A silane fluorene derivative and an organic electroluminescent element containing the same

Abstract

The present invention relates to the technical field of organic electroluminescent materials, and in particular to a silyfluorene derivative as shown in Formula I and an organic electroluminescent element comprising the same. The compound shown in Formula I provided by the present invention improves the thermal stability of the material and the ability to transport carriers. The material of the present invention can be used 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 silyfluorene derivative and application thereof in an organic electroluminescent element. Background Art

[0002] Generally speaking, organic luminescence refers to the phenomenon that light is emitted 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 in the process of industrialization, there are still many problems to be solved. 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. In particular, the luminous efficiency and service life of the light-emitting components have not yet 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. Summary of the invention

[0006] The object of the present invention is to provide a silylfluorene derivative.

[0007] Another object of the present invention is to provide an organic electroluminescent material containing the above-mentioned silane fluorene derivative.

[0008] Another object of the present invention is to provide an organic electroluminescent element and the use of the above-mentioned silyfluorene derivative in the preparation of the organic electroluminescent element.

[0009] To achieve the above object, the present invention adopts the following technical solution:

[0010] A silylfluorene derivative, the structural formula of which is shown in Formula I:

[0011]

[0012] in:

[0013] R a , R b Each independently selected from hydrogen, C1-C 40 Alkyl, substituted or unsubstituted C6-C 60 Aryl, substituted or unsubstituted C6-C 60 Arylamine, or substituted or unsubstituted C2-C 60 The group consisting of heterocyclic aromatic groups;

[0014] W is each independently selected from N or CR 5 , or any two adjacent W are groups represented by formula (II) or formula (III),

[0015]

[0016] A represents CR in the same or different way in each occurrence 6 or N, and "^" indicates any two adjacent groups W in formula (I);

[0017] G is selected from O, S, NAr 3 or CR 7 R 8 ;

[0018] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are each independently selected from hydrogen, deuterium, halogen, nitrile, substituted or unsubstituted C6-C 60 Aryl, substituted or unsubstituted C6-C 60 Condensed ring aromatic group, substituted or unsubstituted C2-C 60 A heterocyclic aromatic group or a group consisting of formula (IV), and in R 1 , R 2 , R 3 , R 4 , R 5 At least two of them are groups represented by formula (IV);

[0019]

[0020] Ar 1 ,Ar 2 ,Ar 3 Each is independently selected from substituted or unsubstituted C6-C 60 Aryl, substituted or unsubstituted C6-C 60 Condensed ring aromatic group, substituted or unsubstituted C6-C 60 Arylamine, or substituted or unsubstituted C2-C 60 The group consisting of heterocyclic aromatic groups, Ar 1 and Ar 2 may be optionally joined or fused to form a substituted or unsubstituted ring containing or not containing N, O, S, Si, B or CR 7 R 8 ;

[0021] L 1 Selected from single bonds, substituted or unsubstituted C6-C 60 Arylene, substituted or unsubstituted C2-C 60 The group consisting of heterocyclic arylene groups;

[0022] R 0 , R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 Each independently selected from the group consisting of hydrogen, deuterium, fluorine, nitrile, a C1-C 40 Straight chain alkyl with C1~C 40 Straight chain heteroalkyl with C3~C 40 A branched or cyclic alkyl group having C3~C 40 branched or cyclic heteroalkyl, substituted or unsubstituted C6-C 60 Aryl or substituted or unsubstituted C2-C 60 Heterocyclic aryl, and any two or more adjacent substituents may be optionally joined or fused to form a substituted or unsubstituted ring, which may or may not contain N, O, S, Si, P or B;

[0023] n is an integer selected from 0 to 5;

[0024] *—Indicates L 1 A connecting bond to formula (I).

[0025] 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.

[0026] Preferably, the silanol derivative is selected from one or more of the following structures:

[0027]

[0028]

[0029] Among them, R 1 , R 2 , R 3 , R 4 , R 5 is hydrogen or a radical of formula (IV) at each occurrence, and in R 1 , R 2 , R 3 , R 4 , R 5 At least two of them are groups represented by formula (IV), preferably, R 1 , R 2 , R 3 , R 4 Each occurrence is a group represented by formula (IV).

[0030] Preferably, G is O, S or CR 7 R 8 .

[0031] Preferably, n is selected from 0, 1 or 2.

[0032] Preferably, the R a , R b is selected from the group consisting of methyl, ethyl or phenyl.

[0033] Preferably, R 5 , R 6 is hydrogen or deuterium.

[0034] Preferably, R 7 , R 8 Each is independently selected from the group consisting of hydrogen, methyl, phenyl and fluorenyl.

[0035] Preferably, in the above compounds, the L 1 Selected from a single bond or the group consisting of the following groups shown in III-1 to III-15:

[0036]

[0037] in,

[0038] Z 11 and Z 12Each 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 C1-C 60 Alkyl, C2-C 60 Alkenyl, C2-C 60 Alkynyl, C1-C 60 Alkoxy, C3-C 60 Cycloalkane, C3-C 60 Cycloalkene, substituted or unsubstituted C6-C 60 Aryl, substituted or unsubstituted C6-C 60 Aryloxy, substituted or unsubstituted C6-C 60 aryl thioether group, or substituted or unsubstituted C2-C 60 The group consisting of heterocyclic aromatic groups;

[0039] Z 13 Indicates substituted or unsubstituted C6-C 60 Aryl, substituted or unsubstituted C6-C 60 Aryloxy, substituted or unsubstituted C6-C 60 aryl thioether group, or substituted or unsubstituted C2-C 60 One or more of heterocyclic aromatic groups;

[0040] 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;

[0041] T2 means O, S, CR ’ R" or NAr ’ ;

[0042] R ’ , R" are each independently selected from hydrogen, deuterium, C1~C 60 Alkyl, C1~C 60 heteroalkyl, substituted or unsubstituted C6-C 60 Aryl, substituted or unsubstituted C6-C 60 Arylamine, or substituted or unsubstituted C2-C 60 The group consisting of heterocyclic aromatic groups, R ’ and R" may be optionally joined or fused to form another multiple substituted or unsubstituted ring, containing or not containing one or more heteroatoms N, P, B, O or S in the formed ring; preferably, R ’ , R" is methyl, phenyl or fluorenyl;

[0043] Ar ’ Choose from C1~C 60 Alkyl, C1~C 60 Heteroalkyl, C3~C60 Cycloalkyl, substituted or unsubstituted C6-C 60 Aryl, substituted or unsubstituted C6-C 60 Condensed ring aromatic group, substituted or unsubstituted C6-C 60 Arylamine, or substituted or unsubstituted C2-C 60 The group consisting of heterocyclic aromatic groups; preferably, Ar ’ is methyl, ethyl, phenyl or naphthyl;

[0044] It represents the bond connecting the substituent to the main structure.

[0045] Aryl radicals in the sense of the present invention contain 6 to 60 carbon atoms and heteroaryl radicals contain 2 to 60 carbon atoms and at least one heteroatom, with the proviso that the sum of carbon atoms and heteroatoms is at least 5, the heteroatoms being preferably selected from N, O or S. Aryl and heteroaryl radicals are in particular radicals derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene, Perylene, fluoranthene, tetracene, pentacene, benzopyrene, biphenyl, isophenyl, terphenyl, triphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, cis- or trans-indenocarbazole, cis- or trans-indolocarbazole, trimerized indene, isotrimerized indene, spirotrimerized indene, spiroistrimerized indene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline , isoquinoline, acridine, phenanthridine, benzo[5,6]quinoline, benzo[6,7]quinoline, benzo[7,8]quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthymidazole, phenanthroimidazole, pyridimidazole, pyrazinimidazole, quinoxalinoimidazole, oxazole, benzoxazole, naphthymidazole, anthraoxazole, phenanthrooxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, hexaazatriphenylene, benzopyridazine, pyrimidine, benzene pyrimidine, quinoxaline, 1,5-diazaanthracene, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenoxazine, phenothiazine, fluorescein ring, naphthyridine, azacarbazole, benzocarboline, carboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine, quinazoline and benzothiadiazole or radicals derived from combinations of these systems.

[0046] In the present invention, the term "substituted or unsubstituted" means a group 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 C1-C 60 Alkyl, C2-C 60 Alkenyl, C2-C 60 Alkynyl, C1-C 60 Alkoxy, C3-C 60 Cycloalkyl, C3-C 60 Cycloalkenyl, C6-C 60 Aryl, C6-C 60 Aryloxy, C6-C 60 Aryl sulfide group and C2-C 60 The heterocyclic aryl group may be substituted or unsubstituted with one or more substituents, or may be substituted or unsubstituted with a substituent in which two or more substituents among the substituents exemplified above are linked together.

[0047] Preferably, the silanol derivative is selected from the following group consisting of C01 to C180:

[0048]

[0049]

[0050]

[0051]

[0052]

[0053]

[0054]

[0055]

[0056]

[0057]

[0058]

[0059] Wherein, *—T3—* is selected from *—O—*, *—S—* or one of the following structures:

[0060]

[0061] *—G—* is selected from *—O—*, *—S—* or one of the following structures:

[0062]

[0063] *— and —* represent connecting keys.

[0064] In one aspect, the present invention provides a method for preparing a silanol derivative of formula (I), as shown in the following scheme 1:

[0065] Scenario 1:

[0066] In Scheme 1, the symbols used are as defined in formula (I), and X is Cl, Br, I or OTf;

[0067] Specifically, the compound of formula (I) is prepared by a palladium-catalyzed or base-catalyzed coupling reaction of a compound C having a silylfluorene core structure and a compound D or D′ containing an aromatic amine substituent.

[0068] The palladium catalyst that can be used for the palladium-catalyzed coupling reaction can be selected from: any one of Pd(P-tBu3)2, Pd(PPh3)4, Pd2(dba)3, Pd2(dba)3CHCl3, PdCl2(PPh3)2, PdCl2(CH3CN)2, Pd(OAc)2, Pd(acac)2, Pd / C, PdCl2, [Pd(allyl)Cl]2, etc., or a mixture of two or more thereof.

[0069] 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.

[0070] 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.

[0071] Furthermore, compounds of Formula D and D' can be prepared using conventional organic reactions or can be obtained from commercial sources.

[0072] The present invention also provides a material, the raw material of which includes the above-mentioned silanol derivative organic electroluminescent material, preferably, the 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 capping layer (CPL) material or an electron blocking layer material. The material containing the compound of the present invention has the ability of carrier transport or light extraction.

[0073] The present invention also provides an organic electroluminescent element, which comprises a first electrode, a second electrode, a CPL and one or more organic layers disposed between the first electrode and the second electrode; the material of at least one layer of the organic layer or the CPL comprises the above-mentioned compound.

[0074] The organic electroluminescent element comprises a cathode, an anode, a CPL and at least one luminescent layer. In addition to these layers, it may also comprise other layers, for example, in each case, one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, exciton blocking layers, electron blocking layers and / or charge generation layers. An intermediate layer having, for example, an exciton blocking function may also be introduced between two luminescent 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 luminescent layer, or it may comprise multiple luminescent layers. That is, a variety of luminescent compounds capable of luminescence are used in the luminescent layer. A system having three luminescent layers is particularly preferred, wherein the three layers can display blue, green and red luminescence. If there are more than one luminescent layer, then according to the present invention, at least one of these layers comprises a compound of the present invention.

[0075] Furthermore, the organic electroluminescent element according to the present invention does not contain a separate hole injection layer and / or hole transport layer and / or hole blocking layer and / or electron 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.

[0076] In the other layers of the organic electroluminescent element according to the invention, in particular in the hole transport layer and in the emitting layer and in the CPL, 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 emitting layer according to the invention without inventive effort.

[0077] Furthermore, preference is given to organic electroluminescent components in which one or more layers can be applied by means of a sublimation process, in which the organic electroluminescent components are deposited in a vacuum sublimation apparatus at temperatures below 10 -5 Pa, preferably less than 10 -6 The 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.

[0078] 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 1000 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.

[0079] In addition, preferred are organic electroluminescent elements 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.

[0080] 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 invention without inventive step.

[0081] 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.

[0082] 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.

[0083] Preferably, in the above organic electroluminescent element, the organic layer includes a hole injection layer, a hole transport layer, a hole blocking layer, a light emitting layer, a CPL, an electron transport layer, an electron injection layer or an electron blocking layer.

[0084] The present invention also provides the use of the above compound in preparing an organic electroluminescent element.

[0085] In addition, unless otherwise specified, the raw materials used in the present invention can be obtained commercially, and any range recorded 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.

[0086] The present invention also relates to a mixture comprising at least one compound of formula (I) or the above preferred embodiments and at least one other compound. If the compound according to the present invention is used as a matrix material, the other compound may be a fluorescent or phosphorescent emitter. The mixture may then also contain other materials as additional matrix materials. The present invention also relates to the use of the compound according to the present invention in electronic components. Preferably, as mentioned above, the compound according to the present invention is used in a hole transport layer or as a matrix material in a light-emitting layer. The compounds according to the present invention and the electronic components, in particular organic electroluminescent components, which can be obtained therefrom are distinguished from the prior art by one or more of the following surprising advantages:

[0087] 1. Compared with electronic components obtained using conventional compounds, electronic components obtainable using the compounds of the present invention exhibit very high stability and very long life.

[0088] 2. The electronic components obtainable using the compounds of the present invention exhibit high efficiency, in particular high luminescence efficiency and high external quantum efficiency.

[0089] 3. The compounds of the present invention provide low operating voltage.

[0090] 4. The compounds according to the present invention can be processed using conventional methods, so that cost advantages can also be achieved.

[0091] 5. The films obtainable using the compounds of the present invention exhibit excellent quality, particularly in terms of film uniformity.

[0092] 6. The compounds of the present invention can be produced in a very rapid and easy manner using conventional methods, so that cost advantages can also be achieved.

[0093] The advantages mentioned above are not accompanied by a reduction in other electronic properties.

[0094] It should be noted that variations of the embodiments described in the present invention fall within the scope of the present invention. Each feature disclosed in the present invention may be replaced by an alternative feature having the same, equivalent or similar purpose unless expressly excluded. Therefore, unless otherwise stated, each feature disclosed in the present invention should be regarded as an example of a generic series or an equivalent or similar feature.

[0095] All features of the present invention can be combined with each other in any way, unless specific features and / or steps are mutually exclusive. This is particularly applicable to the preferred features of the present invention. Similarly, features that are not necessarily combined can be used alone (and not in combination). It should also be noted that many features, particularly the features of the preferred embodiments of the present invention, are creative in themselves and should not be considered as only part of the embodiments of the present invention. For these features, independent protection may be sought in addition to or as a substitute for each invention currently claimed.

[0096] The teaching of the technical actions disclosed in the present invention can be extracted and combined with other embodiments. The present invention is explained in more detail by the following examples, but it is not intended to limit the present invention. Based on the description, those skilled in the art will be able to perform the present invention within the disclosed entire scope, and will not pay creative work and will be able to prepare other compounds of the present invention and use them in electronic components, or use method of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0097] Figure 1 A schematic diagram of an organic electroluminescent element 100 is shown.

[0098] Figure 2 A schematic diagram of an organic electroluminescent element 200 is shown. DETAILED DESCRIPTION

[0099] The present invention is further described in detail below with reference to specific embodiments, but is not intended to limit the scope of the present invention.

[0100] 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.

[0101] 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.

[0102] The test instruments and methods for testing the performance of OLED materials and components in the following embodiments are as follows:

[0103] OLED component performance testing conditions:

[0104] Brightness and chromaticity coordinates: tested using a spectral scanner PhotoResearch PR-715;

[0105] Current density and lighting voltage: tested using Keithley 2420 digital source meter;

[0106] Power efficiency: Tested using NEWPORT 1931-C.

[0107] Example 1

[0108] The preparation method of compound C-1 comprises the following steps:

[0109]

[0110] Preparation of compound Int-1:

[0111] Under nitrogen protection, 0.26 mol of 2'-bromo-2,4-dichloro-1,1'-biphenyl was dissolved in 600 mL of dry THF, cooled to -78°C, and 0.39 mol of 2.5 M n-butyl lithium n-hexane solution was added dropwise. The mixture was stirred for 20 minutes, and 0.40 mol of dimethylchlorosilane was added dropwise. The mixture was heated to room temperature and stirred for 24 hours. 200 mL of saturated aqueous ammonium chloride solution was added dropwise. The organic phase was separated, and the aqueous phase was extracted with ethyl acetate. The organic phase was collected, dried, filtered, and the filtrate was concentrated under reduced pressure to dryness. The filtrate was separated and purified by silica gel column to obtain compound Int-1 as a white solid with a yield of 89%.

[0112] Preparation of compound C-1:

[0113] Under nitrogen protection, 18.0 mmol of triphenylphosphine, 3.0 mmol of [RhCl(cod)]2 catalyst and 450 mL of 1,4-dioxane were mixed and stirred at room temperature for 30 minutes. 0.2 mol of Int-1 was added and the temperature was raised to 80°C and stirred for 12 hours. The mixture was concentrated under reduced pressure and purified by silica gel column to obtain a white solid C-1 with a yield of 66%. GC-MS (EI): 278.01, 280.01.

[0114] Referring to the above-mentioned similar synthesis method, the products shown in Table 1 were prepared.

[0115] Table 1 Correspondence between reactants, synthetic products and yields

[0116]

[0117]

[0118]

[0119]

[0120]

[0121] Example 2

[0122] Preparation of compound C01:

[0123]

[0124] 10.0 mmol of C-1 was dissolved in 60 mL of xylene. Under nitrogen protection, 21.0 mmol of phenyldiphenylamine, 25.0 mmol of sodium tert-butoxide, 0.2 mmol of cuprous iodide, 0.1 mmol of Pd2(dba)3 catalyst, and 0.2 mmol of Xantphos were added. The temperature was raised to 110° C. and stirred for reaction for 16 hours. The temperature was lowered to room temperature, 20 mL of water was added for dilution, and the mixture was extracted with toluene. The organic phase was collected, dried, filtered, and the filtrate was concentrated under reduced pressure to dryness. The compound C01 was separated and purified by silica gel column to obtain a yield of 78%. After vacuum sublimation, HPLC: 99.97%, MS (MALDI-TOF): m / z=697.3053 [M+H] + ; 1 HNMR (δ, CDCl3): 7.85~7.83(1H,m); 7.74~7.68(4H,m); 7.62~7.59(2H,m); 7.54~7.50(4H,m); 7.48~7.43(5H,m); 7 .40~7.35(6H,m); 7.25~7.19(4H,m); 7.15(1H,s); 7.11(1H,s); 7.08~7.02(4H,s); 6.99~6.94(2H,m); 0.21(6H,s).

[0125] Referring to the above-mentioned similar synthesis method, the products shown in Table 2 were prepared.

[0126] Table 2 Correspondence table of reactants, synthetic products and yields

[0127]

[0128]

[0129]

[0130]

[0131]

[0132]

[0133]

[0134] Example 3

[0135] Preparation of compound C163:

[0136]

[0137] Under nitrogen protection, 10.0 mmol of C-11 was dissolved in 40 mL of toluene, and 22.0 mmol of 9-phenylcarbazole-3-boric acid, 50.0 mmol of anhydrous potassium carbonate, 0.2 mmol of cuprous iodide, and 0.01 mmol of Pd132 catalyst were added. Then 20 mL of ethanol and 20 mL of water were added, and the mixture was stirred under reflux at elevated temperature for 16 hours. The mixture was cooled to room temperature, diluted with 50 mL of water, extracted with ethyl acetate, and the organic phase was collected, dried, filtered, and the filtrate was concentrated under reduced pressure and purified by silica gel column to obtain compound C163 with a yield of 82%. After vacuum sublimation, HPLC: 99.95%, MS (MALDI-TOF): m / z=770.3433 [M+H] + ; 1 HNMR(δ, CDCl3): 8.39(1H,s); 8.25~8.21(2H,m); 8.12(1H,s); 8.03~7.95(3H,m); 7.74~7.72(1H,d ); 7.69~7.61(8H,m); 7.54~7.46(9H,m); 7.37~7.27(8H,m); 7.23~7.16(6H,m); 7.12~7.08(1H,m).

[0138] Referring to the similar synthesis method mentioned above, the products shown in Table 3 were prepared.

[0139] Table 3 Correspondence between reactants, synthetic products and yields

[0140]

[0141]

[0142]

[0143] Example 4

[0144] An organic electroluminescent element 200, the structure of which is as follows Figure 2As shown, it includes 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, an electron transport layer 107 disposed on the light-emitting layer 106, an electron injection layer 108 disposed on the electron transport layer 107, a cathode layer 109 disposed on the electron injection layer 108, and a CPL layer 110 disposed on the cathode layer, and its preparation includes the following steps:

[0145] 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.

[0146] 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 compound of the present invention is evaporated as a hole injection layer, and the evaporated film thickness is

[0147] 3) Continue to evaporate the compound HTM on the hole injection layer to form a hole transport layer, and the evaporated film thickness is

[0148] 4) Continue to evaporate the compound EBL on the hole transport layer as an electron blocking layer, and the evaporated film thickness is

[0149] 5) PHT is continuously evaporated on the electron blocking layer as the main material and GD110 is evaporated as the doping material. GD110 accounts for 3% of the mass of PHT as the organic light-emitting layer. The evaporated film thickness is

[0150] 6) Continue to evaporate a layer of LiQ and ET06 on the organic light-emitting layer as an electron transport layer, the mass ratio of LiQ and ET06 is 50:50, and the evaporated film thickness is

[0151] 7) Continue to evaporate a layer of LiF on the electron transport layer as an electron injection layer, and the evaporated film thickness is

[0152] 8) On the electron injection layer, magnesium and silver are evaporated as a transparent cathode layer, the mass ratio of magnesium to silver is 1:2, and the thickness of the evaporated film is

[0153] 9) On the transparent cathode layer, a layer of the compound of the present invention is evaporated as the CPL layer of the element, and the evaporated film thickness is The OLED element provided by the present invention is obtained.

[0154] The structures of the compounds HTM, EBL, PHT, GD110, ET06 and LiQ used in Example 4 are as follows:

[0155]

[0156] Example 5

[0157] An organic electroluminescent element 100, the structure of which is as follows Figure 1 As shown, it includes a substrate 101, an anode layer 102 arranged on the substrate 101, a hole injection layer 103 arranged on the anode layer 102, a hole transport layer 104 arranged on the hole injection layer 103, an electron blocking layer 105 arranged on the hole transport layer 104, a light-emitting layer 106 arranged on the electron blocking layer 105, a hole blocking layer 107 arranged on the light-emitting layer 106, an electron transport layer 108 arranged on the hole blocking layer 107, an electron injection layer 109 arranged on the electron transport layer 108, a cathode layer 110 arranged on the electron injection layer 109, and a CPL layer 111 arranged on the cathode layer 110.

[0158] Comparative Example 1

[0159] According to the same steps as in Example 4, the compound of the present invention in step 2) and step 9) was replaced by H-1 to obtain comparative element 1;

[0160]

[0161] Comparative Example 2

[0162] According to the same steps as in Example 4, the compound of the present invention in step 2) and step 9) was replaced by H-2 to obtain comparative element 2;

[0163]

[0164] The organic electroluminescent element prepared by the above process was subjected to the following performance tests:

[0165] 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 current density of the organic electroluminescent element was measured when it reached 10 mA / cm 2The voltage at this time is the driving voltage, and the brightness at this time is measured at the same time; the ratio of brightness to current density is the current efficiency; the LT95% 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 950cd / m 2 The time is in hours, and the performance test data of the obtained components are normalized with reference to the comparative component 1, and the results are listed in Table 4:

[0166] Table 4 Performance test results of each component

[0167]

[0168]

[0169]

[0170]

[0171]

[0172]

[0173] In the above, Ph is a phenyl group, PhPh is a biphenyl group, Nap is a naphthyl group, and Me is a methyl group.

[0174] As shown in Table 4, the light-emitting element prepared by using the silicon fluorene derivative as the hole material and the CPL material also has a high power consumption at 10 mA / cm 2 Under the same conditions, the driving voltage is lower than that of H-1 and H-2, the luminous efficiency is improved, and excellent luminous performance is shown, and the LT95% life span has a significant advantage. This shows that the compound disclosed in the present invention has a better carrier balance ability than the comparative element due to the replacement of the carbon atom at the 9th position of fluorene with a silicon atom. The performance of the compound of the present invention as a hole material can prove that the compound of the present invention is an excellent type of hole material.

[0175] Although the present invention has been described in detail above by general description, specific implementation methods and experiments, it is obvious to those skilled in the art that some modifications or improvements can be made to the present invention. Therefore, these modifications or improvements made without departing from the spirit of the present invention all belong to the scope of protection claimed by the present invention.

Claims

1. A silylfluorene derivative, characterized in that: The structural formula of the silanol derivative is selected from the group shown below: Wherein, *—T3—* is selected from *—O—* or *—G—* is selected from *—O—*, *—S—* or *— and —* represent connecting keys.

2. An organic electroluminescent material, characterized in that: The raw material of the organic electroluminescent material comprises the silane fluorene derivative according to claim 1.

3. An organic electroluminescent element, characterized in that: The invention comprises a first electrode, a second electrode, a CPL and one or more organic layers disposed between the first electrode and the second electrode; the material of at least one layer of the organic layer or the CPL comprises the silicon fluorene derivative according to claim 1.

4. The organic electroluminescent element according to claim 3, characterized in that: The organic layer includes a hole injection layer, a hole transport layer, a hole blocking layer, a light emitting layer, an electron transport layer, an electron injection layer, a CPL or an electron blocking layer.

5. The use of the silyfluorene derivative according to claim 1 in an organic electroluminescent element, characterized in that: The silylfluorene derivative is used for a hole transport layer, a hole blocking layer, a light emitting layer, an electron transport layer, an electron injection layer, a CPL or an electron blocking layer of the organic electroluminescent element.

6. A consumer product comprising an organic electroluminescent element, wherein the organic electroluminescent element comprises: a first electrode, a second electrode, and an organic layer disposed between the first electrode and the second electrode, wherein the organic layer comprises a compound, and the compound comprises the silylide derivative according to claim 1.

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