A spirobiindene derivative and its application

Abstract

The present invention relates to the technical field of organic electroluminescent materials, and in particular to a spirobiindene derivative and its application in electronic components and electronic devices. The structural formula of the spirobiindene derivative is shown in formula (I); the compound shown in formula (I) provided by the present invention has a spirobiindene mother core structure. The compound 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 spirobiindene derivative and its application in organic light-emitting elements and electronic devices. Background Art

[0002] Most of the substances used in organic electroluminescent elements are pure organic substances or organic metal complexes formed by organic substances and metals, and can be divided into hole injectors, hole transporters, luminescent substances, electron transporters, electron injectors, etc. according to their uses. Here, organic substances with relatively small ionization energy are mainly used as hole injectors or hole transporters, and organic substances with large electronegativity are mainly used as electron injectors or electron transporters.

[0003] In addition, the material used as the light-emitting auxiliary layer should preferably meet the following characteristics:

[0004] First, the substances used in organic electroluminescent elements need good thermal stability. The reason is that Joule heat is generated inside the organic electroluminescent element due to the migration of charges. At present, the glass transition temperature of the materials commonly used as hole transport layers is low. Therefore, when driven at low temperatures, the luminous efficiency decreases due to crystallization. Second, in order to reduce the driving voltage, the organic substances adjacent to the cathode and anode need to be designed to have a small charge injection barrier and a high charge mobility. Third, there are always energy barriers at the interface between the electrode and the organic layer, and at the interface between the organic layer and the organic layer, and some charges are inevitably accumulated, so it is necessary to use substances with excellent electrochemical stability.

[0005] Organic electroluminescent devices generally include an anode, a hole injection layer, a hole transport layer, an electroluminescent layer as an energy conversion layer, an electron transport layer and a cathode, which are stacked in sequence. When a voltage is applied to the positive and negative electrodes, the two electrodes generate an electric field. Under the action of the electric field, the electrons on the cathode side move to the electroluminescent layer, and the holes on the anode side also move to the light-emitting layer. The electrons and holes combine in the electroluminescent layer to form excitons, and the excitons are in an excited state and release energy outward, thereby making the electroluminescent layer emit light. Therefore, the luminous efficiency of the light-emitting device depends on the utilization rate of the excitons and the light extraction efficiency. Low light extraction efficiency is one of the common problems of organic light-emitting devices, especially the attenuation caused by reflection caused by the different refractive indices of organic materials between layers, which becomes the main reason for the reduction in device efficiency. In order to reduce this effect, it is necessary to form an organic layer formed by a material with a low refractive index on the side of the light output. However, organic materials have a higher refractive index when they are derived from compounds with unsaturated bonds with high carrier transport and thermal stability.

[0006] Based on the above reasons, the present invention is proposed. Summary of the invention

[0007] The purpose of the present invention is to provide a spirobiindene derivative, in which orthogonal spirobiindene is introduced into triarylamine to increase the proportion of saturated groups in organic materials. The spirobiindene derivative can reduce the refractive index, improve the thermal stability of the material and the ability to transport carriers. The organic electroluminescent element prepared using the spirobiindene derivative can significantly reduce the driving voltage, improve the luminous efficiency and lifespan. Another purpose of the present invention is to provide an application of the compound.

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

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

[0010]

[0011] wherein Ring A represents a 5-membered carbocyclic ring, a 5-membered heterocyclic ring, a 6-membered carbocyclic ring, a 6-membered heterocyclic ring, or there is no Ring A;

[0012] R 1 ~R 8 are each independently selected from hydrogen, deuterium, substituted or unsubstituted C1-C 40 Alkyl, substituted or unsubstituted C2-C 40 Alkenyl, substituted or unsubstituted C1-C 40 Heteroalkyl, substituted or unsubstituted C3-C 40 Cycloalkyl, substituted or unsubstituted C3-C 40 Cycloalkenyl, substituted or unsubstituted C6-C 60 Aryl, substituted or unsubstituted C6-C 60 Arylamine, substituted or unsubstituted C2-C 60 The group consisting of heteroaryl groups, R 1 and R 2 , R 3 and R 4 , R 5 and R 6 , R 7 and R 8 may be optionally joined to form substituted or unsubstituted rings;

[0013] R a , R b Respectively represent one or more to saturated substitution, each independently selected from hydrogen, deuterium, halogen atoms, nitrile groups, substituted or unsubstituted C1-C 40 Alkyl, substituted or unsubstituted C6-C 60 Aryl, substituted or unsubstituted C 10 -C 60 Condensed ring aromatic group, substituted or unsubstituted C6-C 60 Arylamine, substituted or unsubstituted C2-C 60A heterocyclic aromatic group, or a group consisting of a group represented by formula (II), two or more adjacent R a , R b may be arbitrarily joined or fused to form a substituted or unsubstituted ring; and in R a , R b At least one of them is a group represented by formula (II);

[0014]

[0015] L 1 Selected from single bonds, substituted or unsubstituted C6-C 60 Arylene, or substituted or unsubstituted C2-C 60 The group consisting of heteroarylene;

[0016] m is an integer from 0 to 5;

[0017] y is an integer from 1 to 5;

[0018] Ar 1 ,Ar 2 Each is independently selected from substituted or unsubstituted C6-C 60 Aryl, substituted or unsubstituted C 10 -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;

[0019] *—Indicates the location of the bond.

[0020] In the substituted or unsubstituted ring formed by bonding or cyclization described in the present invention, "ring" refers to a substituted or unsubstituted hydrocarbon ring, or a substituted or unsubstituted heterocycle. A condensed ring refers to a condensed aliphatic ring, a condensed aromatic ring, a condensed aliphatic heterocycle, a condensed aromatic heterocycle, or a combination thereof.

[0021] The spirobiindene derivative according to the present invention is represented by the above chemical formula (I), wherein the basic skeleton is formed by combining the formula (I) with at least one group of the formula (II). Compared with the previously known B-1 to B-3 structures, the compound represented by the formula (I) of the present invention is not only electrochemically stable, has excellent hole mobility and electron blocking ability, but also has a high glass transition temperature and excellent thermal stability.

[0022]

[0023] Therefore, the spirobiindene derivative of the present invention has excellent hole transporting ability and electron blocking ability, and can be used as a material for any one of the hole injection layer, hole transport auxiliary layer, or electron blocking layer of the organic layer of the organic electroluminescent element. It is preferably used as a material for any one of the hole transport auxiliary layer and the electron blocking layer, and more preferably used as a material for the electron blocking layer.

[0024] Specifically, the compound shown in the formula (I) of the present invention is a plurality of substituted or unsubstituted spirobiindene derivatives, thereby compared with the known indene derivatives B-1, B-2 and B-3, has a smaller refractive index, stronger hole transport ability and electron blocking ability, can show relatively high luminous efficiency and high glass transition temperature. Thus, when the spirobiindene derivative shown in the formula (I) of the present invention is used for an organic electroluminescent element, not only can excellent thermal stability and carrier transport ability, especially electron blocking ability and luminous ability be expected, but also the driving voltage of the element can be reduced, efficiency and lifespan can be improved, and as the latest electron blocking layer material, the excellent efficiency rise caused by the triplet-triplet fusion effect can be shown due to the high triplet energy level.

[0025] In addition, the spirobiindene derivative represented by formula (I) of the present invention is 1 ~R 8 and R a , R b By introducing a substituent, the HOMO and LUMO energy levels are adjusted according to the type of the substituent, thereby having a wider electrochemical energy level difference Eg, and in an organic electroluminescent element using such a compound, the hole transport property and the electron blocking property can be improved.

[0026] In addition, the spirobiindene derivatives shown in formula (I) of the present invention are introduced into the above-mentioned basic skeleton by a variety of substituted or unsubstituted formula (II) groups, and the molecular weight of the compound is significantly increased, thereby increasing the glass transition temperature, thereby having a higher thermal stability than the previous luminescent materials. Therefore, the performance and life characteristics of the organic electroluminescent element containing the compound according to the present invention can be greatly improved. The organic electroluminescent element with improved performance and life characteristics can ultimately maximize the performance of the full-color organic light-emitting panel.

[0027] The aryl group in the sense of the present invention contains 6 to 60 carbon atoms, and the heteroaryl group contains 2 to 60 carbon atoms and at least one heteroatom, provided that the total number of carbon atoms and heteroatoms is at least 5; the heteroatom is preferably selected from N, O or S. In this case, the two or more rings of the heteroaryl group may be attached to each other simply or in a condensed form, and further, may also include a condensed form with the aryl group. As non-limiting examples of such heteroaryl groups, there can be mentioned six-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl; polycyclic rings such as phenoxathiyl, indolizinyl, indolyl, purinyl, quinolyl, benzothiazolyl, carbazolyl; and 2-furanyl, N-imidazolyl, 2-isoxazolyl, 2-pyridinyl, 2-pyrimidinyl, etc.

[0028] Alkyl in the sense of the present invention is a straight-chain or branched alkyl radical containing 1 to 40 carbon atoms, in which individual hydrogen atoms or -CH2- groups may also be substituted; an alkenyl or alkynyl radical containing at least two carbon atoms, and, by way of non-limiting example, an alkyl, alkenyl or alkynyl radical is preferably taken to mean the following radicals: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, neopentyl, cyclopentyl, n-hexyl, neohexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl.

[0029] Alkoxy is preferably taken to mean alkoxy having 1 to 40 carbon atoms, methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, sec-pentoxy, 2-methylbutoxy, n-hexyloxy, cyclohexyloxy, n-heptyloxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy and 2,2,2-trifluoroethoxy.

[0030] The heteroalkyl group is preferably an alkyl group having 1 to 40 carbon atoms and refers to a group in which a single hydrogen atom or a -CH2- group is replaced by an oxygen, sulfur or halogen atom, and as non-limiting examples, alkoxy, alkylthio, fluorinated alkoxy, fluorinated alkylthio, in particular methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, trifluoromethylthio 4-fluoro-1,4-difluoro-2,4-difluoro-3,4-difluoro-4,4-difluoro-5,4-difluoro-6,4-difluoro-7,4-difluoro-8,4-difluoro-9,4-difluoro-10,4-difluoro-11,4-difluoro-12,4-difluoro-13,4-difluoro-14,4-difluoro-15,4-difluoro-26,4-difluoro-16,4-difluoro-17,4-difluoro-28,4-difluoro-18,4-difluoro-29,4-difluoro-30,4-difluoro-31,4-difluoro-32,4-difluoro-33,4-difluoro-34,4-difluoro-35,4-difluoro-36,4-difluoro-37,4-difluoro-38,4-difluoro-39,4-difluoro-40,4-difluoro-41,4-difluoro-42,4-difluoro-54,4-difluoro-39

[0031] Generally speaking, the cycloalkyl and cycloalkenyl groups according to the present invention can be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptyl, cycloheptenyl, wherein one or more -CH2- groups can be replaced by the above groups; in addition, one or more hydrogen atoms can also be replaced by deuterium atoms, halogen atoms or nitrile groups.

[0032] The heterocycloalkyl group used in the present invention refers to a monovalent functional group obtained by removing one hydrogen atom from a non-aromatic hydrocarbon having an atomic nucleus number of 3 to 40. In this case, one or more carbon atoms, preferably 1 to 3 carbon atoms in the ring are substituted by heteroatoms such as N, O or S. Non-limiting examples thereof include tetrahydrofuranyl, tetrahydrothienyl, morpholinyl, piperazinyl and the like.

[0033] The condensed ring aromatic group used in the present invention refers to a monovalent functional group obtained by removing one hydrogen atom from an aromatic hydrocarbon having 10 to 60 carbon atoms and combining two or more rings. In this case, the two or more rings may be attached to each other in a simple or condensed form. Non-limiting examples thereof include phenanthrenyl, anthracenyl, fluoranthenyl, pyrenyl, triphenylene, perylene, Ji et al.

[0034] The arylamine group used in the present invention refers to an amine substituted by an aryl group having 6 to 60 carbon atoms, and non-limiting examples of the arylamine group include diphenylamine, N-phenyl-1-naphthylamine, N-(1-naphthyl)-2-naphthylamine, etc. The heteroarylamine group refers to an amine substituted by an aryl group having 6 to 60 carbon atoms and a heteroaryl group having 2 to 60 carbon atoms, and non-limiting examples of the heteroarylamine group include N-phenylpyridine-3-amine, N-([1,1'-biphenyl]-4-yl)dibenzo[b,d]furan-2-amine, N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluorene-2-amine, etc.

[0035] The aryloxy group used in the present invention refers to R'O - The monovalent functional group represented by is an aryl group having a carbon number of 6 to 60. Non-limiting examples of such an aryloxy group include phenoxy, naphthoxy, biphenyloxy and the like.

[0036] The alkylsilyl group used in the present invention refers to a silyl group substituted by an alkyl group having 1 to 40 carbon atoms, and the number of carbon atoms constituting the alkylsilyl group is at least 3. Non-limiting examples of the alkylsilyl group include trimethylsilyl and triethylsilyl. The arylsilyl group refers to a silyl group substituted by an aryl group having 6 to 60 carbon atoms.

[0037] The arylphosphino group used in the present invention refers to a diarylphosphino group substituted with an aryl group having 6 to 60 carbon atoms, and non-limiting examples of the arylphosphino group include diphenylphosphino group, di(4-trimethylsilylphenyl)phosphino group, etc. The aryloxyphosphino group is a diarylphosphino group in which the phosphorus atom is oxidized to the highest valence state.

[0038] The aryl boryl group used in the present invention refers to a diaryl boryl group substituted by an aryl group having 6 to 60 carbon atoms, and non-limiting examples of the aryl boryl group include diphenyl boryl and di(2,4,6-trimethylphenyl)boryl. The alkyl boryl group refers to a dialkyl boryl group substituted by an alkyl group having 1 to 40 carbon atoms, and non-limiting examples of the alkyl boryl group include di-tert-butyl boryl and diisobutyl boryl.

[0039] Preferably, the aryl, heteroaryl or heterocyclic aryl is selected from phenyl, naphthyl, anthracenyl, benzanthryl, phenanthrenyl, pyrenyl, yl, peryl, fluoranthene, tetraphenyl, pentacene, benzopyrenyl, biphenyl, phenylene, terphenyl, triphenyl, quadriphenyl, fluorenyl, spirobifluorenyl, dihydrophenanthryl, triphenylene, dihydropyrenyl, tetrahydropyrenyl, cis- or trans-indenofluorenyl, cis- or trans-indenocarbazolyl, indolecarbazolyl, benzofuranocarbazolyl, benzothiophenocarbazolyl, benzocarbazolyl, dibenzocarbazolyl, azadibenzo[g,iD]naphtho[2,1,8-cde]azulene, trimerized indenyl, isotrimerized indenyl, spirotrimerized indenyl, spiroisotrimerized indenyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, indolyl, isoindolyl, carbazolyl, pyridinyl, quinolyl, isoquinolyl, acridinyl, phenanthridinyl, benzo[5,6]quinolyl, benzo[6,7]quinolyl, benzo[7,8]quinolyl, phenothiazinyl, phenoxazinyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxalinoimidazolyl, oxazolyl, benzoxazolyl, naphthoxazolyl, anthrazolyl, phenanthroxazolyl, isoxazolyl, 1,2- Thiazolyl, 1,3-thiazolyl, benzothiazolyl, pyridazinyl, hexaazatriphenylene radical, 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 radical, 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.

[0040] In the present invention, as shown in formula (I), the spirobiindene derivative is preferably selected from the group consisting of the following structures:

[0041]

[0042]

[0043]

[0044] Among them, R a , R b , R 1 ~R 8 , L 1 ,m,Ar 1 ,Ar 2 The meaning is the same as that of formula (I);

[0045] L 2 Selected from single bonds, substituted or unsubstituted C6-C 60 Arylene, or substituted or unsubstituted C2-C 60 The group consisting of heteroarylene;

[0046] n is an integer from 0 to 5;

[0047] Ar 3 ,Ar 4 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.

[0048] Furthermore, the R 1 ~R 8 are each independently selected from hydrogen, deuterium, substituted or unsubstituted C1-C 40 Alkyl, substituted or unsubstituted C3-C 40 Cycloalkyl, substituted or unsubstituted C6-C 60 Aryl, substituted or unsubstituted C6-C 60 A group consisting of aromatic amine groups.

[0049] Furthermore, m is 0, 1 or 2.

[0050] Furthermore, the n is 0, 1 or 2.

[0051] Preferably, the R 1 ~R 8 Each is independently selected from the group consisting of hydrogen, deuterium, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, cyclopentyl, isopentyl, hexyl, cyclohexyl, cycloheptyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted triphenylene, substituted or unsubstituted carbazolyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzofuranyl, and substituted or unsubstituted dibenzothiophenyl.

[0052] According to an embodiment of the present invention, the R 1 ~R 8 Each is independently selected from hydrogen or methyl.

[0053] Furthermore, the Ar 1 ,Ar 2 ,Ar 3 ,Ar 4 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 carbazolyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted fluoranthene, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothiophenyl, substituted or unsubstituted dibenzofuranyl, or substituted or unsubstituted dibenzothiophenyl.

[0054] Preferably, the L 1 , L 2 Each is independently selected from a single bond or a group consisting of the following groups shown in III-1 to III-23:

[0055]

[0056] The dotted line represents the connection site of the group. In this case, the binding position of the group shown in the above formulas III-1 to III-23 is not limited and can be ortho, meta, or para. 1 , L 2 can be independently selected from deuterium, halogen atoms, nitrile groups, C1-C 40 Alkyl, C6-C 60 Aryl and C2-C 60 In the group consisting of heterocyclic aromatic groups, one or more substituents are substituted. In this case, when there are multiple substituents, the multiple substituents are preferably the same as or different from each other.

[0057] 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 40 Alkyl, C2-C 40 Alkenyl, C2-C 40 Alkynyl, C1-C 40 Alkoxy, C3-C 40 Cycloalkyl, C3-C 40 Cycloalkenyl, C6-C 60 Aryl, C6-C 60 Aryloxy, C6-C 60Aryl 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.

[0058] Preferably, the spirobiindene derivative is selected from the compounds represented by the following formulae D100-D225:

[0059]

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066] Wherein, *—X—*, *—T—* are each independently selected from *—O—*, *—S—* or one of the following structures:

[0067]

[0068] *— and —* represent connecting keys.

[0069] The present invention also provides an organic electroluminescent material with a low refractive index, the raw material of which includes the above-mentioned spirobiindene derivative; the organic electroluminescent material including the spirobiindene derivative of the present invention has the ability of carrier transmission and electron blocking.

[0070] The present invention also provides the use of the above-mentioned spirobiindene derivative in the preparation of an organic electroluminescent element.

[0071] The present invention also provides an organic electroluminescent element, which comprises: a first electrode, a second electrode, a capping layer and one or more organic layers disposed between the first electrode and the second electrode; the material of at least one of the organic layers or the capping layer comprises the above-mentioned spirobiindene derivative.

[0072] The organic electroluminescent element comprises a cathode, an anode and at least one light-emitting 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 light-emitting layers. However, it should be noted that each of these layers does not necessarily have to be present. The organic electroluminescent device 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 can 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 spirobiindene derivative of the present invention.

[0073] 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 electron blocking layer or the hole transport 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.

[0074] In the other layers of the organic electroluminescent element according to the invention, in particular in the hole injection and hole transport layers and in the electron injection and electron transport layers, 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.

[0075] Furthermore, preference is given to organic electroluminescent components in which one or more layers are applied by means of a sublimation process, in which the organic electroluminescent components are applied 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.

[0076] Likewise preferred is an organic electroluminescent component in which one or more layers are 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.

[0077] Furthermore, preference is given to organic electroluminescent elements in which one or more layers are produced from solution, for example by spin coating, or by means of any desired printing method, for example screen printing, flexographic printing, lithography, photoinduced thermography, thermal transfer, inkjet printing or nozzle printing. Soluble compounds, for example obtained by suitable substitution. 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 solution and one or more further layers are applied by vapor deposition.

[0078] 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.

[0079] The present invention therefore also relates to a method for producing an organic electroluminescent element according to the invention, applying at least one layer by means of a sublimation method and / or characterized in that at least one layer is applied by means of an organic vapor phase deposition method or by means of carrier gas sublimation and / or characterized in that at least one layer is applied from a solution by spin coating or by means of a printing method.

[0080] Furthermore, the present invention relates to a composition comprising at least one of the spirobiindene derivatives of the invention indicated above. The same preferences as indicated above for the organic electroluminescent element apply to the compounds of the invention. In particular, further compounds may preferably be included in addition to the spirobiindene derivatives. The processing of the spirobiindene derivatives of the invention from the liquid phase, for example by spin coating or by printing methods, requires preparations for the processing of the compounds of the invention. These preparations may, for example, be solutions, dispersions or emulsions. For this purpose, mixtures 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 alcohol, 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.

[0081] Preferably, 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 or an electron blocking layer.

[0082] Furthermore, the hole transport layer, hole transport layer or electron blocking layer comprises the spirobiindene derivative of the present invention.

[0083] Furthermore, the electron blocking layer comprises the spirobiindene derivative of the present invention.

[0084] The present invention also provides a consumer electronic device, which includes the organic electroluminescent element described above. The consumer electronic device described in the present invention can be one of the following devices: flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for internal or external lighting and / or signaling, head-up displays, fully transparent or partially transparent displays, flexible displays, laser printers, telephones, cellular phones, tablet computers, tablet phones, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, video cameras, viewfinders, micro displays with a diagonal of less than 2 inches, 3-D displays, virtual reality or augmented reality displays, vehicles, video walls containing multiple displays tiled together, theater or stadium screens, light therapy devices, and signboards. .

[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] Beneficial effects achieved by the present invention:

[0087] The spirobiindene derivative shown in formula (I) provided by the present invention introduces triarylamine into the spirobiindene of orthogonal structure to increase the proportion of saturated groups in organic materials, reduce the refractive index of molecules, and improve the hole mobility and electron blocking performance of the material at the same time. Due to the hole mobility, electron blocking property, good thermal stability and low refractive index, it can be applied to the organic layer of organic electroluminescent elements. In particular, when the spirobiindene derivative shown in formula (I) of the present invention is applied to an electron blocking layer or a hole transport layer, an organic electroluminescent element with lower driving voltage, higher efficiency and longer life compared with previous electron blocking materials can be manufactured, and further, a full-color display panel with improved performance and life can also be manufactured. BRIEF DESCRIPTION OF THE DRAWINGS

[0088] 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 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 110, and a capping layer (CPL) 111. The device 100 may be manufactured by depositing the described layers in order.

[0089] Figure 2Schematic 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 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 depositing the described layers 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

[0090] The following examples are used to illustrate the present invention but are not intended to limit the scope of the present invention.

[0091] 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.

[0092] 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.

[0093] The test instruments and methods for testing the performance of OLED materials and components in the following embodiments are as follows:

[0094] OLED component performance testing conditions:

[0095] Brightness and chromaticity coordinates: tested using a spectral scanner PhotoResearch PR-715;

[0096] Current density and driving voltage: tested using a digital source meter Keithley 2420;

[0097] Power efficiency: Tested using NEWPORT 1931-C.

[0098] Example 1

[0099] The preparation method of compound D116 comprises the following steps:

[0100] Step 1: Preparation of intermediate Int-1

[0101]

[0102] Under nitrogen protection, 20.0 mmol of sub-1, 22.0 mmol of sub-2 and 80 mL of dry THF were stirred and dissolved, cooled to 0°C, 43.0 mmol of 60% sodium hydride was added in batches, stirred for reaction for 2 hours, heated to reflux for reaction for 2 hours, cooled to room temperature, 20 mL of ice water was added dropwise, the organic phase was separated, the aqueous phase was extracted with ethyl acetate, the organic phase was collected, dried, filtered, the filtrate was concentrated under reduced pressure, and purified by silica gel column to obtain compound Int-1 as a white solid with a yield of 92%.

[0103] Step 2: Preparation of intermediate Int-2

[0104]

[0105] Under nitrogen protection, 20.0 mmol of Int-1 was dissolved in 100 mL of toluene, 20.0 mL of trifluoroacetic acid was added, and 70.0 mmol of triethylsilane was slowly added dropwise. The reaction was stirred for 12 hours, and 50 mL of ice water was added. The organic phase was separated, and the aqueous phase was extracted with toluene. The organic phase was collected, dried, filtered, and the filtrate was concentrated under reduced pressure. It was separated and purified by silica gel column to obtain compound Int-2 as a white solid with a yield of 89%.

[0106] Step 3: Preparation of compound D116

[0107]

[0108] Under nitrogen protection, 24.0 mmol of intermediate Int-2, 20.0 mmol of sub-3, 30.0 mmol of sodium tert-butoxide, 0.02 mmol of Pd2(dba)3 catalyst, 0.04 mmol of Xantphos and 80 mL of toluene were heated to 100°C and stirred for reaction for 15 hours, cooled to room temperature, diluted with 50 mL of water, extracted with toluene, 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 D116;

[0109] X=C(Me)2, yellow solid, yield: 87%, MS (MALDI-TOF): m / z=580.2942[M+H] + ; 1HNMR (δ, CDCl3): 8.25(1H,s); 7.90~7.88(1H,d); 7.72~7.69(2H,m); 7.67~7.62(2H,m); 7.52~7.48(1H,m); 7.39~7.28(5H,m); 7 .17~7.04(6H,m); 7.01~6.94(2H,m); 6.85~6.78(3H,m); 2.93~2.90(2H,m); 2.87~2.83(2H,m); 2.63~2.59(4H,m); 1.68(6H,s).

[0110] X=Ad, yellow solid, yield: 85%, MS (MALDI-TOF): m / z=672.3564[M+H] + ; 1 HNMR (δ, CDCl3): 8.25 (1H, s); 7.90~7.88 (1H, d); 7.72~7.69 (2H, m); 7.67~ 7.62(2H,m); 7.52~7.48(1H,m); 7.39~7.28(5H,m); 7.17~7.04(6H,m); 7.0 1~6.94(2H,m); 6.85~6.78(3H,m); 2.93~2.90(2H,m); 2.87~2.83(2H,m); 2 .63~2.59(4H,m); 1.70~1.61(5H,m); 1.39~1.28(4H,m); 1.05~0.89(5H,m).

[0111] X=FR, yellow solid, yield: 83%, MS (MALDI-TOF): m / z=702.3101[M+H] + ; 1 HNMR (δ, CDCl3): 7.96~7.90(3H,m); 7.72~7.69(2H,m); 7.67~7.62(2H,m); 7.52~7.48(1H,m); 7.46~7.37(6H,m); 7.35~7.28(3H,m); 7 .19~7.12(5H,m); 7.10~7.04(4H,m); 6.96~6.94(1H,m); 6.84~6.77(4H,m); 2.94~2.89(2H,m); 2.87~2.83(2H,m); 2.63~2.59(4H,m).

[0112] X=NPh, yellow solid, yield: 86%, MS (MALDI-TOF): m / z=629.2964[M+H] + ; 1HNMR(δ, CDCl3): 8.52(1H,s); 8.24~8.23(1H,d); 8.09~8.06(1H,m); 7.92~7.8 9(1H,m);7.62~7.59(2H,m);7.57~7.54(1H,m);7.50~7.47(2H,m);7.44~7.35 (5H,m); 7.30~7.24(4H,m); 7.19~7.14(3H,m); 7.10~7.05(4H,m); 7.01~6.99( 2H,d); 6.78(1H,s); 2.94~2.89(2H,m); 2.87~2.83(2H,m); 2.63~2.59(4H,m).

[0113] Example 2

[0114] The preparation method of compound D191 comprises the following steps:

[0115] Step 1: Preparation of intermediate Int-3

[0116]

[0117] Referring to the synthesis method of the first step of Example 1, only sub-1 in the first step of Example 1 was replaced by sub-4 to prepare the intermediate Int-3 as a yellow solid with a yield of 95%.

[0118] Step 2: Preparation of intermediate Int-4

[0119]

[0120] Referring to the synthesis method of the second step of Example 1, only Int-1 in the second step of Example 1 was replaced by Int-3 to prepare the intermediate Int-4 as a yellow solid with a yield of 90%.

[0121] Step 3: Preparation of compound D191

[0122]

[0123] Under nitrogen protection, 24.0 mmol of Int-4 was dissolved in 80 mL of toluene, and then 20.0 mmol of sub-5, 30.0 mmol of anhydrous sodium tert-butoxide, 0.02 mmol of Pd2(dba)3 catalyst, and 0.04 mmol of 10% tri-tert-butylphosphine toluene solution were added, and the temperature was raised to 100°C and stirred for reaction for 15 hours, then cooled to room temperature, 50 mL of water was added to dilute, and the mixture was extracted with toluene. The organic phase was collected, dried, filtered, and the filtrate was concentrated under reduced pressure to dryness, and separated and purified by silica gel column to obtain compound D191;

[0124] X=O, yellow solid, yield: 84%, MS (MALDI-TOF): m / z=604.2578[M+H] + ; 1 HNMR (δ, CDCl3): 7.86~7.84(1H,m); 7.75~7.90(4H,m); 7.75~7.69(4H,m); 7.67~7.57(3H,m); 7.54~7.48(3H,m); 7 .41~7.32(5H,m); 7.17~7.13(1H,m); 7.10~7.05(3H,m); 6.98~6.96(1H,d); 3.18~3.13(4H,m); 2.71~2.65(4H,m).

[0125] X=S, yellow solid, yield: 80%, MS (MALDI-TOF): m / z=620.2352[M+H] + ; 1 HNMR (δ, CDCl3): 8.04(1H,s); 7.86~7.81(2H,m); 7.75~7.69(3H,m); 7.66~7.57(5H,m); 7.52~7.46(2H,m); 7.4 4~7.37(4H,m); 7.25~7.20(3H,m); 7.17~7.13(2H,m); 7.10~7.05(3H,m); 3.19~3.13(4H,m); 2.71~2.65(4H,m).

[0126] X=Nnap, yellow solid, yield: 83%, MS (MALDI-TOF): m / z=729.3283[M+H] + ; 1 HNMR (δ, CDCl3): 8.23(1H,s); 8.16(1H,s); 7.92~7.86(3H,m); 7.75~7.69(4H,m); 7.67~7.61(3H,m); 7.52~7.47(3H,m); 7.44~7 .38(4H,m); 7.36~7.30(6H,m); 7.26~7.21(2H,m); 7.17~7.13(1H,m); 7.09~7.04(4H,m); 3.19~3.13(4H,m); 2.71~2.65(4H,m).

[0127] Example 3 to Example 126

[0128] Referring to the above-mentioned similar synthesis method, the compounds shown in Table 1 below were prepared:

[0129] Table 1

[0130]

[0131]

[0132]

[0133]

[0134]

[0135]

[0136]

[0137]

[0138] In the above embodiments, *—X—*, *—T—* are each independently selected from *—O—*, *—S—* or one of the following structures:

[0139]

[0140] *— and —* represent connecting keys.

[0141] Embodiment 126

[0142] An OLED element 100, such as Figure 1 As shown, the OLED element of this embodiment is a top emission element, including a substrate 101, an anode 102 arranged on the substrate 101, a hole injection layer 103 arranged on the anode 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, an organic light emitting layer 106 arranged on the electron blocking layer 105, a hole blocking layer 107 arranged on the organic 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 110 arranged on the electron injection layer 109, and a capping layer 111 on the cathode. The preparation method of the OLED element without the hole blocking layer 107 comprises the following steps:

[0143] 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.

[0144] 2) Place the treated ITO glass substrate in a vacuum chamber and evacuate the chamber to a vacuum of less than 1×10 -5Pa, and silver is evaporated on the above ITO film as the anode layer, and the thickness of the evaporated film is Continue to evaporate compounds HI01 and HI02 as hole injection layers, where HI02 is 3% of the mass of HI01 and the evaporated film thickness is

[0145] 3) Continue to evaporate the compound HTM on the hole injection layer to form a hole transport layer, and the evaporated film thickness is

[0146] 4) The compound represented by formula (I) of the present invention is continuously evaporated on the hole transport layer as an electron blocking layer, and the evaporated film thickness is

[0147] 5) Compound RH015 as the main material and RD015 as the doping material are continuously deposited on the electron blocking layer, RD015 is 5% of the mass of RH015, and the organic light-emitting layer obtained by evaporation has a film thickness of

[0148] 6) A layer of LiQ and compound ET028 is continuously evaporated on the organic light-emitting layer as the electron transport layer of the element, wherein the compound ET028 is 50% of the mass of LiQ and the evaporated film thickness is

[0149] 7) Continue to evaporate a layer of LiF on the electron transport layer as an electron injection layer, and the evaporated film thickness is

[0150] 8) On the electron injection layer, magnesium and silver are evaporated as the transparent cathode layer of the element. The mass ratio of magnesium to silver is 1:10, and the thickness of the evaporated film is

[0151] 9) On top of the transparent cathode layer, a layer of CPD 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.

[0152] The structure of the compound used in Example 126 is as follows:

[0153]

[0154] Embodiment 127

[0155] An organic electroluminescent element 200, the structure of which is as follows Figure 2As shown, it comprises 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 electroluminescent element 200 is prepared by a similar preparation method as in Example 126.

[0156] Comparative Example 1

[0157] According to the same steps as in Example 126, the compound of formula (I) of the present invention in step 4) was replaced with H01 to obtain comparative element 1;

[0158]

[0159] The organic electroluminescent element prepared by the above process was subjected to the following performance tests:

[0160] The driving voltage and current efficiency of the organic electroluminescent elements prepared in the above-mentioned Examples 126, 127 and Comparative Example 1 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 LT95% life test is as follows: use a brightness meter at 10000cd / m 2 At the same brightness, the current is kept constant and the brightness decay of the organic electroluminescent element is measured to be 9500cd / m 2 The data listed in Table 2 are relative data compared with the comparative element 1.

[0161] Table 2

[0162]

[0163]

[0164]

[0165]

[0166] As shown in Table 2, the OLED element prepared by the compound of the present invention has a lower driving voltage than H01 at the same brightness, and the current efficiency is significantly improved, up to 1.25 times that of the comparison element, and the LT95% life of the element is 10000cd / m 2The spirobiindene derivative of the present invention has very excellent performance under the initial brightness condition and the accelerated aging test, indicating that the spirobiindene derivative of the present invention is an electron blocking layer material with excellent performance.

[0167] 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 spirobiindene derivative, characterized in that: The spirobiindene derivative is selected from the group consisting of the following structures: Among them, R a , R b is hydrogen; R 1 ~R 8 is hydrogen or methyl; L 1 is a single bond; m is 0; Ar 1 ,Ar 2 Each is independently selected from the group consisting of phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, phenanthryl, triphenylene, carbazolyl, fluorenyl, anthracenyl, fluoranthenyl, benzofuranyl, benzothiophenyl, dibenzofuranyl, and dibenzothiophenyl.

2. A spirobiindene derivative, characterized in that: The spirobiindene derivative is selected from the compounds shown below: Wherein, *—X—*, *—T—* are each independently selected from *—O—*, *—S—* or one of the following structures: *— and —* represent connecting keys.

3. Use of the spirobiindene derivative according to any one of claims 1 to 2 in the preparation of an organic electroluminescent element.

4. An organic electroluminescent element, characterized in that: It includes: A first electrode, a second electrode, a capping layer, and one or more organic layers disposed between the first electrode and the second electrode; The material of at least one of the organic layer and the capping layer comprises the spirobiindene derivative according to any one of claims 1 to 2.

5. The organic electroluminescent element according to claim 4, 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 or an electron blocking layer; The hole transport layer or the electron blocking layer comprises the spirobiindene derivative according to any one of claims 1 to 2.

6. A consumer electronic device, characterized in that: It comprises the organic electroluminescent element as claimed in claim 4.

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