 2.

[0138] Table 1

[0139]

[0140]

[0141] Table 2

[0142]

[0143] Example 5

[0144] An organic electroluminescent multi-host material, including compound M and compound N. Compound M is any one shown as M-1 to M-224, preferably any compound M prepared in Examples 1-4; compound N is any compound shown as N-1 to N-929, preferably any one of N-4, N-37, N-389, N-423, N-439, N-669, N-686, N-728, N-860, N-891, N-912, N-925; wherein, the synthesis process of each compound is as follows:

[0145] 1. Synthesis route of N-4

[0146]

[0147] 1.1 Synthesis of Intermediate N-4B’

[0148] Under nitrogen purge, add 20 g (1.0 eq) of 4a (CAS: 444796-09-2), 9.87 g (1.0 eq) of 4b (CAS: 4688-76-0), 1.7 g (2% eq) of Pd(PPh 3 ) 4 , 8.37 g (2.0 eq) of NaHCO 3 , 180 mL of tetrahydrofuran (4a:tetrahydrofuran = 1 g:9 mL) and 60 mL of ultrapure water (4a:ultrapure water = 1 g:3 mL) to a 500 mL three-necked flask equipped with a magnetic stirrer. React completely at 65 °C for 2 h. Purify by column chromatography to obtain 10 g of product N-4B’.

[0149] 1.2 Synthesis of Intermediate N-4B

[0150] Add 10 g (1.0 eq) of intermediate N-4B’, 20.5 g (6.0 eq) of anhydrous FeCl 3 , 100 mL of anhydrous dichloromethane (N-4B’:dichloromethane = 1 g:10 mL) to a 250 mL three-necked flask equipped with a magnetic stirrer. React completely at -10 °C for 1 h. Purify by column chromatography to obtain 7 g of product N-4B.

[0151] 1.3 Synthesis of Compound N-4

[0152] Under nitrogen purge, add 7 g (1.0 eq) of N-4B, 4.0 g (1.1 eq) of N-4A (CAS: 35887-50-4), 0.27 g (2% eq) of Pd 2 (dba) 3 , 2.85 g (2.0 eq) of t-BuONa, 70 mL of anhydrous toluene (N-4B:anhydrous toluene = 1 g:10 mL) to a 250 mL three-necked flask equipped with a magnetic stirrer. React completely at 100 °C for 2 h. Purify by column chromatography to obtain 5 g of product N-4.

[0153] Elemental analysis: C 48 H 32 N 2 Theoretical values: C, 90.54; H, 5.07; N, 4.40; Measured values: C, 90.53; H, 5.08; N, 4.41; HRMS(ESI) m / z (M+): Theoretical value: 636.26; Measured value: 637.55.

[0154] 2. Synthesis Route of N-5

[0155]

[0156] Under nitrogen purge, 7 g (1.0 eq) of intermediate N-4B, 4.82 g (1.1 eq) of N-5A (CAS: 1401351-42-5), and 0.27 g (2% eq) of Pd 2 (dba) 3 , 2.85 g (2.0 eq) of t-BuONa, and 70 mL of anhydrous toluene (intermediate N-4B:anhydrous toluene = 1 g:10 mL) were added to a 250 mL three-necked flask equipped with magnetic stirring. The reaction was complete after 2 h at 100 °C. The product was obtained by column purification, weighing 5 g.

[0157] Elemental analysis: C 52 H 34 N 2 Theoretical values: C, 90.93; H, 4.99; N, 4.08; Measured values: C, 90.92; H, 4.98; N, 4.10; HRMS (ESI) m / z (M+): Theoretical value: 686.27; Measured value: 687.22.

[0158] 3. Synthetic route of N-14

[0159]

[0160] Under nitrogen purge, 7 g (1.0 eq) of intermediate N-4B, 4.4 g (1.1 eq) of N-14A (CAS: 1357009-66-5), and 0.27 g (2% eq) of Pd 2 (dba) 3 , 2.85 g (2.0 eq) of t-BuONa, and 70 mL of anhydrous toluene (intermediate 2:anhydrous toluene = 1 g:10 mL) were added to a 250 mL three-necked flask equipped with magnetic stirring. The reaction was complete after 2 h at 100 °C. The product was obtained by column purification, weighing 5 g.

[0161] Elemental analysis: C 50 H 32 N 2 Theoretical values: C, 90.88; H, 4.88; N, 4.24; Measured values: C, 90.86; H, 4.88; N, 4.26; HRMS (ESI) m / z (M+): Theoretical value: 660.25; Measured value: 661.37.

[0162] 4. Synthetic routes of N-20, N-37, N-46, N-65, N-68, N-78, N-113, N-275, N-281, N-358, N-369, N-389

[0163] The synthesis conditions are the same as those for N-14, except that the raw materials N-nA, N-nB, the structures and yields of the products are different, as shown in Table 3 below; the elemental analysis results of the prepared compounds are shown in Table 4.

[0164] Table 3

[0165]

[0166]

[0167]

[0168] Table 4

[0169]

[0170]

[0171] 5. Synthesis route of N-423

[0172]

[0173] Add 20 g of 423a (i.e., 4b), 29.9 g of 423b (CAS: 67019-91-4), 2.3 g of Pd[P(C 6 H 5 ) 3 4 、27.9 g of K 2 CO 3 、280 mL of toluene, 120 mL of H 2 O, and 120 mL of ethanol into a 1000 mL three-necked flask equipped with a mechanical stirrer, a reflux condenser, and a thermometer. Replace the gas with nitrogen three times and react at 85 °C under nitrogen protection. React for 150 min starting from the temperature rise. After the reaction is completed, add 120 mL of water to quench the reaction. After liquid separation, rotary evaporate to obtain an oily substance (wet weight 44 g), and obtain 25 g of N-423B' after vacuum pumping.

[0174] ​Add 25 g of the crude product of N-423B' (oily substance) and 750 mL of dichloromethane (N-423B':DCM = 1 g:30 mL) to a 2 L three-necked flask equipped with a stirrer and a thermometer. Control the temperature at -5 °C, and add ferric chloride in two batches, adding 3 equivalents of ferric chloride every 15 min, and control the temperature at -5 °C. After the reaction is completed, slowly add 750 mL of ethanol (N-423B':ethanol = 1 g:30 mL), and control the temperature below 0 °C. After adding, continue stirring for 0.5 h, and yellowish-white solids will precipitate. Filter, wash the filter cake with 250 mL of ethanol (N-423B':ethanol = 1 g:1 mL) to obtain yellow solids. Then dissolve it in 1.75 L of chlorobenzene, de-solventize and crystallize, and when it naturally cools to 60 °C, add 250 mL of n-hexane solution dropwise and filter to obtain 20 g of the crude product N-423B.

[0175]

[0176] Add 25 g of N-423A (CAS: 32228-99-2), 40.48 g of N-423B (CAS: 2035812-74-7), 1.86 g of Pd 2 (dba) 3 , 1.67 g of sphos, 24.4 g of t-BuONa, and 500 mL of toluene to a 1000 mL three-necked flask equipped with a mechanical stirrer, a reflux condenser, and a thermometer. Replace the gas with nitrogen three times, and react at 110 °C under the protection of nitrogen. React for 120 min starting from the temperature increase. After the reaction is completed, add 120 mL of water to quench the reaction, separate the layers, spin-dry, pass through a column, and dry to obtain 35 g of the crude product N-423.

[0177] Elemental analysis: C 42 H 27 NO; Theoretical values: C, 89.81; H, 4.85; N, 2.49; O, 2.85; Measured values: C, 89.78; H, 4.86; N, 2.51; HRMS(ESI) m / z(M+): Theoretical value: 561.21; Measured value: 562.29.

[0178] 6. Synthetic route of N-425

[0179]

[0180] Add 14 g of N-425A (CAS: 1401351-43-6), 18.8 g of N-423B (CAS: 2035812-74-7), 0.86 g of Pd 2 (dba) 3, 1.9 g of sphos, 9.1 g of t-BuONa, and 150 mL of toluene. Replace the gas with nitrogen three times and react at 110 °C under nitrogen protection. React for 120 min starting from the temperature rise. After the reaction is completed, add 150 mL of water to quench the reaction. After liquid separation, spin-dry, slurry with ethanol, and then desolvate and crystallize with toluene to obtain 16 g of crude product N-425.

[0181] Elemental analysis: C 46 H 29 Theoretical values for C, H, N, and O: C, 90.32; H, 4.78; N, 2.29; O, 2.62; Measured values: C, 90.30; H, 4.77; N, 2.32; HRMS(ESI) m / z (M+): Theoretical value: 611.22; Measured value: 612.45.

[0182] 7. Synthetic routes of N-424, N-434, N-439, N-447, N-470, N-486, N-505, N-517, N-520, N-529, N-533, N-629, N-641, N-669, N-685, N-728, N-860, N-874

[0183] The synthesis conditions are the same as those for N-425, with the differences being the raw materials N-nA, N-nB, the structure and yield of the product, as shown in Table 5 below; the elemental analysis results of the prepared compounds are shown in Table 6.

[0184] Table 5

[0185]

[0186]

[0187]

[0188]

[0189]

[0190] Table 6

[0191]

[0192]

[0193] 8. Synthetic route of N-912

[0194]

[0195] 35.2 g (100 mmol) of 2,7-dibromo-9,9-dimethyl-9H-fluorene (CAS: 28320-31-2), 21.8 g (110 mmol) of 2-biphenylylboronic acid, 2.31 g (2 mmol) of Pd(PPh 3 ) 4 , 75 ml of 2 M Na 2 CO 3 , a mixture of 150 ml of EtOH and 300 ml of toluene was degassed and placed under nitrogen, and then heated at 100 °C for 12 hours. After completion of the reaction, the mixture was cooled to room temperature. The organic layer was extracted with ethyl acetate and water, dried over anhydrous magnesium sulfate, the solvent was removed and the residue was purified by column chromatography on silica gel to give the product 2-(biphenyl-2-yl)-7-bromo-9,9-dimethyl-9H-fluorene as a white solid (26.8 g, 63.0 mmol, 63%).

[0196] In a 3000 ml three-necked flask which was degassed and filled with nitrogen, 26.8 g (60 mmol) of 2-(biphenyl-2-yl)-7-bromo-9,9-dimethyl-9H-fluorene was dissolved in anhydrous dichloromethane (1500 ml), then 97.5 g (600 mmol) of iron(III) chloride was added and the mixture was stirred for one hour. 500 ml of methanol was added to the mixture and the organic layer was separated and the solvent was removed in vacuo. The residue was purified by column chromatography on silica gel (hexane-dichloromethane) to give the white solid N-912A (12-bromo-10,10-dimethyl-10H-indeno[1,2-b]triphenylene (10.7 g, 25.3 mmol, 40%).

[0197]

[0198] A mixture of 20 g (41.3 mmol) of N-(biphenyl-4-yl)-9,9'-spirobi[fluorene]-2-amine (CAS: 1258514-95-2), 14 g (49.5 mmol) of 1-bromo-4-iodobenzene, 2.4 g (12.4 mmol) of copper(I) iodide, 17.1 g (123.9 mmol) of potassium carbonate and 300 ml of DMF was refluxed overnight under nitrogen. After completion of the reaction, it was then cooled to room temperature. The organic layer was extracted with ethyl acetate and water, dried over anhydrous magnesium sulfate, the solvent was removed and the residue was purified by column chromatography on silica gel (hexane-dichloromethane) to give 26.3 g (yield 43%) of the product N-(biphenyl-4-yl)-N-(4-bromo-phenyl)-9,9'-spirobi[fluorene]-2-amine as a white solid.

[0199] A mixture of 10 g (15.6 mmol) of N-(biphenyl-4-yl)-N-(4-bromophenyl)-9,9'-spirobi[fluorene]-2-amine, 4.75 g (18.72 mmol) of bis(pinacolato)diboron, 0.18 g (0.156 mmol) of tetrakis(triphenylphosphine)palladium, 2 g (20.28 mmol) of potassium acetate and 300 ml of 1,4-dioxane was degassed and placed under nitrogen, and then heated at 90 °C for 16 h. After completion of the reaction, the mixture was cooled to room temperature. The organic layer was extracted with ethyl acetate and water, dried over anhydrous magnesium sulfate, the solvent was removed and the product was purified by column using a mixture of hexane and ethyl as eluent, to give 8.77 g of a pale yellow product N-912B (N-(biphenyl-4-yl)-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-9,9'-spirobifluorene-2-amine, (yield 82%)).

[0200]

[0201] A mixture of 15 g (35.43 mmol) of 12-bromo-10,10-dimethyl-10H-indeno[1,2-b]triphenylene (N-912A), 29.1 g (42.51 mmol) of N-(biphenyl-4-yl)-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-9,9'-spirobifluorene-2-amine (N-912B), 0.41 g (0.35 mmol) of tetrakis(triphenylphosphine)palladium, 23 ml of 2M Na 2 CO 3 3, 100 ml of EtOH and 200 ml of toluene was degassed and placed under nitrogen, and then heated at 100 °C for 8 h. After completion of the reaction, the mixture was cooled to room temperature. The organic layer was extracted with dichloromethane and water, dried over anhydrous magnesium sulfate, the solvent was removed and the residue was purified by column chromatography (hexane-dichloromethane) packed with silica gel, to give 17.5 g of the product as a yellow solid (N-912, yield 55%).

[0202] Elemental analysis: C 70 H 47 N theoretical values: C, 93.20; H, 5.25; N, 1.55; found: C, 93.16; H, 5.27; N, 1.57; HRMS(ESI) m / z (M+): theoretical value: 901.37; found: 902.21.

[0203] 9. Synthetic route of N-895

[0204]

[0205] A mixture of 5 g (11.8 mmol) of 12-bromo-10,10-dimethyl-10H-indeno[1,2-b]triphenylene (N-912A), 6.8 g (14.1 mmol) of N-(biphenyl-4-yl)-9,9'-spirobifluorene-2-amine (CAS: 1258514-95-2), 0.03 g (0.11 mmol) of palladium(II) acetate, 0.04 g (0.11 mmol) of 2-(dicyclohexylphosphino)biphenyl, 1.7 g (17.7 mmol) of sodium tert-butoxide and 100 ml of toluene was refluxed overnight under nitrogen. After the reaction was completed, it was then cooled to room temperature. The organic layer was extracted with dichloromethane and water, dried over anhydrous magnesium sulfate, the solvent was removed and the residue was purified by column chromatography (hexane-dichloromethane) packed with silica gel to obtain 5.8 g of the product as a yellow solid (N-895, yield 60%).

[0206] Elemental analysis: C 64 H 43 Theoretical values for C, H, N: C, 93.06; H, 5.25; N, 1.70; Found: C, 93.02; H, 5.25; N, 1.73; HRMS (ESI) m / z (M+): Theoretical value: 825.34; Found: 826.19.

[0207] 10. Synthetic routes of N-891, N-899, N-901, N-906, N-918, N-925

[0208] The synthesis conditions were the same as those for N-895, except that the starting materials N-nA, N-nB and the structures and yields of the products were different, as shown in Table 7 below; the elemental analysis results of the prepared compounds are shown in Table 8.

[0209] Table 7

[0210]

[0211]

[0212] Table 8

[0213]

[0214] Example 6

[0215] An organic electroluminescent device, the structure of which from bottom to top is in turn: a substrate with an anode layer, a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer (EBL), a light emitting layer (EML), a hole blocking layer (HBL), an electron transport layer (ETL), an electron injection layer (EIL) and a cathode. The specific preparation process is as follows:

[0216] (1) Substrate cleaning: The glass substrate coated with transparent ITO is ultrasonically treated in an aqueous cleaning agent (the composition and concentration of the aqueous cleaning agent: ethylene glycol-based solvent ≤ 10 wt%, triethanolamine ≤ 1 wt%), rinsed in deionized water, ultrasonically degreased in a mixed solvent of acetone:ethanol (volume ratio 1:1), baked in a clean environment until all moisture is completely removed, and then cleaned with ultraviolet light and ozone.

[0217] (2) Evaporation of the organic light-emitting functional layer:

[0218] Place the above-mentioned glass substrate with the anode layer in a vacuum chamber, evacuate to 1×10 -6 to 2×10 -4 Pa, and vacuum-evaporate a mixture of NDP-9 and HT on the anode layer film, where the mass ratio of NDP-9 to HT is 3:97, as the hole injection layer, with an evaporation thickness of 10 nm; among them, the structures of NDP-9 and HT are as follows:

[0219]

[0220] (3) Evaporate the hole transport layer (material: HT) on the hole injection layer, with an evaporation film thickness of 80 nm.

[0221] (4) Evaporate the light-emitting layer on the hole transport layer. The specific preparation method is: vacuum-evaporate the light-emitting host material and the dopant material (piq) 2 Ir(acac) in a co-evaporation manner. The composition of the host material and the dopant material is shown in Table 9;

[0222] Table 9

[0223] Serial number EML material Device N1M1 <![CDATA[N-4:M-17:(piq) 2 Mass ratio of Ir(acac) = 47.5:47.5:5]]> Device N2M2 <![CDATA[N-37:M-24:(piq) 2 Mass ratio of Ir(acac) = 47.5:47.5:5]]> Device N3M3 <![CDATA[N-389:M-94:(piq) 2 Mass ratio of Ir(acac) = 47.5:47.5:5]]> Device N4M4 <![CDATA[N-423:M-113:(piq) 2 Mass ratio of Ir(acac) = 47.5:47.5:5]]> Device N5M5 <![CDATA[N-439:M-127:(piq) 2 Mass ratio of Ir(acac) = 47.5:47.5:5]]> Device N6M6 <![CDATA[N-669:M-131:(piq) 2 Mass ratio of Ir(acac) = 47.5:47.5:5 <!-- 69 -->]]> Device N7M7 <![CDATA[N-728:M-173:(piq) 2 Mass ratio of Ir(acac) = 47.5:47.5:5]]> Device N8M8 <![CDATA[N-860:M-174:(piq) 2 Mass ratio of Ir(acac) = 47.5:47.5:5]]> Device N9M1 <![CDATA[N-891:M-17:(piq) 2 Mass ratio of Ir(acac) = 47.5:47.5:5]]> Device N10M9 <![CDATA[N-686:M-139:(piq) 2 Mass ratio of Ir(acac) = 47.5:47.5:5]]> Device N11M2 <![CDATA[N-912:M-24:(piq) 2 Mass ratio of Ir(acac) = 47.5:47.5:5]]> Device N12M4 <![CDATA[N-925:M-113:(piq) 2 Mass ratio of Ir(acac) = 47.5:47.5:5]]> Device N1M1' <![CDATA[N-4:M-17:(piq) 2 Mass ratio of Ir(acac) = 38:57:5]]> Device N10M9' <![CDATA[N-686:M-139:(piq) 2 Mass ratio of Ir(acac) = 38:57:5]]> Device N9M2 <![CDATA[N-891:M-24:(piq) 2 Mass ratio of Ir(acac) = 47.5:47.5:5]]> Device N11M7 <![CDATA[N-912:M-173:(piq) 2 Mass ratio of Ir(acac) = 47.5:47.5:5]]>

[0224] The total evaporation film thickness is 38 nm; among them, (piq) 2 The structure of Ir(acac) is as follows:

[0225]

[0226] (5) Evaporate an electron transport layer on the light-emitting layer. The specific preparation method is: vacuum-evaporate the electron transport layer material in a co-evaporation manner. The material is ET-1 and LiQ with a mass ratio of 1:1, and the total evaporation film thickness is 30 nm. Among them, the structures of ET-1 and LiQ are as follows:

[0227]

[0228] (6) Vacuum-evaporate an electron injection layer on the electron transport layer. The material of the electron injection layer is LiQ, and the total evaporation film thickness is 1 nm;

[0229] (7) Al is evaporated on the electron injection layer, and the total evaporation film thickness is 80 nm.

[0230] Comparative Example 1

[0231] The difference between this comparative example and Example 6 lies in that during the process of fabricating the device, the composition of the host material used in step (5) is different, as shown in Table 10 specifically; other steps and parameter conditions are the same as those in Example 6.

[0232] Table 10

[0233] Serial number EML material Device N1 N-4: Mass ratio of (piq)2Ir(acac) = 95:5 Device N9 N-891: Mass ratio of (piq)2Ir(acac) = 95:5 Device M1 M-17: Mass ratio of (piq)2Ir(acac) = 95:5 Device C CBP: Mass ratio of (piq)2Ir(acac) = 95:5 Device RC REF-1: Mass ratio of CBP:(piq)2Ir(acac) = 47.5:47.5:5 Device M1C M-17: Mass ratio of CBP:(piq)2Ir(acac) = 47.5:47.5:5

[0234] In the above table, the structures of CBP (4,4'-bis(N-carbazolyl)-1,1'-biphenyl, CAS: 58328-31-7) and REF-1 (CAS: 1070884-53-5) are as follows:

[0235]

[0236] Experimental Example

[0237] The devices prepared by using Example 6 and Comparative Example 1 are subjected to performance tests, and the specific test conditions are as follows:

[0238] The characteristics such as the current, voltage, brightness, and emission spectrum of the device are synchronously tested by using a PR 650 spectral scanning luminance meter and a Keithley K 2400 digital source meter system;

[0239] Optoelectronic characteristic test condition: The current density is 10 mA / cm 2 ;

[0240] Lifetime test: The current density is 50 mA / cm 2 , and the time (in hours) is recorded when the device brightness drops to 95% of the original brightness.

[0241] The above device performance test results are shown in Table 11 and Table 12.

[0242] Table 11

[0243]

[0244]

[0245] Table 12

[0246] Driving voltage (V) Current efficiency (Cd / A) Lifetime T95 (hrs) Device N1M1 3.35 25.44 254.2 Device N2M2 3.37 24.78 255.4 Device N3M3 3.40 23.71 249.7 Device N4M4 3.28 26.47 267.4 Device N5M5 3.31 25.99 260.3 Device N6M6 3.35 24.97 259.5 Device N7M7 3.44 24.10 244.7 Device N8M8 3.30 27.54 264.2 Device N9M1 3.33 26.78 284.5 Device N10M9 3.21 27.58 297.1 Device N11M2 3.42 25.14 260.3 Device N12M4 3.40 24.85 250.1 Device N1M1' 3.24 28.47 291.7 Device N10M9' 3.17 30.22 299.5 Device N9M2 3.38 25.12 255.4 Device N11M7 3.40 25.55 256.7 Device C 4.80 5.00 5.0 Device RC 4.27 19.76 48 Device M1C 3.66 22.24 188.7

[0247] From the data in Table 11 above, it can be seen that when the host materials in the luminescent material are selected as Compound N and Compound M in combination, a synergistic effect can be achieved. Compared with using Compound N or Compound M alone as the organic electroluminescent host material, the combination of the two has a lower turn-on voltage, improves the luminous efficiency of the device, and increases the service life of the device. From the data in Table 12, it can be known that when the present invention uses Compound N and Compound M as the organic electroluminescent host material and applies it to the organic functional layer, a synergistic effect will occur between Compound N and Compound M, enabling the device to have a lower driving voltage (below 3.44 V), a higher current efficiency (above 23 Cd / A), and a longer life (above 240 h).

[0248] From the data in Table 12, it can be seen that for the Compound N developed in the present invention, after it is combined with Compound M, the performance improvement of the device is significantly more remarkable than the combination between other similar-structured compounds (CBP) and Compound M disclosed in the prior art. Refer to Device M1C in which M-17 and CBP are combined. At the same time, from Device RC in which REF-1 and CBP are combined, it can be seen that the performance of the device obtained by combining Compound M and Compound N in the present invention is significantly better than that of the devices obtained by combining other similar-structured compounds, further proving the performance advantages of the devices of the present invention.

[0249] At the same time, Compound N of the present invention preferably adopts the structure described in Formula (1). In this Compound N, a triarylamine structure is connected to the phenanthrocarbazole parent structure. Such a material is not only suitable as a luminescent host material, especially for a red-light host material, a hole-transporting material, and an electron-blocking material, but also suitable as an electron-transporting material and a hole-blocking material, which can greatly improve the luminous efficiency of the device and the device has a longer life. Therefore, such compounds can be used in the field of organic electroluminescent displays. Specifically, such compounds are used as a hole injection material or a hole-transporting material in an organic electroluminescent display, and can also be used as a luminescent host material or a luminescent material in a fluorescent device.

[0250] As can be seen from the above, the light-emitting device prepared by combining Compound M and Compound N developed in the present invention can significantly improve the carrier injection efficiency, reduce the interlayer energy level difference, balance the electron and hole transport rates, and can effectively improve the efficiency of the organic light-emitting diode and extend the life of the organic light-emitting diode.

[0251] Obviously, the above embodiments are merely examples given for clear illustration and are not limitations on the implementation manners. For those of ordinary skill in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation manners here. And the obvious changes or modifications derived therefrom still fall within the protection scope of the present invention.

Claims

1. An organic electroluminescent multi-host material composition, characterized in that, it comprises a compound N having the structure shown in formula (1) and a compound M having the structure shown in formula (2); Formula (1): In the formula (1), X is selected from O, S, Se, NAr or CR 6 R 7 ; wherein, Ar is selected from aryl groups having 6 to 30 carbon atoms; R 6 -R 7 are each independently selected from alkyl groups having 1 to 5 carbon atoms; R 1 is -L 1 Ar 1 ; R 2 is -L 2 Ar 2 ; R 3 is -L 3 Ar 3 ; L 1 -L 3 are each independently selected from a linking group, a substituted or unsubstituted C6 - C30 arylene group, a substituted or unsubstituted C3 - C30 heteroarylene group; Ar 1 -Ar 3 at least one of which is the remaining Ar 1 -Ar 3 are each independently selected from hydrogen, deuterium, a halogen; represents a linking group, and the R 4 is -L 4 Ar 4 , and the R 5 is -L 5 Ar 5 ; L 4 -L 5 are each independently selected from a linking group, a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C3-C30 heteroarylene group, Ar 4 -Ar 5 are each independently selected from hydrogen, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group; Equation (2): In the formula (2), X 1 -X 8 are all CR, or any one of them is N and the rest are CR; X 9 -X 12 are all CR, or any one of them is N and the rest are CR; R is selected from hydrogen or deuterium; L is selected from a linking bond; Ar 8 -Ar 9 are each independently selected from a substituted or unsubstituted C6-C30 aryl group, a C3-C30 heteroaryl group; the above-mentioned substituted groups are selected from one or a combination of two of deuterium, halogen, cyano, C1-C6 alkyl, C3-C30 cycloalkyl, C6-C30 aryl, and C3-C30 heteroaryl; the mass ratio of the compound N to the compound M is 4:6 - 6:

4.

2. The organic electroluminescent multi-host material composition according to claim 1, characterized in that, Ar 8 -Ar 9 Each independently selected from substituted or unsubstituted groups such as: phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, triphenylene, group, dimethylfluorenyl, spirobifluorenyl, fluoranthenyl, diphenylfluorenyl, benzodimethylfluorenyl, benzodiphenylfluorenyl, benzospirobifluorenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, phenylcarbazolyl, dipyridyl, pyrimidinyl, triazinyl.

3. The organic electroluminescent multi-host material composition according to claim 1, characterized in that, the structure of the compound M is as shown in any one of M-1 to M-224:

4. The organic electroluminescent multi-host material composition according to any one of claims 1-3, characterized in that, The Ar 4 -Ar 5 Each independently selected from a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, and a substituted or unsubstituted dibenzoselenophenyl group.

5. The organic electroluminescent multi-host material composition according to any one of claims 1-3, characterized in that, The Ar 4 -Ar 5 Each is independently selected from the following substituted or unsubstituted groups: phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, triphenylene, group, dibenzofuranyl, benzonaphthofuranyl, dibenzothiophenyl, dibenzoselenophenyl, triphenylene, dimethylfluorenyl, spirobifluorenyl, fluoranthenyl, carbazolyl, phenylcarbazolyl, diphenylfluorenyl, benzyldimethylfluorenyl, benzodiphenylfluorenyl, benzospirobifluorenyl, pyridyl, pyrimidinyl, triazinyl.

6. The organic electroluminescent multi-host material composition according to any one of claims 1-3, characterized in that, The said Ar 4 -Ar 5 Each independently selected from Among them, R T1 -R T6 are each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C4-C30 heteroaralkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 heterocycloalkyl, substituted or unsubstituted C3-C30 cycloalkenyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryloxy; or R T1 -R T5 any two adjacent ones of which may be fused to form a C6-C30 ring A; Y is selected from O, S, NAr, CR 6 R 7 ; wherein the definitions of Ar, R 6 , R 7 are the same as those in claim 1; When there are multiple Rs T1 -R T6 When there are multiple Rs T1 -R T6 they are each independent of one another, and may be the same or different.

7. The organic electroluminescent multi-host material composition according to claim 6, characterized in that, ring A is selected from a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, and a substituted or unsubstituted phenanthrene ring.

8. The organic electroluminescent multi-host material composition according to claim 1, characterized in that, Ar is selected from the following substituted or unsubstituted groups: phenyl, naphthyl, biphenyl, terphenyl, triphenylene, anthryl, dibenzofuranyl, dibenzothiophenyl.

9. The organic electroluminescent multi-host material composition according to any one of claims 1-3, characterized in that, L 4 -L 5 Each is independently selected from a single bond, a substituted or unsubstituted C6-C30 arylene group.

10. The organic electroluminescent multi-host material composition according to claim 9, characterized in that, L 1 -L 3 Each is independently selected from a linking bond, a phenylene group, a naphthylene group, a terphenyl group, a biphenylene group; or, L 1 -L 3 Each is independently selected from a single bond; and / or, L 4 -L 5 each independently selected from a single bond, phenylene, naphthylene; and / or, the remaining Ar 1 -Ar 3 selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl.

11. The organic electroluminescent multi-host material composition according to claim 10, characterized in that, L 1 selected from linking keys, L 2 selected from phenylene, naphthylene, triphenylene, biphenylene, L 3 is a linking key; and / or, L 4 -L 5 Each is independently selected from a single bond.

12. The organic electroluminescent multi-host material composition according to claim 1, characterized in that, the structure of the compound N is as shown in any one of formula 1-1 to formula 1-17; wherein R 1 -R 7 、L 1 -L 3 、Ar are defined as in claim 1.

13. The organic electroluminescent multi-host material composition according to claim 1, characterized in that, the structure of the compound N shown in formula (1) is as shown in any one of N-1 to N-929:

14. Use of the organic electroluminescent multi-host material composition according to any one of claims 1-13 in a light-emitting device.

15. An organic electroluminescent material, characterized in that, it comprises the organic electroluminescent multi-host material composition according to any one of claims 1-13.

16. An organic electroluminescent device, characterized in that, it comprises an anode and a cathode, and an organic layer disposed between the anode and the cathode; the organic layer comprises the organic electroluminescent multi-host material composition according to any one of claims 1-13.

17. An organic electroluminescent device, characterized in that, it comprises an organic electroluminescent device according to claim 16.

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