CN115710186A - Fluorene derivative and application thereof - Google Patents

Fluorene derivative and application thereof Download PDF

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CN115710186A
CN115710186A CN202211327341.0A CN202211327341A CN115710186A CN 115710186 A CN115710186 A CN 115710186A CN 202211327341 A CN202211327341 A CN 202211327341A CN 115710186 A CN115710186 A CN 115710186A
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substituted
unsubstituted
group
layer
fluorene derivative
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曹建华
张海威
李程辉
王振宇
唐伟
刘赛赛
徐先锋
李利铮
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Shanghai 800 Million Spacetime Advanced Material Co ltd
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Abstract

The invention relates to the technical field of organic electroluminescent materials, in particular to a fluorene derivative and application thereof. The structural formula of the fluorene derivative is shown as a formula (I); the compound shown in the formula (I) has a fluorenylene structure. The compound is applied to an organic electroluminescent elementIn the device, the driving voltage can be obviously reduced, the luminous efficiency is improved, and the service life is prolonged;
Figure DDA0003912387970000011

Description

Fluorene derivative and application thereof
Technical Field
The invention relates to the technical field of organic electroluminescent materials, in particular to a fluorene derivative and application thereof in an organic light-emitting element.
Background
In general, the organic light emitting phenomenon refers to a phenomenon in which light is emitted when electric energy is applied to an organic substance; that is, when an organic layer is disposed 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 a ground state, light and heat are emitted.
In recent years, organic electroluminescent display technologies have become mature, some products have entered the market, but many problems still need to be solved in the industrialization process. In particular, various organic materials used for manufacturing elements have many problems which are not solved, such as carrier injection and transmission performance, electroluminescent performance of the materials, service life, color purity, matching between various materials and between various electrodes, and the like; especially, the luminous efficiency and the service life of the light-emitting element are not practical, which greatly limits the development of the OLED technology. The metal complex phosphorescent material utilizing triplet state luminescence has high luminescence efficiency, and green and red materials of the metal complex phosphorescent material meet the use requirements, but the metal complex phosphorescent material requires a phosphorescent material or a hole material with a high triplet state energy level to be matched with the metal complex phosphorescent material, so that the development of the phosphorescent material or the hole material with the high triplet state energy level is an urgent need of the current development of the OLED.
Under the current technological development, improvements are also needed, both for fluorescent materials and for phosphorescent materials, in particular in terms of operating voltage, efficiency and lifetime for use in organic electroluminescent elements and in terms of thermal stability during sublimation.
In order to overcome the above-described problems and further improve the characteristics of the organic electroluminescent element, development of a more stable and effective substance that can be used as a phosphorescent material or a hole-forming material in the organic electroluminescent element is continuously required.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a fluorene derivative which can improve the thermal stability of materials and the capability of transporting carriers, and an organic electroluminescent element prepared by the fluorene derivative can obviously reduce the driving voltage, improve the luminous efficiency and prolong the service life; another object of the present invention is to provide the use of the compound.
Specifically, the invention provides the following technical scheme:
the invention provides a fluorene derivative, the structural formula of which is shown as the formula (I):
Figure BDA0003912387950000011
wherein the content of the first and second substances,
L 1 selected from the group consisting of single bonds, substituted or unsubstituted C 6 -C 60 Arylene, or substituted or unsubstituted C 2 -C 60 Heteroarylene;
R 1 、R 2 each independently selected from hydrogen, substituted or unsubstituted C 1 -C 40 Alkyl, substituted or unsubstituted C 2 -C 40 Alkenyl, substituted or unsubstituted C 3 -C 40 Cycloalkyl, substituted or unsubstituted C 3 -C 40 Cycloalkenyl, substituted or notSubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 2 -C 60 Heteroaryl, or R 1 And R 2 Cyclizing to form the following formula A 1 ～A 7 The group shown:
Figure BDA0003912387950000021
and R is 1 And R 2 Up to one of which may be selected from substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 2 -C 60 A heteroaryl group;
R 3 selected from hydrogen, deuterium, fluorine, hydroxyl, nitrile group, nitro group, carboxyl group or carboxylate thereof, sulfonic group or sulfonate thereof, phosphoric group or phosphate thereof, and substituted or unsubstituted C 1 -C 40 Alkyl, substituted or unsubstituted C 1 -C 40 Alkoxy, substituted or unsubstituted C 2 -C 40 Alkenyl, substituted or unsubstituted C 1 -C 40 Alkylthio, substituted or unsubstituted C 1 -C 40 Alkoxy, substituted or unsubstituted C 3 -C 40 Cycloalkyl, substituted or unsubstituted C 1 -C 40 Alkyl sulfoxide group, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Aryloxy, substituted or unsubstituted C 6 -C 60 Arylthio, substituted or unsubstituted C 3 -C 40 Silyl, or substituted or unsubstituted C 2 -C 60 Heterocyclic aryl groups; r 3 Is one or more;
Ar 1 、Ar 2 each independently selected from the group consisting of substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Condensed ring aryl, substituted or unsubstituted C 6 -C 60 Arylamino, or substituted or unsubstituted C 2 -C 60 Heterocyclic aryl groups; wherein Ar is 1 、Ar 2 、L 1 Optionally joined or cyclized to form a substituted or unsubstitutedSubstituted ring, with or without heteroatom O, S, N or Si in the formed ring;
Figure BDA0003912387950000022
is represented by the formula 1 Or R 2 The connecting key of (2).
In the present invention, the "ring" refers to a substituted or unsubstituted hydrocarbon ring or a substituted or unsubstituted heterocyclic ring in which adjacent groups are bonded to each other to form a substituted or unsubstituted ring. The condensed ring is a condensed aliphatic ring, a condensed aromatic ring, a condensed aliphatic heterocyclic ring, a condensed aromatic heterocyclic ring, or a combination thereof.
The fluorene derivative according to the present invention is represented by the above chemical formula (I), wherein the fluorene derivative comprises an alkene and a heteroaryl group-containing group L 1 NAr 1 Ar 2 Combine to form a basic skeleton. The compound represented by the formula (I) of the present invention is electrochemically stable and has excellent hole mobility, and has a high glass transition temperature and excellent thermal stability, as compared with conventionally known B-1 to B-4 structures.
Figure BDA0003912387950000023
Accordingly, the fluorene derivative of the present invention has excellent hole transport ability and light emitting characteristics, and thus can be used as a material for any one of a hole injection layer, a hole transport layer, a light emitting layer, and an electron blocking layer of an organic electroluminescent device. The material that can be used as either one of the light-emitting layer and the electron-blocking layer is preferable, and the material that can be used as the electron-blocking layer is more preferable.
Specifically, the compound represented by formula (I) of the present invention has stronger hole transport ability and electron blocking ability, and can exhibit relatively high luminous efficiency and high glass transition temperature, compared to alkenes containing two aryl groups, such as B-1 to B-4, which have a strong ability to donate electron groups, by including fluorene derivatives of alkenes and triarylamines. Accordingly, when the fluorene derivative represented by formula (I) of the present invention is used in an organic electroluminescent device, not only excellent thermal stability and carrier transport ability, particularly electron blocking ability and light emitting ability, but also a reduction in driving voltage of the device, an improvement in efficiency and lifetime, and the like can be expected, and an excellent increase in efficiency due to a triplet-triplet fusion effect can be exhibited as a new electron blocking layer material because of a high triplet level.
Further, the fluorene derivative represented by formula (I) of the present invention is obtained by reacting a fluorene derivative containing triarylamine with an alkene-containing substituent R 1 、R 2 And a substituent R 3 By introducing the compound, the HOMO and LUMO energy levels are adjusted according to the kind of the substituent, so that the compound can have a wide band gap, and can maximally exhibit high hole-transporting properties and electron-blocking properties in an organic electroluminescent element using such a compound.
Further, the fluorene derivative represented by the formula (I) of the present invention is obtained by introducing various substituents L to the basic skeleton 1 And Ar 1 、Ar 2 Particularly, aryl and/or heteroaryl groups have higher thermal stability than conventional light-emitting materials because the molecular weight of the compound is significantly increased and the glass transition temperature is increased. Therefore, the performance and life characteristics of the organic electroluminescent element comprising the compound according to the present invention can be greatly improved. The organic electroluminescent element with improved performance and life characteristics can finally maximize the performance of a full-color organic light-emitting panel.
The fluorene derivative represented by the formula (I) of the present invention contains R 1 And R 2 In this case, preferably, the fluorene derivative is selected from the group consisting of the following structures:
Figure BDA0003912387950000031
wherein n, m are each independently selected from integers of 0 to 40;
p, q are each independently selected from integers of 1 to 40;
R 4 、R 5 each independently selected from hydrogen, deuterium, fluorine, nitrile group, methyl group, tertiary butyl group, phenyl group, biphenyl group and terphenyl groupPhenyl, naphthyl, phenanthryl, triphenylene, carbazolyl, fluorenyl, dibenzofuran, or dibenzothiophene.
Preferably, R is 3 、R 4 、R 5 Each independently hydrogen, tert-butyl or phenyl.
Preferably, n and m are each independently selected from integers of 0 to 10.
Preferably, p and q are each independently selected from integers of 1 to 5.
Preferably, the aryl, heteroaryl or heteroaryl is selected from the group consisting of phenyl, naphthyl, anthryl, benzanthryl, phenanthryl, pyrenyl,
Figure BDA0003912387950000042
A phenyl group, a perylene group, a fluoranthenyl group, a tetracenyl group, a pentacenyl group, a benzopyrenyl group, a biphenyl group, an idophenyl group, a terphenyl group, a fluorenyl group, a spirobifluorenyl group, a dihydrophenanthryl group, a triphenylene group, a dihydropyrenyl group, a tetrahydropyrenyl group, a cis-or trans-indenofluorenyl group, a cis-or trans-indenocarbazolyl group, an indolocarbazole group, a benzofurocarbazolyl group, a benzothienocarbazolyl group, a benzocarbazolyl group, a dibenzocarbazolyl group, an azadibenzo [ g, iD ] group]Naphtho [2,1,8-cde]Azulene, trimeric indenyl, isotridecyl, spirotrimeric indenyl, spiroisotridecyl, furyl, benzofuryl, isobenzofuryl, dibenzofuryl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, indolyl, isoindolyl, carbazolyl, pyridyl, 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, quinoxaloimidazolyl, oxazolyl, benzoxazolyl, naphthooxazolyl, anthraoxazolyl, phenanthroixazolyl, isoxazolyl, 1,2-thiazolyl, 1,3-thiazolyl, benzothiazolyl, pyridazinyl, hexaazabenzophenanthryl, benzopyrazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1,5-diazaanthraceneGroups derived from these groups include, for example, a group selected from the group consisting of a phenyl group, 2,7-diazpyrenyl group, 2,3-diazpyrenyl group, 1,6-diazpyrenyl group, 1,8-diazpyrenyl group, 4,5-diazpyrenyl group, 4,5,9,10-tetraazaperynyl group, pyrazinyl group, phenazinyl group, phenothiazinyl group, fluoresceinyl group, naphthyridinyl group, azacarbazolyl group, benzocarbazinyl group, carbolinyl group, phenanthrolinyl group, 1,2,3-triazolyl group, 1,2,4-triazolyl group, benzotriazolyl group, 1,2,3-oxadiazolyl group, 1,2,4-oxadiazolyl group, 34 zxft 3734-oxadiazolyl group, 1,3,4-oxadiazolyl group, 5852-thiadiazolyl group, 3575-thiadiazolyl group, 3625-zxft 3725-543838-diaziridinyl group, 74xft-7446-triazinyl group, 74xft-7446-triazolyl group, and a tetrazolyl group derived from a group, a group derived from a combination of these groups.
Further, said Ar 1 、Ar 2 Each independently selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted biphenylyl, substituted or unsubstituted terphenylyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted dibenzofuranyl, or substituted or unsubstituted dibenzothiophene.
In the fluorene derivative represented by the formula (I) of the present invention, L 1 The fluorene derivative containing the alkene and the NAr 1 Ar 2 The attached functional group, in this case, preferably, L is 1 Selected from a single bond or a group consisting of the following groups III-1 to III-23:
Figure BDA0003912387950000041
wherein the dotted line represents the linking site of the group, and in this case, the binding site of the group represented by the above formulas III-1 to III-23 is not limited, and may be ortho, meta, or para. L mentioned above 1 Can be independently selected from deuterium, halogen atom, nitrile group and C 1 -C 40 Alkyl radical, C 6 -C 60 Aryl and C 2 -C 60 When the substituent is plural, it is preferable that plural substituents are the same as or different from each other.
In the present invention, the term "substituted or unsubstituted" means a compound selected from the group consisting of hydrogen, deuterium, a halogen atom, a hydroxyl group, a nitrile group, a nitro group, an amino group, an amidino 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, and C 1 -C 40 Alkyl radical, C 2 -C 40 Alkenyl radical, C 2 -C 40 Alkynyl, C 1 -C 40 Alkoxy radical, C 3 -C 40 Cycloalkyl radical, C 3 -C 40 Cycloalkenyl radical, C 6 -C 60 Aryl radical, C 6 -C 60 Aryloxy radical, C 6 -C 60 An arylthioether group and C 2 -C 60 The heterocyclic aryl group may be substituted or unsubstituted with 1 or more substituents, or may be substituted or unsubstituted with substituents formed by connecting 2 or more substituents among the above-exemplified substituents.
Aryl in the sense of the present invention contains 6 to 60 carbon atoms and heteroaryl contains 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 heteroatom is preferably selected from N, O or S. In this case, two or more rings of the heteroaryl group may be attached to each other simply or in a condensed form, and further, may include a form condensed with the aryl group. As non-limiting examples of such heteroaryl groups, six-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl; polycyclic rings such as phenoxathiyl, indolizinyl, indolyl, purinyl, quinolinyl, benzothiazolyl, carbazolyl, and the like; and 2-furyl, N-imidazolyl, 2-isoxazolyl, 2-pyridyl, 2-pyrimidyl and the like.
Alkyl in the sense of the present invention contains 1 to 40 carbon atoms and where the individual hydrogen atoms or-CH 2 -a linear alkyl group or an alkyl group with a branched chain, the groups of which may also be substituted; alkenyl or alkynyl groups contain at least two carbon atoms, as non-limiting examplesAlkyl, alkenyl or alkynyl are preferably taken to mean the following groups: 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.
Alkoxy, preferably alkoxy having from 1 to 40 carbon atoms, is to be understood as meaning methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, sec-pentoxy, 2-methylbutoxy, n-hexoxy, cyclohexyloxy, n-heptoxy, cycloheptoxy, n-octoxy, cyclooctoxy, 2-ethylhexoxy, pentafluoroethoxy and 2,2,2-trifluoroethoxy.
Heteroalkyl is preferably alkyl having 1 to 40 carbon atoms, meaning that the individual hydrogen atoms or-CH 2 The radicals substituted by oxygen, sulfur or halogen atoms, 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, trifluoromethoxy, pentafluoroethoxy, pentafluoroethylthio, 2,2,2-trifluoroethoxy, 2,2,2-trifluoroethylthio, vinyloxy, propenyloxy, propenylthio, butenyloxy, pentenyloxy, pentenylthio, cyclopentenyloxy, cyclopentenylthio, hexenyloxy, hexenylthio, cyclohexenyloxy, cyclohexenylthio, ethynyloxy, ethynylthio, propynyloxy, propynylthio, butynyloxy, butynylthio, pentynyloxy, pentynylthio, hexynyloxy, hexynylthio, as non-limiting examples.
In general, the cycloalkyl, cycloalkenyl groups according to the invention can be cyclopropyl, cyclobutyl, cycloPentyl, cyclohexyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptyl, cycloheptenyl, wherein one or more-CH 2 The radicals may be replaced by the radicals mentioned above; furthermore, one or more hydrogen atoms may also be replaced by deuterium atoms, halogen atoms or nitrile groups.
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 a nuclear number of 3 to 40. At this point, more than one carbon, preferably 1 to 3 carbons, in the ring is substituted with a heteroatom such as N, O or S. As non-limiting examples thereof, there are tetrahydrofuran, tetrahydrothiophene, morpholine, piperazine and the like.
The fused ring aryl group used in the present invention is a monovalent functional group obtained by combining two or more rings and removing one hydrogen atom from an aromatic hydrocarbon having 6 to 60 carbon atoms. In this case, two or more rings may be attached to each other simply or in a condensed form. As non-limiting examples thereof, may be mentioned phenanthryl, anthracyl, fluoranthenyl, pyrenyl, triphenylenyl, perylenyl, perylene,
Figure BDA0003912387950000051
And the like.
The arylamine group used in the present invention means an amine substituted with an aryl group having 6 to 60 carbon atoms, and non-limiting examples of the arylamine group include a diphenylamine group, an N-phenyl-1-naphthylamine group, an N- (1-naphthyl) -2-naphthylamine group and the like. The heteroarylamine group means an amine substituted with an aryl group having 6 to 60 carbon atoms and a heteroaryl group having 2 to 60 carbon atoms, and as non-limiting examples of the heteroarylamine group, there are N-phenylpyridin-3-amine group, N- ([ 1,1 '-biphenyl ] -4-yl) dibenzo [ b, d ] furan-2-amine group, N- ([ 1,1' -biphenyl ] -4-yl) -9,9-dimethyl-9H-fluoren-2-amine group, and the like.
Alkoxy as used herein means RO - The monovalent functional group is represented by R is an alkyl group having 1 to 40 carbon atoms and may have a linear, branched or cyclic structure. Non-limiting examples of such alkoxy groups include methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentyloxy, cyclopentyloxy, cyclohexyloxy, and the like.
Aryloxy as used in the present invention means R' O - The monovalent functional group is represented by R' which is an aryl group having 6 to 60 carbon atoms. As non-limiting examples of such aryloxy groups, there are phenoxy, naphthoxy, biphenyloxy and the like.
The alkylsilyl group used in the present invention means a silyl group substituted with an alkyl group having 1 to 40 carbon atoms, and the number of carbon atoms constituting the alkylsilyl group is at least 3, and as non-limiting examples of the alkylsilyl group, trimethylsilyl group, triethylsilyl group, and the like are given. The arylsilyl group means a silyl group substituted with an aryl group having 6 to 60 carbon atoms.
The arylphosphorus group used in the present invention means a diarylphosphorus group substituted with an aryl group having 6 to 60 carbon atoms, and non-limiting examples of the arylphosphorus group include a diphenylphosphoryl group, a bis (4-trimethylsilylphenyl) phosphorus group and the like. The aryloxyphosphorus group is a group in which the phosphorus atom of the diarylphosphorus group is oxidized to the highest valence state.
The arylboron group used in the present invention means a diarylboron group substituted with an aryl group having 6 to 60 carbon atoms, and non-limiting examples of the arylboron group include a diphenylboron group, a bis (2,4,6-trimethylbenzene) boron group, and the like. The alkylboron group means a dialkylboron group substituted with an alkyl group having 1 to 40 carbon atoms, and non-limiting examples of the alkylboron group include a di-tert-butylboron group, a diisobutylboron group and the like.
Preferably, the fluorene derivative is selected from compounds represented by the following formula D475 to D606:
Figure BDA0003912387950000061
Figure BDA0003912387950000071
Figure BDA0003912387950000081
Figure BDA0003912387950000091
Figure BDA0003912387950000101
Figure BDA0003912387950000111
Figure BDA0003912387950000121
wherein, x-T 1 —*、*—T 2 Each independently selected from-O-, -S-, or one of the structures shown below:
Figure BDA0003912387950000122
* -and-represent a connecting bond.
The present invention also provides a method for preparing the fluorene derivative as described above, as shown in scheme 1:
in the case of the scheme 1,
Figure BDA0003912387950000131
in scheme 1, the symbols used are as defined in formula (I), and X is 1 Is Cl, br or OTf;
the raw materials for synthesizing the compound shown in the formula (I) can be purchased from commercial sources, the method principle, the operation process, the conventional post treatment, the column purification, the recrystallization purification and other means are well known by the synthesizers in the field, and the synthesis process can be completely realized to obtain the target product.
Specifically, the compound of formula (I) is prepared from iodo benzene derivatives S0 and R 1 、R 2 Decarboxylation substitution reaction of substituted alpha-bromoacrylic acidAn intermediate S1; intermediates S1 and Ar 1 Ar 2 NL 1 Subjecting the boronic acid or boronic acid pinacol ester to SUZUKI coupling reaction to prepare a compound of formula (I) or reacting the compound with Ar 1 Ar 2 The compound of formula (I) of the present invention is prepared by Buchwald-Hartwig coupling reaction of NH. Intermediate Ar 1 Ar 2 NL 1 Boronic acid or boronic acid pinacol ester of (A) and Ar 1 Ar 2 The NH is prepared by a palladium-catalyzed or base-catalyzed coupling reaction.
As palladium catalysts which can be used for the palladium-catalyzed coupling reaction, there may be selected: pd (P- t Bu 3 ) 2 、Pd(PPh 3 ) 4 、Pd 2 (dba) 3 、Pd 2 (dba) 3 CHCl 3 、PdCl 2 (PPh 3 ) 2 、PdCl 2 (CH 3 CN) 2 、Pd(OAc) 2 、Pd(acac) 2 、Pd/C、PdCl 2 、[Pd(allyl)Cl] 2 And the like, or a mixture of two or more thereof is used.
In addition, the base used in the palladium-catalyzed coupling reaction or base-catalyzed coupling reaction may 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 and the like, and mixtures of one or two or more thereof.
The coupling reaction may be carried out in an organic solvent, wherein the organic solvent may be selected from: ether solvents such as diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, ethylene glycol ethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ether, diethylene glycol diethyl ether, or anisole, aromatic hydrocarbon solvents such as benzene, toluene, or xylene, chlorobenzene, dichlorobenzene, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, and sulfolane, and one kind or a mixture of two or more kinds thereof can be used.
The invention also provides an organic electroluminescent material, the raw material of which comprises the fluorene derivative; the organic electroluminescent material comprising the fluorene derivative of the present invention has a carrier transporting ability.
The invention also provides the application of the fluorene derivative in preparing organic electroluminescent elements.
The present invention also provides an organic electroluminescence element including: the organic light-emitting diode comprises a first electrode, a second electrode, a capping layer and more than one organic layer arranged between the first electrode and the second electrode; the material of at least one of the organic layer or the capping layer includes the fluorene derivative described above.
The organic electroluminescent element includes a cathode, an anode, and at least one light-emitting layer. In addition to these layers, it may also comprise further layers, for example in each case one or more hole-injecting, hole-transporting, hole-blocking, electron-transporting, electron-injecting, exciton-blocking, electron-blocking and/or charge-generating layers. An intermediate layer having, for example, exciton blocking function can likewise be introduced between the two light-emitting layers. However, it should be noted that each of these layers need not be present. The organic electroluminescent device described herein may include one light emitting layer, or it may include a plurality of light emitting layers. That is, a plurality of light-emitting compounds capable of emitting light are used in the light-emitting layer. Particularly preferred are systems with three light-emitting layers, wherein the three layers can exhibit blue, green and red light emission. If more than one light-emitting layer is present, at least one of these layers comprises the fluorene derivative of the present invention according to the present invention.
Further, the organic electroluminescent element according to the invention does not comprise a separate hole injection layer and/or hole transport layer and/or hole blocking layer and/or electron transport layer, i.e. the light-emitting layer is directly adjacent to the electron blocking layer or hole transport layer or the anode and/or the light-emitting layer is directly adjacent to the electron transport layer or electron injection layer or the cathode.
In the other layers of the organic electroluminescent element according to the invention, in particular in the hole-injecting and hole-transporting layer and in the electron-injecting and electron-transporting layer, all materials can be used in the manner conventionally used according to the prior art. A person skilled in the art will thus be able to use all materials known for organic electroluminescent elements in combination with the luminescent layer according to the invention without inventive effort.
Preference is furthermore given to organic electroluminescent elements in which one or more layers are applied by means of a sublimation process in which the temperature in a vacuum sublimation apparatus is below 10 -5 Pa, preferably less than 10 -6 Pa is applied by vapor deposition. However, the initial pressure may also be even lower, e.g. below 10 -7 Pa。
Preference is likewise given to organic electroluminescent elements in which one or more layers are applied by means of an organic vapor deposition method or by means of carrier gas sublimation, where 10 -5 The material is applied under a pressure between Pa and 1 Pa. A particular example of this method is the organic vapour jet printing method, in which the material is applied directly through a nozzle and is therefore structured.
Preference is furthermore 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, offset printing, photoinitiated thermal imaging, thermal transfer, ink-jet printing or nozzle printing. Soluble compounds, for example, are obtained by appropriate substitution. These methods are also particularly suitable for oligomers, dendrimers and polymers. Furthermore, hybrid methods are possible, in which, for example, one or more layers are applied from solution and one or more further layers are applied by vapor deposition.
These methods are generally known to those skilled in the art, and they can be applied to an organic electroluminescent element comprising the compound according to the present invention without inventive labor.
The invention therefore also relates to a method for producing an organic electroluminescent element according to the invention, at least one layer being applied by means of a sublimation method, and/or at least one layer being applied by means of an organic vapour deposition method or by means of carrier gas sublimation, and/or at least one layer being applied from solution by spin coating or by means of a printing method.
Furthermore, the present invention relates to fluorene derivatives comprising at least one of the above indicated invention. The same preferences as indicated above for the organic electroluminescent elements apply to the compounds according to the invention. In particular, it is preferable that other compounds may be contained in addition to the fluorene derivative. Processing of the fluorene derivatives of the present invention from the liquid phase, for example by spin coating or by printing methods, requires the processing of formulations of the compounds of the present invention. These formulations 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, (-) -fenchone, 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 -terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanone, cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, methyl benzoate, 1-methylpyrrolidone, p-cymene, phenetole, 3835-diisopropylbenzene, dibenzyl ether, triethylmethyl butyl glycol, triethylbutyl glycol, tripropyl glycol, diethylbutyl glycol, tripropyl glycol, or mixtures of these solvents.
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.
Further, the light emitting layer or the electron blocking layer comprises the fluorene derivative of the present invention.
Further, the electron blocking layer comprises the fluorene derivative of the present invention.
The invention also provides a consumer product comprising the organic electroluminescent element.
In addition, unless otherwise specified, all starting materials for use in the present invention are commercially available, and any range recited herein includes any value between the endpoints and any subrange between the endpoints and any value between the endpoints or any subrange between the endpoints.
The invention has the following beneficial effects:
the fluorene derivative represented by formula (I) provided by the present invention is excellent in hole mobility, electron blocking property, thermal stability and light emitting property, and thus can be applied to an organic layer of an organic electroluminescent device. In particular, when the fluorene derivative represented by formula (I) of the present invention is used in an electron blocking layer or a light emitting layer, an organic electroluminescent element having a lower driving voltage, higher efficiency, and a longer lifetime than those of conventional electron blocking materials can be manufactured, and furthermore, a full-color display panel having improved performance and lifetime can be manufactured.
Drawings
Fig. 1 shows a schematic diagram of an organic light emitting device 100. The illustrations are not necessarily drawn to scale. The device 100 may include a substrate 101, an anode layer 102, a hole injection layer 103, a hole transport layer 104, an electron blocking layer 105, a light emitting layer 106, a hole blocking layer 107, an electron transport layer 108, an electron injection layer 109, a cathode layer 110, and a capping layer (CPL) 111. The device 100 may be fabricated by sequentially depositing the described layers.
Fig. 2 shows a schematic diagram of an organic light emitting device 200 with two light emitting layers. The device comprises a substrate 201, an anode layer 202, a hole injection 203, a hole transport layer 204, a first light emitting layer 205, an electron transport layer 206, a charge generation layer 207, a hole injection layer 208, a hole transport layer 209, a second light emitting layer 210, an electron transport layer 211, an electron injection layer 212, and a cathode layer 213. The device 200 may be prepared by sequentially depositing the described layers. Since the most common OLED devices have one light emitting layer, while device 200 has a first light emitting layer and a second light emitting layer, the light emitting peak shapes of the first light emitting layer and the second light emitting layer may be overlapping or cross-overlapping or non-overlapping. In the corresponding layers of the device 200, materials similar to those described with respect to the device 1 may be used. Fig. 2 provides one example of how some layers may be added from the structure of device 100.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
In the description of the present invention, "a plurality" means two or more unless otherwise specified; the terms "upper", "lower", and the like, indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience in describing the present invention and simplifying the description, but do not indicate or imply that the referred devices or elements must have a specific orientation, be constructed and operated in a specific orientation, and thus, should not be construed as limiting the present invention.
The experimental procedures used in the following examples are conventional unless otherwise specified. The experimental raw materials and the related equipments used in the following examples are commercially available unless otherwise specified, and the percentages are by mass unless otherwise specified.
The following examples are provided for testing the performance of OLED materials and devices using the following test apparatus and method:
OLED element performance detection conditions:
luminance and chromaticity coordinates: testing with a photosresearch PR-715 spectrum scanner;
current density and lighting voltage: testing using a digital source table Keithley 2420;
power efficiency: tested using NEWPORT 1931-C.
Example 1
A process for preparing compound D558, comprising the steps of:
the first step is as follows: preparation of intermediate A1
Figure BDA0003912387950000151
Under the protection of nitrogen, 20.0mmol of 4 '-chloro-2-iodo-1,1' -biphenyl was dissolved inTo 50mL of DMSO, 26.0mmol of 2-bromoacrylic acid derivative SM-2, 2.0mmol of palladium acetate, and 4.0mmol of P (o-tol) 3 40.0mmol of anhydrous potassium carbonate and 40.0mmol of anhydrous potassium acetate, heating to 110 ℃, stirring for reaction for 12 hours, cooling to room temperature, pouring the reaction liquid into 250mL of water, filtering, washing a filter cake with water, and separating and purifying a solid by using a silica gel column to obtain an intermediate A1 which is a white solid with the yield of 58%.
With reference to the analogous synthetic procedures described above, the following intermediates were prepared:
Figure BDA0003912387950000152
Figure BDA0003912387950000161
Figure BDA0003912387950000171
Figure BDA0003912387950000181
Figure BDA0003912387950000191
the second step is that: preparation of Compound D558
Figure BDA0003912387950000192
Under the protection of nitrogen, 12.0mmol of the intermediate A1, 10.0mmol of diarylamine, 15.0mmol of sodium tert-butoxide and 0.01mmol of Pd 2 (dba) 3 Catalyst, 0.04mmol of 10% tri-tert-butylphosphine toluene solution and 50mL of toluene, heating to 100 ℃, stirring for reaction for 15 hours, cooling to room temperature, adding 50mL of water for dilution, extracting with dichloromethane, collecting organic phaseDrying, filtering, concentrating the filtrate under reduced pressure, and separating and purifying with silica gel column to obtain compound D558;
T 1 ，T 2 is CMe 2 White solid, yield: 78%, MS (MALDI-TOF): m/z =698.3803[ M ] +H] + ； 1 HNMR(δ、CDCl 3 )：8.28(1H,s)；7.87～7.86(2H,m)；7.77～7.76(2H,m)；7.49～7.43(3H,m)；7.36～7.28(6H,m)；7.26～7.20(5H,m)；7.16～7.12(2H,m)；4.05(2H,s)；2.11～2.10(10H,d)；1.96(2H,s)；1.68(12H,s)。
T 1 Is 9,9-fluorenyl, T 2 Is CMe 2 White solid, yield: 76%, MS (MALDI-TOF): m/z =820.3951[ m + H ]] + ； 1 HNMR(δ、CDCl 3 )：8.28(1H,s)；7.87～7.85(3H,m)；7.78～7.76(3H,m)；7.52～7.42(7H,m)；7.38～7.26(8H,m)；7.24～7.16(5H,m)；7.14～7.12(2H,m)；4.05(2H,s)；2.11～2.10(10H,d)；1.96(2H,s)；1.68(6H,s)。
With reference to the above synthetic method, the following compounds shown in table 1 were prepared:
TABLE 1
Figure BDA0003912387950000193
Figure BDA0003912387950000201
Figure BDA0003912387950000211
Figure BDA0003912387950000221
Figure BDA0003912387950000231
Figure BDA0003912387950000241
Figure BDA0003912387950000251
Example 2
Preparation of compound D597:
Figure BDA0003912387950000252
under the protection of nitrogen, mixing 10.0mmol of intermediate A32, 12.0mmol of pinacol borate SM-3, 36.0mmol of anhydrous potassium carbonate and 40mL of toluene, adding 0.01mmol of Pd132 catalyst, 20mL of ethanol and 20mL of water, heating to reflux, stirring, reacting for 12 hours, cooling to room temperature, adding 50mL of water for dilution, extracting with dichloromethane, collecting an organic phase, drying, filtering, concentrating the filtrate under reduced pressure, and separating and purifying by using a silica gel column to obtain a compound D597, T597 1 ：CMe 2 White solid, yield: 78%, MS (MALDI-TOF): m/z =746.3795[ M + H ]] + ； 1 HNMR(δ、CDCl 3 )：8.29(1H,s)；8.09(1H,s)；7.90～7.88(1H,d)；7.79～7.76(1H,m)；7.74～7.68(4H,m)；7.65～7.60(2H,m)；7.56～7.42(5H,m)；7.40～7.33(5H,m)；7.30～7.26(3H,m)；7.23～7.14(7H,m)；7.07～7.02(2H,m)；1.68(6H,s)；1.07(9H,s)。
T 1 Is 9,9-fluorenyl, white solid, yield: 75%, MS (MALDI-TOF): m/z =868.3957[ M + H ]] + ； 1 HNMR(δ、CDCl 3 )：8.28(1H,s)；8.09(1H,s)；7.90～7.81(4H,m)；7.79～7.76(1H,m)；7.74～7.68(4H,m)；7.65～7.60(2H,m)；7.56～7.42(7H,m)；7.40～7.32(6H,m)；7.30～7.26(6H,m)；7.23～7.14(6H,m)；7.07～7.02(2H,m)；1.07(9H,s)。
With reference to the analogous synthetic procedures described above, the following compounds shown in table 2 were prepared:
TABLE 2
Figure BDA0003912387950000253
Figure BDA0003912387950000261
Example 3
Preparation of compound D604:
Figure BDA0003912387950000262
under the protection of nitrogen, 12.0mmol of intermediate A47, 10.0mmol of diarylamine SM-4, 15.0mmol of sodium tert-butoxide and 60mL of toluene are mixed, and 0.1mmol of Pd is added 2 (dba) 3 Heating a catalyst, 0.1mmol of cuprous iodide and 0.3mmol of 10% tri-tert-butylphosphine toluene solution to 100 ℃, stirring and reacting for 12 hours, cooling to room temperature, adding 50mL of water for dilution, extracting with dichloromethane, collecting an organic phase, drying, filtering, concentrating the filtrate under reduced pressure, and separating and purifying by using a silica gel column to obtain a compound D604;
T 1 ：CMe 2 white solid, yield: 84%, MS (MALDI-TOF): m/z =628.3022[ M ] +H] + ； 1 HNMR(δ、CDCl 3 )：8.27(1H,s)；7.98～7.97(1H,d)；7.90～7.88(1H,d)；7.83～7.81(2H,m)；7.72～7.69(2H,m)；7.67～7.62(4H,m)；7.52～7.48(1H,m)；7.39～7.28(7H,m)；7.25～7.18(3H,m)；7.16～7.12(3H,m)；7.08～7.02(3H,m)；2.75(3H,s)；1.68(6H,s)。
T 1 Is 9,9-fluorenyl, white solid, yield: 82%, MS (MALDI-TOF): m/z =750.3177[ m ] +H] + ； 1 HNMR(δ、CDCl 3 )：7.96～7.90(5H,m)；7.72～7.69(2H,m)；7.67～7.62(4H,m)；7.52～7.48(1H,m)；7.46～7.32(10H,m)；7.22～7.12(7H,m)；7.16～7.07(4H,m)；6.87～6.81(3H,m)；2.75(3H,s)。
With reference to the above-described analogous synthetic procedures, the following compounds shown in table 3 were prepared:
TABLE 3
Figure BDA0003912387950000263
In the above embodiment, - [ T ] 1 —*、*—T 2 Each is independently selected from-O-, -S-, or one of the following structures:
Figure BDA0003912387950000264
* -and-represent a connecting bond.
Example 4
An OLED element, as shown in fig. 1, the OLED element of this embodiment is a top emission light element, and 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, an organic light emitting layer 106 disposed on the electron blocking layer 105, a hole blocking layer 107 disposed on the organic light emitting layer 106, an electron transport layer 108 disposed on the hole blocking layer 107, an electron injection layer 109 disposed on the electron transport layer 108, and a cathode 110 disposed on the electron injection layer 109 and a capping layer 111 disposed on the cathode, and the method for manufacturing the OLED element without the hole blocking layer 107 includes the following steps:
1) The glass substrate coated with the ITO conductive layer is subjected to ultrasonic treatment in a cleaning agent for 30 minutes, washed in deionized water, subjected to ultrasonic treatment in an acetone/ethanol mixed solvent for 30 minutes, baked to be completely dry in a clean environment, irradiated by an ultraviolet light cleaning machine for 10 minutes, and bombarded on the surface by a low-energy cation beam.
2) Placing the processed ITO glass substrate in a vacuum chamber, and vacuumizing to less than 1 × 10 -5 Pa, depositing silver on the ITO film as anode layer to obtain a deposited film with a thickness of
Figure BDA0003912387950000271
Continue to useRespectively evaporating compounds HI01 and F4TCNQ as hole injection layers, wherein F4TCNQ is 3% of HI01 by mass, and the thickness of the evaporated film is
Figure BDA0003912387950000272
3) Continuously depositing a compound HTM on the hole injection layer to form a hole transport layer, wherein the deposition film has a thickness of
Figure BDA0003912387950000273
4) The compound represented by the formula (I) of the present invention is continuously deposited on the hole transport layer as an electron blocking layer to a thickness of
Figure BDA0003912387950000274
5) The compound BH018 as a host material and BD041 as a doping material were continuously evaporated on the electron blocking layer, the mass of BD041 is 8% of that of BH018, and the organic light-emitting layer of the device was formed by evaporation to have a film thickness of
Figure BDA0003912387950000275
6) Continuously evaporating a layer of LiQ and a compound ET028 on the organic light-emitting layer to be used as an electron transport layer of the element, wherein the mass of the compound ET028 is 50 percent of that of the LiQ, and the thickness of the evaporated film is equal to that of the element
Figure BDA0003912387950000276
7) Continuously evaporating a layer of LiF on the electron transport layer to form an electron injection layer, wherein the thickness of the evaporated film is
Figure BDA0003912387950000277
8) And evaporating metal magnesium and silver on the electron injection layer to form a transparent cathode layer of the element, wherein the mass ratio of magnesium to silver is 1
Figure BDA0003912387950000278
9)A CPL layer as element is evaporated on the transparent cathode layer with a thickness of
Figure BDA0003912387950000279
The OLED element provided by the invention is obtained.
The compound used in example 4 above has the following structure:
Figure BDA00039123879500002710
example 5
An organic electroluminescent device 200 is shown in fig. 2, and comprises a substrate 201, an anode layer 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 layer 213.
Comparative example 1
Following the same procedure as in example 4, the compound of the present invention of formula (I) in step 4) was replaced with H01 to give comparative element 1;
Figure BDA0003912387950000281
comparative example 2
Following the same procedure as in example 4, substituting the compound of the present invention of formula (I) in step 4) with H02 gave comparative element 2;
Figure BDA0003912387950000282
comparative example 3
Following the same procedure as in example 4, the compound of the present invention of formula (I) in step 4) was replaced with H03 to give comparative element 3;
Figure BDA0003912387950000283
comparative example 4
Following the same procedure as in example 4, the compound of the present invention of formula (I) in step 4) was replaced with H04 to give comparative element 4;
Figure BDA0003912387950000284
the organic electroluminescent element prepared by the above process was subjected to the following performance tests:
the driving voltage and current efficiency of the organic electroluminescent elements prepared in examples 4 and 5 and comparative examples 1 to 4 and the lifetime of the elements were measured using a digital source meter and a luminance meter. Specifically, the voltage was raised at a rate of 0.1V per second, and it was determined that the luminance of the organic electroluminescent element reached 1000cd/m 2 The current voltage is the driving voltage, and the current density at the moment is measured; the ratio of the brightness to the current density is the current efficiency; the LT95% lifetime test is as follows: using a luminance meter at 1000cd/m 2 The luminance degradation of the organic electroluminescent element was measured to 950cd/m while maintaining a constant current at luminance 2 Time in hours. The data listed in table 4 are relative data compared to comparative element 1.
TABLE 4
Figure BDA0003912387950000291
Figure BDA0003912387950000301
Figure BDA0003912387950000311
Figure BDA0003912387950000321
In the above table, me is methyl, ph is phenyl, phPh is biphenyl, nap is naphthyl, FR is 9,9-fluorenyl, and Ad is adamantyl.
As can be seen from table 4, the driving voltage of the device prepared from the fluorene derivative of the present invention is lower than that of H01 under the same brightness, the current efficiency is improved significantly, which is up to 1.3 times that of the comparative device, and the LT95% lifetime of the device is greatly improved.
Compared with the compound of the invention, the compound H01 in the comparative example 1 is different from the compound of the invention in that fluorene is connected with two phenyl groups through an olefinic bond, and the compound of the invention introduces an alkyl group on the fluorene, so that the conjugation capability is reduced, the performance of the compound on molecular film formation and charge blocking is more excellent, the transmission of carriers in an element is more balanced, and the performance of the element is obviously improved.
Compared with the compound of the invention, the compound H02 in the comparative example 2 is different in that two fluorenyl groups are connected through an olefinic bond, the plane conjugation capability is enhanced, and carbon carbene plasma is more easily formed, so that the electron transport performance is improved, the hole transport and electron blocking performance is reduced, and the voltage is high and the efficiency is reduced. The compound of the invention introduces alkyl or cycloalkyl on fluorene to prevent carbon carbene plasma from being formed, and the electron blocking performance is improved, so that the compound has more excellent performance on molecular film formation and charge blocking, and the charge transmission in the element is more balanced, thereby the element performance is obviously improved.
The compound H03 in comparative example 3 is different from the compound of the present invention in that the planar conjugation ability of fluorenene is enhanced, the hole transport and charge blocking properties are decreased, resulting in high voltage and reduced efficiency. The compound of the invention introduces alkyl or aralkyl substituent on the olefinic bond, the hole transmission performance is improved, therefore, the compound has more excellent molecular film forming and charge blocking performance, the charge transmission in the element is more balanced, and the element performance is obviously improved.
Compared with the compound of the invention, the compound H04 in the comparative example 4 is different in that a fused electron-donating group is introduced on the basis of fluorene, so that the planar conjugation capability is enhanced, the charge transport performance is improved, the transfer of excitons in the element is unbalanced, the voltage is increased, and the efficiency is reduced. The compound of the invention blocks excitons from moving towards the anode after introducing alkyl, so that the charge transmission in the element is more balanced, and the element performance is obviously improved.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, it is intended that all such modifications and alterations be included within the scope of this invention as defined in the appended claims.

Claims (10)

1. A fluorene derivative having a structural formula represented by formula (I):
Figure FDA0003912387940000011
wherein the content of the first and second substances,
L 1 selected from the group consisting of single bonds, substituted or unsubstituted C 6 -C 60 Arylene, or substituted or unsubstituted C 2 -C 60 Heteroarylene;
R 1 、R 2 each independently selected from hydrogen, substituted or unsubstituted C 1 -C 40 Alkyl, substituted or unsubstituted C 2 -C 40 Alkenyl, substituted or unsubstituted C 3 -C 40 Cycloalkyl, substituted or unsubstituted C 3 -C 40 Cycloalkenyl, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 2 -C 60 Heteroaryl, or R 1 And R 2 Cyclizing to form the following formula A 1 ～A 7 The group shown:
Figure FDA0003912387940000012
and R is 1 And R 2 Up to one of which may be selected from substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 2 -C 60 A heteroaryl group;
R 3 selected from hydrogen, deuterium, fluorine, hydroxyl, nitrile group, nitro group, carboxyl group or carboxylate thereof, sulfonic group or sulfonate thereof, phosphoric group or phosphate thereof, and substituted or unsubstituted C 1 -C 40 Alkyl, substituted or unsubstituted C 1 -C 40 Alkoxy, substituted or unsubstituted C 2 -C 40 Alkenyl, substituted or unsubstituted C 1 -C 40 Alkylthio, substituted or unsubstituted C 1 -C 40 Alkoxy, substituted or unsubstituted C 3 -C 40 Cycloalkyl, substituted or unsubstituted C 1 -C 40 Alkyl sulfoxide group, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Aryloxy, substituted or unsubstituted C 6 -C 60 Arylthio, substituted or unsubstituted C 3 -C 40 Silyl, or substituted or unsubstituted C 2 -C 60 Heterocyclic aryl groups; r 3 Is one or more;
Ar 1 、Ar 2 each independently selected from the group consisting of substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Condensed ring aryl, substituted or unsubstituted C 6 -C 60 Arylamino, or substituted or unsubstituted C 2 -C 60 Heterocyclic aryl groups; wherein Ar is 1 、Ar 2 、L 1 Optionally joined or cyclized to form a substituted or unsubstituted ring with or without the heteroatom O, S, N or Si in the ring formed;
Figure FDA0003912387940000022
is represented by the formula 1 Or R 2 The connecting bond of (1).
2. The fluorene derivative according to claim 1, wherein the fluorene derivative is selected from the group consisting of the following structures:
Figure FDA0003912387940000021
Figure FDA0003912387940000031
wherein n, m are each independently selected from integers of 0 to 40;
p, q are each independently selected integers from 1 to 40;
R 4 、R 5 each independently selected from the group consisting of hydrogen, deuterium, fluorine, nitrile, methyl, tert-butyl, phenyl, biphenylyl, terphenylyl, naphthyl, phenanthryl, triphenylene, carbazolyl, fluorenyl, dibenzofuran, or dibenzothiophene.
3. Fluorene derivative according to claim 1 or 2, wherein R is 3 、R 4 、R 5 Each independently hydrogen, tert-butyl or phenyl;
n, m are each independently selected from integers of 0 to 10;
p, q are each independently selected from integers of 1 to 5.
4. The fluorene derivative according to claim 1, wherein Ar is Ar 1 、Ar 2 Each independently selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted biphenylyl, substituted or unsubstituted terphenylyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted dibenzofuranyl, or substituted or unsubstituted dibenzothiophene.
5. Fluorene derivatives according to claim 1The compound is characterized in that L is 1 Selected from a single bond or a group consisting of the following groups III-1 to III-23:
Figure FDA0003912387940000032
Figure FDA0003912387940000041
wherein the dotted line represents the attachment site of the group.
6. The fluorene derivative according to any one of claims 1 to 5, wherein the fluorene derivative is selected from compounds represented by the following formulae D475 to D606:
Figure FDA0003912387940000042
Figure FDA0003912387940000051
Figure FDA0003912387940000061
Figure FDA0003912387940000071
Figure FDA0003912387940000081
Figure FDA0003912387940000091
Figure FDA0003912387940000101
wherein, x-T 1 —*、*—T 2 Each is independently selected from-O-, -S-, or one of the following structures:
Figure FDA0003912387940000102
* -and-represent a connecting bond.
7. Use of a fluorene derivative according to any one of claims 1 to 6 for the production of an organic electroluminescent element.
8. An organic electroluminescent element, characterized by comprising: the organic light-emitting diode comprises a first electrode, a second electrode, a capping layer and more than one organic layer arranged between the first electrode and the second electrode; a material of at least one of the organic layer or the capping layer includes the fluorene derivative according to any one of claims 1 to 6.
9. The organic electroluminescent element according to claim 8, wherein the organic layer comprises 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.
10. A consumer product comprising the organic electroluminescent element according to claim 8.
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