A trisanthracene derivative and its application

Abstract

The present invention relates to the technical field of organic electroluminescent materials, and in particular to a phenyltriphenylene derivative and its application in an organic electroluminescent element. The phenyltriphenylene derivative is shown in formula (I) and has a triarylamine stereostructure of phenyltriphenylene; the derivative is applied in an organic electroluminescent element to significantly reduce the driving voltage, improve the luminous efficiency and lifespan;

Description

Technical Field

[0001] The invention relates to the technical field of organic electroluminescent materials, and in particular to a benzotricyclopentadiene derivative, an organic material, and an application thereof in an organic electroluminescent element. Background Art

[0002] Generally speaking, organic luminescence refers to the phenomenon of light emission when electrical energy is applied to an organic substance; that is, when an organic layer is arranged between an anode and a cathode, if a voltage is applied between the two electrodes, holes are injected from the anode into the organic layer, and electrons are injected from the cathode into the organic layer; when the injected holes and electrons meet, excitons are formed, and when the excitons transition to the ground state, light and heat are emitted.

[0003] In recent years, organic electroluminescent display technology has become mature, and some products have entered the market, but there are still many problems to be solved in the process of industrialization. In particular, there are many problems that have not been solved in the various organic materials used to make components, such as carrier injection and transmission performance, material electroluminescent performance, service life, color purity, matching between various materials and between electrodes, etc.; in particular, the luminous efficiency and service life of the light-emitting components have not met the practical requirements, which greatly limits the development of OLED technology. The metal complex phosphorescent materials that use triplet luminescence have high luminous efficiency, and their green and red light materials have met the use requirements, but the metal complex phosphorescent materials require phosphorescent materials or hole materials with high triplet energy levels to match them. Therefore, the development of phosphorescent materials or hole materials with high triplet energy levels is an urgent need for the current development of OLED.

[0004] Under the current technological development, both fluorescent materials and phosphorescent materials need to be improved, especially in terms of operating voltage, efficiency and life span used in organic electroluminescent elements and thermal stability during sublimation.

[0005] Therefore, in order to overcome the above-mentioned problems of the prior art and further improve the characteristics of the organic electroluminescent element, there continues to be a demand for the development of more stable and effective substances that can be used as phosphorescent materials or hole materials in the organic electroluminescent element.

[0006] In view of this, the present invention is proposed. Summary of the invention

[0007] The purpose of the present invention is to provide a benzotricyclopentyl derivative, which contains a benzotricyclopentyl structure. An organic electroluminescent element prepared using the benzotricyclopentyl derivative can significantly reduce the driving voltage, improve the luminous efficiency and life; another purpose of the present invention is to provide the use of the benzotricyclopentyl derivative in an organic electroluminescent element.

[0008] Specifically, the present invention provides the following technical solutions:

[0009] The present invention provides a benzotricyclopentadiene, the structural formula of which is shown in formula (I):

[0010]

[0011] in,

[0012] R 1 ~R 5 Each independently selected from hydrogen, deuterium, nitrile, C 1 -C 40 Alkyl, C 3 -C 40 Cycloalkyl, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Condensed ring aromatic group, substituted or unsubstituted C 6 -C 60 Arylamine, substituted or unsubstituted C 2 -C 60 The group consisting of heteroaryl groups, and in R 1 , R 2 , R 3 At least one of them is a group represented by formula (II);

[0013] x, y, and z are each independently selected from integers of 0 to 4;

[0014]

[0015] Ar 1 ,Ar 2 are each independently selected from substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Condensed ring aromatic group, substituted or unsubstituted C 6 -C 60 Arylamine, or substituted or unsubstituted C 2 -C 60 The group consisting of heteroaryl;

[0016] n is an integer selected from 0 to 5;

[0017] L is selected from a single bond, a substituted or unsubstituted C 6 -C 60 arylene, or substituted or unsubstituted C 2 -C 60 The group consisting of heteroarylene.

[0018] *—indicates the position where L is bonded to phenyltriphenylene.

[0019] In the present invention, in a substituted or unsubstituted ring formed by bonding adjacent groups to each other, "ring" means a substituted or unsubstituted hydrocarbon ring or a substituted or unsubstituted heterocyclic ring.

[0020] Preferably, the aryl and heteroaryl groups refer to groups derived from the following substances: phenyl, naphthyl, anthracenyl, benzanthryl, phenanthrenyl, pyrenyl, yl, peryl, fluoranthenyl, tetraphenyl, pentacene, benzopyrenyl, biphenyl, phenylene, terphenyl, triphenyl, quadriphenyl, fluorenyl, spirobifluorenyl, dihydrophenanthryl, triphenylene, dihydropyrenyl, tetrahydropyrenyl, cis- or trans-indenofluorenyl, cis- or trans-indenocarbazolyl, cis- or trans-indolcarbazolyl, trimerized indenyl, isotrimerized indenyl, spirotrimerized indenyl, spiroisotrimerized indenyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, indole , 1,2-thiazolyl, 1,3-thiazolyl, benzothiazolyl, pyridinyl, 1,2-thiazolyl, 1,3-thiazolyl, 1,4-diphenylamine, 1,6-diphenylamine, 1,8-diphenylamine, 1,2-diphenylamine, 1,6-diphenylamine, 1,8-diphenylamine, 1,8-diphenylamine, 1,2-diphenylamine, 1,3 ... Azatriphenylene group, benzopyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1,5-diazaanthryl, 2,7-diazapyrenyl, 2,3-diazapyrenyl, 1,6-diazapyrenyl, 1,8-diazapyrenyl, 4,5-diazapyrenyl, 4,5,9,10-tetraazaperyl, pyrazinyl, phenazinyl, phenoxazinyl, phenothiazinyl, fluorescein ring group, naphthyridinyl, azacarbazolyl, benzocarbolinyl, carbolinyl, phenanthrolinyl, 1,2,3-triazolyl, 1,2,4-triazolyl, benzotriazolyl, 1,2,3-oxadiazolyl , 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, 1,3,5-triazinyl, 1,2,4-triazinyl, 1,2,3-triazinyl, tetrazolyl, 1,2,4,5-tetrazinyl, 1,2,3,4-tetrazinyl, 1,2,3,5-tetrazinyl, purinyl, pteridinyl, indolizinyl, quinazolinyl, benzothiadiazolyl or a group derived from a combination of these systems.

[0021] Preferably, the R 1 ~R 5At each occurrence, each is independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, nitrile, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted quaterphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted triphenylene, substituted or unsubstituted anthracenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, and substituted or unsubstituted carbazolyl.

[0022] Preferably, the R 1 is a group represented by formula (II), and x is 1 or 2.

[0023] Preferably, the R 2 is a group represented by formula (II), and y is 1 or 2.

[0024] Preferably, the R 3 It is a group represented by formula (II), and z is 1 or 2.

[0025] Preferably, the R 1 , R 2 , R 3 At each occurrence, each is independently selected from the group consisting of hydrogen, methyl, isopropyl, isobutyl, tert-butyl, nitrile, substituted or unsubstituted phenyl;

[0026] R 4 , R 5 Each is independently selected from the group consisting of hydrogen, methyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylene, substituted or unsubstituted anthracenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, and substituted or unsubstituted carbazolyl.

[0027] Preferably, the Ar 1 ,Ar 2 Each is independently selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted quaterphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylene, substituted or unsubstituted anthracenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted fluorenyl, and substituted or unsubstituted carbazolyl.

[0028] Preferably, L is selected from the group consisting of a single bond, a substituted or unsubstituted phenylene, a substituted or unsubstituted biphenylene, a substituted or unsubstituted naphthylene, a substituted or unsubstituted phenanthrylene, a substituted or unsubstituted triphenylene, a substituted or unsubstituted anthraceneene, a substituted or unsubstituted dibenzofuranylene, a substituted or unsubstituted dibenzothiophenylene, a substituted or unsubstituted fluorenylene, and a substituted or unsubstituted carbazolylene.

[0029] Preferably, n is 0, 1 or 2.

[0030] Furthermore, the L is selected from a single bond or a group consisting of the following groups shown in III-1 to III-16:

[0031]

[0032] in,

[0033] Z 11 , Z 12 Each is independently selected from hydrogen, deuterium, a halogen atom, a hydroxyl group, a nitrile group, a nitro group, an amino group, an amidine group, a hydrazine group, a hydrazone group, a carboxyl group or a carboxylate thereof, a sulfonic acid group or a sulfonate thereof, a phosphoric acid group or a phosphate thereof, a C 1 -C 60 Alkyl, C 2 -C 60 The alkenyl group, C 2 -C 60 Alkynyl, C 1 -C 60 Alkoxy, C 3 -C 60 Cycloalkane, C 3 -C 60 Cycloalkene, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Aryloxy, substituted or unsubstituted C 6 -C 60 aryl thioether group, or substituted or unsubstituted C 2 -C 60 The group consisting of heterocyclic aromatic groups;

[0034] Z 13 Indicates substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Aryloxy, substituted or unsubstituted C 6 -C 60 aryl thioether group, or substituted or unsubstituted C 2 -C 60One or more of heterocyclic aromatic groups;

[0035] y1 represents an integer from 1 to 4; y2 represents an integer from 1 to 6; y3 represents an integer from 1 to 3; y4 represents an integer from 1 to 5;

[0036] T 1 represents O, S, CR'R" or NAr';

[0037] R', R" are each independently selected from hydrogen, deuterium, C 1 -C 60 Alkyl, C 1 -C 60 Heteroalkyl, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Arylamine, or substituted or unsubstituted C 2 -C 60 The group consisting of heterocyclic aromatic groups, R’ and R" may be optionally joined or fused to form one or more additional substituted or unsubstituted rings, containing or not containing one or more heteroatoms N, P, B, O or S in the formed rings; preferably, R', R" are methyl, phenyl or fluorenyl;

[0038] Ar' is selected from C 1 -C 60 Alkyl, C 1 -C 60 Heteroalkyl, C 3 -C 60 Cycloalkyl, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Condensed ring aromatic group, substituted or unsubstituted C 6 -C 60 Arylamine, or substituted or unsubstituted C 2 -C 60 The group consisting of heterocyclic aromatic groups; preferably, Ar' is methyl, ethyl, phenyl or naphthyl;

[0039] It represents the connecting bond between L and N or the main structure.

[0040] In the present invention, the term "substituted or unsubstituted" means a group selected from hydrogen, deuterium, fluorine, hydroxyl, nitrile, nitro, amino, amidine, hydrazine, hydrazone, carboxyl or its carboxylate, sulfonic acid or its sulfonate, phosphoric acid or its phosphate, C 1 -C 40 Alkyl, C 2 -C40 The alkenyl group, C 2 -C 40 Alkynyl, C 1 -C 40 Alkoxy, C 3 -C 40 Cycloalkyl, C 3 -C 40 Cycloalkenyl, C 6 -C 60 The aromatic group, C 6 -C 60 The aryloxy group, C 6 -C 60 The aryl sulfide group and C 2 -C 60 The heterocyclic aromatic group may be substituted or unsubstituted with one or more substituents, or may be substituted or unsubstituted with a substituent formed by connecting two or more substituents among the substituents exemplified above.

[0041] Preferably, the structure of the benzotricyclopentadiene derivative is selected from the group consisting of the following C602 to C772:

[0042]

[0043]

[0044]

[0045]

[0046]

[0047]

[0048]

[0049]

[0050] Among them, *—T 2 —* is selected from *—O—*, *—S—* or one of the following structures:

[0051]

[0052] *— and —* represent connecting keys.

[0053] The raw materials for synthesizing the compound represented by formula (I) can be purchased from commercial sources. The principle, operation process, conventional post-treatment, column purification, recrystallization purification and other means of this method are well known to synthesizers in the art and can fully realize the synthesis process to obtain the target product.

[0054] Specifically, the compound represented by formula (I) is prepared by substituted benzotricyclopentadiene through a SUZUKI coupling reaction, a Buchwald-Hartwig coupling reaction, or the like. 1 Ar 2 N-(L) n B(OH) 2 or Ar 1 Ar 2 NH is prepared by palladium-catalyzed or base-catalyzed coupling reactions.

[0055] The palladium catalyst that can be used for the palladium-catalyzed coupling reaction can be selected from: Pd(P- t Bu 3 ) 2 、Pd(PPh 3 ) 4 , Pd 2 (dba) 3 , Pd 2 (dba) 3 CHCl 3 , PdCl 2 (PPh 3 ) 2 , PdCl 2 (CH 3 CN) 2 、Pd(OAc) 2 、Pd(acac) 2 、Pd / C、PdCl 2 、[Pd(allyl)Cl] 2 Any one of the above may be used, or a mixture of two or more may be used.

[0056] In addition, the base used in the palladium-catalyzed coupling reaction or the base-catalyzed coupling reaction can be selected from: sodium tert-butoxide, potassium tert-butoxide, sodium hydride, lithium hydride, sodium tert-amylate, sodium ethoxide, sodium methoxide, sodium carbonate, potassium carbonate, cesium carbonate, lithium, potassium hydride, triethylamine, cesium fluoride, etc., and a mixture of one or two or more thereof.

[0057] The coupling reaction can be carried out in an organic solvent, wherein the organic solvent can be selected from: ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, ethylene glycol ethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ether, diethylene glycol diethyl ether, or ether solvents such as anisole, benzene, toluene, xylene and other aromatic hydrocarbon agents, chlorobenzene, dichlorobenzene, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, cyclopentane, etc., and one or a mixture of two or more can be used.

[0058] The present invention also provides an organic electroluminescent material, the raw material of which includes the above-mentioned benzotricyclopentyl derivative; the organic electroluminescent material including the benzotricyclopentyl derivative of the present invention has the ability of carrier transmission or light extraction.

[0059] Preferably, the organic electroluminescent material is a hole injection layer material, a hole transport layer material, a hole blocking layer material, a light emitting layer material, an electron transport layer material, an electron injection layer material, a light extraction layer material or an electron blocking layer material.

[0060] The present invention also provides an organic electroluminescent element, which comprises: a first electrode, a second electrode, a light extraction layer and one or more organic layers disposed between the first electrode and the second electrode; at least one of the organic layer and the light extraction layer comprises the above-mentioned benzotricyclopentadiene derivative.

[0061] The organic electroluminescent element comprises a first electrode, a second electrode, a light extraction layer and at least one light-emitting layer. In addition to these layers, it may also comprise other layers, for example, in certain cases, one or more hole injection layers, hole transport layers, electron blocking layers, electron transport layers, electron injection layers, hole blocking layers and / or charge generation layers. An intermediate layer having, for example, an exciton blocking function may also be introduced between two light-emitting layers. However, it should be noted that each of these layers does not necessarily have to be present. The organic electroluminescent element described herein may comprise one light-emitting layer, or it may comprise multiple light-emitting layers. That is, a variety of light-emitting compounds capable of emitting light are used in the light-emitting layer. A system having three light-emitting layers is particularly preferred, wherein the three layers may display blue, green and red light emission. If there are more than one light-emitting layer, then according to the present invention, at least one of these layers comprises a compound of the present invention.

[0062] Furthermore, the organic electroluminescent element of the present invention does not contain a separate hole injection layer and / or hole transport layer, that is, the light-emitting layer is directly adjacent to the hole injection layer or the anode, and / or the light-emitting layer is directly adjacent to the electron transport layer or the electron injection layer or the cathode.

[0063] In the other layers of the organic electroluminescent element according to the invention, in particular in the hole transport layer and the luminescent layer, as well as in the light extraction layer, all materials can be used in the manner commonly used according to the prior art. A person skilled in the art will therefore be able to use all materials known about organic electroluminescent elements in combination with the luminescent layer according to the invention without inventive effort.

[0064] Furthermore, preference is given to organic electroluminescent elements in which one or more layers can be applied by means of a sublimation process, wherein the sublimation reaction takes place in a vacuum sublimation apparatus at temperatures below 10 °C. -5 Pa, preferably less than 10 -6The material is applied by vapor deposition at an initial pressure of 10 Pa. However, the initial pressure may also be even lower, for example below 10 -7 Pa.

[0065] Likewise preferred are organic electroluminescent components in which one or more layers can also be applied by means of an organic vapor phase deposition method or by means of carrier gas sublimation, wherein at 10 -5 The material is applied at a pressure of between 100 Pa and 1 Pa. A particular example of this method is the organic vapor jet printing method, in which the material is applied directly through a nozzle and is thus structured.

[0066] In addition, organic electroluminescent elements are preferably used in which one or more layers are produced from a solution, for example by spin coating, or by any desired printing method, for example screen printing, flexographic printing, lithography, photoinduced thermography, thermal transfer, inkjet printing or nozzle printing. Soluble compounds, for example, are obtained by appropriate substitution of the compounds of formula (I). These methods are also particularly suitable for oligomers, dendrimers and polymers. Also possible are hybrid methods, in which, for example, one or more layers are applied from a solution and one or more further layers are applied by vapor deposition.

[0067] These methods are generally known to those skilled in the art, and they can apply them to organic electroluminescent elements comprising the compounds according to the present invention without inventive step.

[0068] Therefore, the present invention also relates to a method for producing an organic electroluminescent element according to the present invention, comprising applying at least one layer by means of a sublimation method and / or applying at least one layer by means of an organic vapor deposition method or by means of carrier gas sublimation and / or applying at least one layer from a solution by spin coating or by means of a printing method.

[0069] In addition, the present invention relates to compounds of the present invention comprising at least one indicated above. The same preferences as indicated above for organic electroluminescent elements apply to the compounds of the present invention. In particular, the compounds may also preferably comprise other compounds. Processing the compounds of the present invention from the liquid phase, for example by spin coating or by a printing method, requires preparations for processing the compounds of the present invention, which preparations may be, for example, solutions, dispersions or emulsions. For this purpose, a mixture of two or more solvents may preferably be used. Suitable and preferred solvents are, for example, toluene, anisole, o-xylene, m-xylene or p-xylene, methyl benzoate, mesitylene, tetralin, o-dimethoxybenzene, tetrahydrofuran, methyltetrahydrofuran, tetrahydropyran, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxytoluene, (-)-fennel, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, α-terpenes benzothiazole, butyl benzoate, isopropylbenzene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, methyl benzoate, 1-methylpyrrolidone, p-cymene, phenethyl ether, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane, or a mixture of these solvents.

[0070] The present invention also provides an application of an organic electroluminescent element, wherein the organic electroluminescent element is used in any one of the following devices:

[0071] Flat panel display device;

[0072] Flexible display device;

[0073] Fixtures for lighting flat panels of a single colour or white colour; or

[0074] Flexible lighting device with single color or white color.

[0075] Beneficial effects achieved by the present invention:

[0076] The benzotricyclopentadiene derivative shown in formula (I) provided by the present invention has a high glass transition temperature and thermal stability, has excellent ability to transmit holes and electrons, and the molecule is easy to form a uniform film under vacuum conditions. The benzotricyclopentadiene derivative is applied in an organic electroluminescent element to significantly reduce the driving voltage, improve the luminous efficiency and lifespan. BRIEF DESCRIPTION OF THE DRAWINGS

[0077] Figure 1 A schematic diagram of an organic light-emitting device 100 is shown. The illustration is not necessarily drawn to scale. The device 100 may include a substrate 101, an anode layer 102, a hole injection layer 103, a hole transport layer 104, an electron blocking layer 105, a light-emitting layer 106, a hole blocking layer 107, an electron transport layer 108, an electron injection layer 109, a cathode layer 110, and a capping layer (CPL) 111. The device 100 may be manufactured by depositing the described layers in order.

[0078] Figure 2 Schematic diagram of an organic light-emitting device 200 showing two light-emitting layers. The device includes a substrate 201, an anode 202, a hole injection 203, a hole transport layer 204, a first light-emitting layer 205, an electron transport layer 206, a charge generation layer 207, a hole injection layer 208, a hole transport layer 209, a second light-emitting layer 210, an electron transport layer 211, an electron injection layer 212, and a cathode 213. The device 200 can be prepared by depositing the layers described in sequence. Because the most common OLED device has one light-emitting layer, and the device 200 has a first light-emitting layer and a second light-emitting layer, the light emission peaks of the first light-emitting layer and the second light-emitting layer can be overlapping, cross-overlapping, or non-overlapping. In the corresponding layers of the device 200, materials similar to those described with respect to the device 100 can be used. Figure 2 One example is provided of how some layers may be added from the structure of device 100 . DETAILED DESCRIPTION

[0079] The following examples are used to illustrate the present invention but are not intended to limit the scope of the present invention.

[0080] In the description of the present invention, unless otherwise specified, “plurality” means two or more than two; the orientations or positional relationships indicated by the terms “upper”, “lower”, etc. are based on the orientations or positional relationships shown in the accompanying drawings, and are only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as a limitation on the present invention.

[0081] The experimental methods used in the following examples are all conventional methods unless otherwise specified. The experimental raw materials and related equipment used in the following examples are all commercially available unless otherwise specified, and the percentages are all mass percentages unless otherwise specified.

[0082] In addition, unless otherwise specified, any range described in the present invention includes the end value and any numerical value between the end values ​​and any sub-range formed by the end value or any numerical value between the end values.

[0083] The test instruments and methods for testing the performance of OLED materials and components in the following embodiments are as follows:

[0084] OLED component performance testing conditions:

[0085] Brightness and chromaticity coordinates: tested using a spectral scanner PhotoResearch PR-715;

[0086] Current density and lighting voltage: tested using Keithley 2420 digital source meter;

[0087] Power efficiency: Tested using NEWPORT 1931-C.

[0088] Example 1

[0089] The preparation method of compound C621 comprises the following steps:

[0090] Step 1: Preparation of intermediate Int-1

[0091]

[0092] 10.0 mmol of 1-bromoanthraquinone (prepared by the method disclosed in reference patent CN113651858A) was dissolved in 100 mL of acetone, and 11.0 mmol of 1,1-dimethylbenzyl chloride, 11.0 mmol of potassium hydroxide and 1.0 mmol of benzyltriethylammonium chloride were added. Under nitrogen protection, the temperature was raised and refluxed for 10 hours, cooled to room temperature, concentrated and dried under reduced pressure, 50 mL of water was added, and extracted with dichloromethane. The organic phase was collected and purified by silica gel column to obtain compound Int-1 as a white solid with a yield of 63%.

[0093] Step 2: Preparation of intermediate Int-2

[0094]

[0095] Under nitrogen protection, 10.0 mmol of Int-1 was dissolved in 80 mL of THF. Under nitrogen protection, 20.0 mmol of solid sodium borohydride was added in batches. The mixture was reacted at room temperature for 12 hours, concentrated under reduced pressure, 100 mL of water was added, extracted with ethyl acetate, the organic phase was collected, dried, filtered, and the filtrate was concentrated under reduced pressure. The filtrate was separated and purified on a silica gel column to obtain compound Int-2 as a white solid with a yield of 92%.

[0096] Step 3: Preparation of intermediate A1

[0097]

[0098] Under nitrogen protection, 20.0 mmol of intermediate Int-2 was dissolved in 60 mL of dichloromethane, 20 mL of formic acid was added, and the mixture was stirred for 2 hours. The mixture was concentrated under reduced pressure and purified by silica gel column to obtain compound A1 as a white solid with a yield of 90%.

[0099] Referring to the above-mentioned similar synthesis method, the compounds shown in Table 1 below were prepared:

[0100]

[0101]

[0102] Step 3: Preparation of compound C621

[0103]

[0104] Under nitrogen protection, 22.0 mmol of intermediate A1 was dissolved in 50 mL of dry toluene, and 20.0 mmol of tert-phenylbenzidine, 30.0 mmol of sodium tert-butoxide, 0.2 mmol of Pd 2 (dba) 3 and 0.4 mmol of XantPhos, heated to 100°C and stirred for reaction for 12 hours, cooled to room temperature, added 50 mL of water, separated the organic phase, extracted the aqueous phase with toluene, combined the organic phases, dried, filtered, and the filtrate was concentrated under reduced pressure and purified by silica gel column to obtain compound C621 as a white solid with a yield of 82%. MS (MALDI-TOF): m / z=692.3325[M+H] + ; 1 HNMR (δ, CDCl 3 ): 7.74~7.56(9H,m); 7.51~7.45(4H,m); 7.41~7.35(2H,m); 7.31~7.29(1H,m); 7.25~7.09(8H, m); 7.06~7.02(2H,m); 6.95~6.83(7H,m); 4.96(1H,s); 4.34(1H,s); 1.43(3H,s); 1.17(3H,s).

[0105] Referring to the above-mentioned similar synthesis method, the compounds shown in Table 2 below were prepared:

[0106] Table 2

[0107]

[0108]

[0109]

[0110]

[0111]

[0112]

[0113]

[0114] Example 2

[0115] The preparation method of compound C763 comprises the following steps:

[0116] Step 1: Preparation of intermediate Int-3

[0117]

[0118] Under nitrogen protection, 20.0 mmol of A1 was dissolved in 40 mL of DMF, and 22.0 mmol of biboric acid pinacol ester, 30.0 mmol of anhydrous potassium acetate, and 0.2 mmol of PdCl were added. 2 (dppf), heat to 90°C and stir to react for 12 hours, cool to room temperature, pour the reaction solution into 200 mL of ice water, extract with ethyl acetate, collect the organic phase, dry, filter, concentrate the filtrate under reduced pressure, and separate and purify on a silica gel column to obtain compound Int-3 as a white solid. Yield: 87%.

[0119] Step 2: Preparation of intermediate Int-4

[0120]

[0121] Under nitrogen protection, 22.0 mmol of intermediate Int-3 was dissolved in 40 mL of toluene, and 20.0 mmol of p-bromoiodobenzene, 60.0 mmol of sodium carbonate, 0.01 mmol of Pd0132, 20 mL of ethanol and 20 mL of water were added. The temperature was raised to reflux and stirred for reaction for 12 hours, then cooled to room temperature, 50 mL of water was added, the organic phase was separated, the aqueous phase was extracted with toluene, the organic phases were combined and dried, filtered, and the filtrate was concentrated under reduced pressure and purified by silica gel column to obtain compound Int-4 as a white solid. The yield was 86%.

[0122] Step 3: Preparation of compound C763

[0123]

[0124] Under nitrogen protection, 22.0 mmol of intermediate Int-4 was dissolved in 50 mL of dry toluene, and 20.0 mmol of diarylamine, 30.0 mmol of sodium tert-butoxide, 0.2 mmol of Pd 2 (dba)3 and 0.4 mmol of XantPhos, heated to 100°C and stirred for reaction for 12 hours, cooled to room temperature, added 50 mL of water, filtered, the filter cake was washed with water and ethanol, dried and separated and purified by silica gel column to obtain compound C763 as a white solid, yield: 82%, MS (MALDI-TOF): m / z = 781.3596 [M+H] + ; 1 HNMR (δ, CDCl 3 ): 8.52(1H,s); 8.18(1H,s); 7.93~7.91(1H,m); 7.75~7.70(4H,m); 7.58~7.46(9H,m); 7.42~7.33(8H,m); 7. 31~7.26(5H,m); 7.22~7.15(4H,m); 7.12~7.06(3H,m); 5.06(1H,s); 4.08(1H,s); 1.43(3H,s); 1.16(3H,s).

[0125] Referring to the above-mentioned similar synthesis method, the following compounds shown in Table 3 were prepared:

[0126] Table 3

[0127]

[0128]

[0129]

[0130] Example 3

[0131] Preparation of compound C770:

[0132]

[0133] Under nitrogen protection, 20.0 mmol of A8 was dissolved in 40 mL of toluene, 20 mL of ethanol and 20 mL of water, and 24.0 mmol of 4-diphenylaminophenylboronic acid pinacol ester, 60.0 mmol of anhydrous potassium carbonate, 0.2 mmol of Pd(PPh 3 ) 4 The mixture was heated to reflux and stirred for 12 hours, cooled to room temperature, extracted with ethyl acetate, the organic phase was collected, dried, filtered, and the filtrate was concentrated under reduced pressure and purified by silica gel column to obtain compound C770 as a white solid. The yield was 87%. MS (MALDI-TOF): m / z = 783.3757 [M+H] + ; 1 HNMR (δ, CDCl 3): 7.71(2H,s); 7.55~7.46(4H,m); 7.37~7.32(4H,m); 7.30~7.15(13H,m); 7.13~7. 02(11H,m); 6.98~6.93(4H,m); 5.12(1H,s); 3.97(1H,s); 1.43(3H,s); 1.16(3H,s).

[0134] Referring to the above-mentioned similar synthesis method, the compounds shown in Table 4 below were prepared:

[0135] Table 4

[0136]

[0137] In the above embodiment, *—T 2 —* is selected from *—O—*, *—S—* or one of the following structures:

[0138]

[0139] *— and —* represent connecting keys.

[0140] Example 4

[0141] An organic electroluminescent device 100, the structure of which is as follows Figure 1 As shown, the device comprises a substrate 101, an anode layer 102 disposed on the substrate 101, a hole injection layer 103 disposed on the anode layer 102, a hole transport layer 104 disposed on the hole injection layer 103, an electron blocking layer 105 disposed on the hole transport layer 104, a light-emitting layer 106 disposed on the electron blocking layer 105, a hole blocking layer 107 disposed on the light-emitting layer 106, an electron transport layer 108 disposed on the hole blocking layer 107, an electron injection layer 109 disposed on the electron transport layer 108, a cathode layer 110 disposed on the electron injection layer 109, and a CPL layer 111 disposed on the cathode layer, wherein the device preparation method does not include the hole blocking layer 107 comprises the following steps:

[0142] 1) The glass substrate coated with the ITO conductive layer was ultrasonically treated in a cleaning agent for 30 minutes, rinsed in deionized water, ultrasonically treated in an acetone / ethanol mixed solvent for 30 minutes, baked in a clean environment until completely dry, irradiated with an ultraviolet cleaning machine for 10 minutes, and bombarded with a low-energy cation beam.

[0143] 2) Place the treated ITO glass substrate in a vacuum chamber and evacuate to 1×10 -5 ~9×10 -3 Pa, and silver is evaporated on the above ITO film as the anode layer, and the thickness of the evaporated film is The vapor-deposited compounds HI01 and HI102 are used as the hole injection layer, where HI102 is 3% of the mass of HI01 and the vapor-deposited film thickness is

[0144] 3) Continue to evaporate the compound HTM on the hole injection layer to form a hole transport layer, and the evaporated film thickness is

[0145] 4) The compound represented by formula (I) of the present invention is continuously evaporated on the hole transport layer to form an electron blocking layer, and the evaporated film thickness is

[0146] 5) PHT is continuously evaporated on the electron blocking layer as the main material and GD020 is evaporated as the doping material. GD020 accounts for 3% of the mass of PHT as the organic light-emitting layer. The evaporated film thickness is

[0147] 6) Continue to evaporate a layer of LiQ and ET020 on the organic light-emitting layer as an electron transport layer, the mass ratio of LiQ and ET020 is 50:50, and the evaporated film thickness is

[0148] 7) Continue to evaporate a layer of LiF on the electron transport layer as an electron injection layer, and the evaporated film thickness is

[0149] 8) On the electron injection layer, magnesium and silver are evaporated as a transparent cathode layer, the mass ratio of magnesium to silver is 1:10, and the evaporated film thickness is

[0150] 9) On top of the transparent cathode layer, a layer of NPB is evaporated as the CPL layer of the element. The thickness of the evaporated film is The OLED element provided by the present invention is obtained.

[0151] The structures of compounds HI01, HI102, HTM, PHT, GD020, ET020 and LiQ used in Example 4 are as follows:

[0152]

[0153]

[0154] Example 5

[0155] An organic electroluminescent device 200, the structure of which is as follows Figure 2As shown, the device 200 includes a substrate 201, an anode 202, a hole injection layer 203, a hole transport layer 204, a first light emitting layer 205, an electron transport layer 206, a charge generation layer 207, a hole injection layer 208, a hole transport layer 209, a second light emitting layer 210, an electron transport layer 211, an electron injection layer 212, and a cathode 213. The device 200 can be prepared by sequentially depositing the described layers by the preparation method of Example 4. In the corresponding layers of the device 200, materials similar to those described with respect to the device 100 can be used.

[0156] Comparative Example 1

[0157] According to the same steps as in Example 4, the compound represented by formula (I) in step 4) was replaced by B-1 to obtain comparative element 1; the structural formula of B-1 is as follows:

[0158]

[0159] Comparative Example 2

[0160] According to the same steps as in Example 4, the compound represented by formula (I) in step 4) was replaced by B-2 to obtain comparative element 2; the structural formula of B-2 is as follows:

[0161]

[0162] The driving voltage and current efficiency of the organic electroluminescent elements prepared in Example 4 and Comparative Examples 1 and 2, as well as the life of the elements, were measured using a digital source meter and a brightness meter. Specifically, the voltage was increased at a rate of 0.1 V per second, and the brightness of the organic electroluminescent element was measured when it reached 1000 cd / m 2 The voltage at which the light is on is the driving voltage, and the current density at this time is measured at the same time; the ratio of brightness to current density is the current efficiency; the LT90% life test is as follows: use a brightness meter at 1000cd / m 2 At the same brightness, the current is kept constant and the brightness decay of the organic electroluminescent element is measured to be 900cd / m 2 The data listed in Table 5 are relative data compared with Comparative Element 1.

[0163] Table 5 Performance test results of each component

[0164]

[0165]

[0166]

[0167]

[0168]

[0169] As shown in Table 5, the light-emitting element prepared by using the benzotricyclopentadiene derivative as the electron blocking layer material of the present invention also has a high 2 Under the same conditions, the driving voltage is lower than that of B-1 and B-2, and the luminous efficiency and LT90% life performance are significantly improved. The luminous efficiency is as high as 1.4 times that of the comparison element, indicating that the parent core of the compound of the present invention has high stability and is an electron blocking layer material with excellent performance.

[0170] The difference between the benzotricyclopentadiene derivatives of the present invention and the compounds B-1 and B-2 of the comparative examples is that B-1 and B are orthogonal structures of benzotricyclopentadiene, which have great steric hindrance and are not conducive to the close stacking of molecules. The benzotricyclopentadiene derivatives of the present invention have a saturated methylene group and plane rotation conjugation, and the steric hindrance is reduced. The performance of the benzotricyclopentadiene derivatives in molecular film formation and charge transfer is excellent, and the charge transfer inside the element is more balanced. Therefore, the performance of the element is improved, and the compounds of the present invention are more excellent in the performance of the light-emitting element.

[0171] Although the present invention has been described in detail above with general descriptions and specific embodiments, it is obvious to those skilled in the art that some modifications or improvements may be made thereto based on the present invention. Therefore, these modifications or improvements made without departing from the spirit of the present invention all fall within the scope of protection claimed by the present invention.

Claims

1. A benzene - fused triptycene derivative, characterized in that, its structural formula is selected from the group consisting of the following C602 to C772: wherein, *—T 2 —* is selected from one of *—O—*, *—S—* or the following structures: *— and —* represent a bonding connection.

2. An organic electroluminescent material, characterized in that, its raw materials include the benzene - fused triptycene derivative described in claim 1.

3. An organic electroluminescent device, characterized in that, it includes: a first electrode, a second electrode, a light extraction layer, and one or more organic layers disposed between the first electrode and the second electrode; at least one of the organic layer and the light extraction layer includes the benzene - fused triptycene derivative described in claim 1.

4. The organic electroluminescent device according to claim 3, characterized in that, the organic layer includes at least one of the following layers: a hole injection layer, a hole transport layer, an electron blocking layer, a light - emitting layer, an electron transport layer, an electron injection layer, and a hole blocking layer; one or more selected layers among the layers are formed by a deposition process or a solution process.

5. The organic electroluminescent device according to claim 3 or 4, characterized in that, the organic electroluminescent device is used in any one of the following devices: a flat panel display device; a flexible display device; a monochromatic or white flat panel lighting device; or a monochromatic or white flexible lighting device.

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