CN116444435B - Fluorene derivative, electronic element and electronic device - Google Patents

Fluorene derivative, electronic element and electronic device Download PDF

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CN116444435B
CN116444435B CN202310373447.2A CN202310373447A CN116444435B CN 116444435 B CN116444435 B CN 116444435B CN 202310373447 A CN202310373447 A CN 202310373447A CN 116444435 B CN116444435 B CN 116444435B
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fluorene derivative
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CN116444435A (en
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曹建华
冯静
张九敏
何连贞
董梁
申旭
梁红红
秦子杰
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Zhejiang Bayi Space Time Advanced Materials 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 in electronic elements and electronic devices. The structural formula of the fluorene derivative is shown as formula (I); the compound shown in the formula (I) provided by the invention has a seven-membered ring and more than one multi-membered ring structure. The compound is applied to an organic electroluminescent element, so that the driving voltage can be obviously reduced, the luminous efficiency can be improved, and the service life can be prolonged;

Description

Fluorene derivative, electronic element and electronic device
Technical Field
The invention relates to the technical field of organic electroluminescent materials, in particular to a fluorene derivative and application thereof in organic light-emitting elements and electronic devices.
Background
Most of the materials used in the organic electroluminescent element are pure organic materials or organometallic complexes of organic materials and metals, and they are classified into hole injection materials, hole transport materials, light emitting materials, electron transport materials, electron injection materials, and the like, depending on the application. Here, an organic substance having a relatively small ionization energy is mainly used as the hole injection substance or the hole transport substance, and an organic substance having a relatively large electronegativity is mainly used as the electron injection substance or the electron transport substance. Further, the substance used as the light-emitting auxiliary layer preferably satisfies the following characteristics.
In each case, the material used in the organic electroluminescent element needs to have good thermal stability because joule heat is generated by charge transfer in the organic electroluminescent element, and at present, a material generally used as a hole transport layer has a low glass transition temperature, and therefore, a phenomenon occurs in which light emission efficiency is lowered due to crystallization occurring at the time of driving at a low temperature. Second, in order to reduce the driving voltage, it is necessary that the organic material adjacent to the cathode and anode is designed to have a small charge injection barrier and a high charge mobility. Third, there is always an energy barrier at the interface of the electrode and the organic layer, and at the interface of the organic layer and the organic layer, and some charges are inevitably accumulated, so that it is necessary to use a substance excellent in electrochemical stability.
The organic electroluminescent device generally includes 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 sequentially stacked. When voltage is applied to the cathode and the anode, the two electrodes generate an electric field, electrons at the cathode side move to the electroluminescent layer under the action of the electric field, holes at the anode side also move to the luminescent layer, the electrons and the holes are combined in the electroluminescent layer to form excitons, and the excitons are in an excited state to release energy outwards, so that the electroluminescent layer emits light.
,KR1020180113731、CN201710407382.3、CN201610183587.3、CN201380045022.3、CN201180044705.8、CN201910765403.8 Et al in the prior art disclose materials that can be used to prepare hole transport layers in organic electroluminescent devices. However, there remains a need to continue to develop new materials to further improve the performance of electronic components.
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 using the fluorene derivative can obviously reduce driving voltage, improve luminous efficiency and prolong service life; it is a further object of the present invention to provide the use of the compounds.
Specifically, the invention provides the following technical scheme:
the invention provides a fluorene derivative, which has a structural formula shown in a formula (I):
wherein,
X is selected from O, S or CR 11R12;
Each R 1～R12 is independently selected from the group consisting of hydrogen, deuterium, fluorine, hydroxyl, nitrile, substituted or unsubstituted C 1-C40 alkyl, substituted or unsubstituted C 1-C40 alkoxy, substituted or unsubstituted C 2-C40 alkenyl, substituted or unsubstituted C 1-C40 alkylthio, substituted or unsubstituted C 1-C40 heteroalkyl, substituted or unsubstituted C 3-C40 cycloalkyl, substituted or unsubstituted C 3-C40 cycloalkenyl, substituted or unsubstituted C 6-C60 aryl, substituted or unsubstituted C 6-C60 aryloxy, substituted or unsubstituted C 6-C60 arylthio, substituted or unsubstituted C 6-C60 arylamino, substituted or unsubstituted C 3-C40 silyl, substituted or unsubstituted C 2-C60 heteroaryl, or a group of formula (II), and at least one is a group of formula (II);
R 10 is one or more, and two or more R 10 can be optionally combined or cyclized to form a substituted or unsubstituted ring;
L 1 is selected from the group consisting of a single bond, a substituted or unsubstituted C 6-C60 arylene, or a substituted or unsubstituted C 2-C60 heteroarylene;
ar 1、Ar2 is each independently selected from the group consisting of substituted or unsubstituted C 6-C60 aryl, substituted or unsubstituted C 6-C60 fused ring aryl, substituted or unsubstituted C 6-C60 arylamine group, or substituted or unsubstituted C 2-C60 heterocyclic aryl; wherein Ar 1、Ar2、L1 may be optionally bonded or cyclized to form a substituted or unsubstituted ring with or without heteroatom O, S, N or Si in the ring formed;
n is an integer from 0 to 5.
In the substituted or unsubstituted ring formed by joining or ring closure as described in the present invention, "ring" means a substituted or unsubstituted hydrocarbon ring, or a substituted or unsubstituted heterocyclic ring. The condensed ring means 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-mentioned chemical formula (I), and comprises a basic skeleton formed by the combination of formula (I) and L 1NAr1Ar2. The compound represented by the formula (I) of the present invention is electrochemically stable, has excellent hole mobility and electron blocking ability, and has a high glass transition temperature and excellent thermal stability, as compared with the conventionally known B-1 to B-4 structures.
Thus, the fluorene derivative of the present invention is excellent in hole transporting ability and electron blocking ability, and thus can be used as a material for any one of a hole injection layer, a hole transport auxiliary layer, and an electron blocking layer of an organic electroluminescent element. The material that can be used as any one of the hole transport auxiliary 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 the formula (I) of the present invention has smaller steric hindrance, stronger hole transporting ability and electron blocking ability, and can exhibit relatively high luminous efficiency and high glass transition temperature, as compared with the known fluorene derivative B-1, naphthoindene derivative B-2 and polycyclic B-3, B-4, by a plurality of substituted or unsubstituted seven-membered heterocyclic derivatives. Thus, when the fluorene derivative represented by the formula (I) of the present invention is used for an organic electroluminescent element, not only excellent thermal stability and carrier transporting ability, particularly electron blocking ability and light emitting ability, but also reduction in driving voltage of the element, improvement in efficiency, lifetime, and the like can be expected, and excellent efficiency increase due to triplet-triplet fusion effect can be exhibited due to high triplet energy level as a latest electron blocking layer material.
Further, the fluorene derivative represented by formula (I) of the present invention can have a wide band gap by adjusting HOMO and LUMO energy levels according to the kind of substituent by introducing from the parent nucleus containing the substituent R 1～R10 and L 1NAr1Ar2, and can exhibit the highest hole transport property and electron blocking property in an organic electroluminescent element using such a compound.
In addition, the fluorene derivative represented by formula (I) of the present invention has higher thermal stability than conventional luminescent materials by significantly increasing the molecular weight of the compound by introducing various substituents L 1 and Ar 1、Ar2, particularly aryl and/or heteroaryl groups, into the basic skeleton. Therefore, the performance and lifetime characteristics of the organic electroluminescent element comprising the compound according to the present invention can be greatly improved. The organic electroluminescent element thus improved in performance and lifetime characteristics can eventually maximize the performance of the full-color organic light-emitting panel.
Aryl groups in the sense of the present invention contain 6 to 60 carbon atoms, heteroaryl groups contain 2 to 60 carbon atoms and at least one heteroatom, provided 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, or may further include a condensed form with the aryl group. As non-limiting examples of such heteroaryl groups, six-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, and the like can be cited; polycyclic rings such as phenoxazolyl, indolizinyl, indolyl, purinyl, quinolinyl, benzothiazolyl, carbazolyl, and the like; 2-furyl, N-imidazolyl, 2-isoxazolyl, 2-pyridyl, 2-pyrimidinyl, and the like.
Alkyl in the sense of the present invention contains 1 to 40 carbon atoms and wherein the individual hydrogen atoms or the-CH 2 -groups may also be substituted straight-chain alkyl or branched alkyl groups; alkenyl or alkynyl groups contain at least two carbon atoms, and alkyl, alkenyl or alkynyl groups are preferably considered to mean, by way of non-limiting example, 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 is preferably an alkoxy group having 1 to 40 carbon atoms, which is taken to mean methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, sec-pentoxy, 2-methylbutoxy, n-hexoxy, cyclohexyloxy, n-heptoxy, cycloheptyloxy, n-octoxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy and 2, 2-trifluoroethoxy.
Heteroalkyl groups, preferably alkyl groups having 1 to 40 carbon atoms, refer to groups in which a separate hydrogen atom or-CH 2 -group is replaced by an oxygen, sulfur, halogen atom, as non-limiting examples, alkoxy, alkylthio, fluoroalkoxy, fluoroalkylthio, 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-trifluoroethoxy, 2-trifluoroethylthio, ethyleneoxy, ethylenethio, propyleneoxy, propylenethio, butylenethio, butyleneoxy, pentenyloxy, pentenylthio, cyclopentenyloxy, cyclopentenylthio, hexenyloxy, hexenylthio, cyclohexene thio, acetylenyloxy, acetylenylthio, propynyloxy, butynylthio, pentynyloxy, pentynylthio, hexyloxy, hexylynylthio.
In general, cycloalkyl, cycloalkenyl groups according to the invention may be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptyl, cycloheptenyl, wherein one or more-CH 2 -groups may be replaced by the above groups; in addition, one or more hydrogen atoms may be replaced by deuterium atoms, halogen atoms, or nitrile groups.
The heterocycloalkyl group used in the present invention means a monovalent functional group obtained by removing one hydrogen atom from a non-aromatic hydrocarbon having a atomic number of 3 to 40. At this time, one or more carbons, preferably 1 to 3 carbons, in the ring are substituted with a heteroatom such as N, O or S. As non-limiting examples thereof, tetrahydrofuran, tetrahydrothiophene, morpholine, piperazine, and the like are given.
The condensed ring aryl group used in the present invention means a monovalent functional group obtained by removing one hydrogen atom from an aromatic hydrocarbon having 6 to 60 carbon atoms, which is a combination of two or more rings. In this case, two or more rings may be attached to each other singly or in a condensed form. As non-limiting examples thereof, there may be mentioned phenanthryl, anthracyl, fluoranthracyl, pyrenyl, triphenylenyl, perylenyl,A base, etc.
As the arylamine group used in the present invention, an arylamine group refers to an amine substituted with an aryl group having 6 to 60 carbon atoms, and as non-limiting examples of the arylamine group, there are a diphenylamino group, an N-phenyl-1-naphthylamine group, an N- (1-naphthyl) -2-naphthylamine group and the like. The heteroarylamino 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 heteroarylamino group, there are N-phenylpyridine-3-amino, N- ([ 1,1 '-biphenyl ] -4-yl) dibenzo [ b, d ] furan-2-amino, N- ([ 1,1' -biphenyl ] -4-yl) -9, 9-dimethyl-9H-fluorene-2-amino, and the like.
The aryloxy group used in the present invention means a monovalent functional group represented by R 'O-and R' 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, there are trimethylsilyl group, triethylsilyl group and the like. Arylsilyl refers to silyl groups substituted with aryl groups having from 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 as non-limiting examples of the arylphosphorus group, there are diphenylphosphorus group, bis (4-trimethylsilylbenzene) phosphorus group and the like. The phosphorus atom of the aryl phosphorus oxide group is the diaryl phosphorus group is oxidized to the highest valence state.
The arylboron group used in the present invention means a diarylboroyl group substituted with an aryl group having 6 to 60 carbon atoms, and as non-limiting examples of the arylboron group, there are diphenyl boron group, bis (2, 4, 6-trimethylbenzene) boron group and the like. The alkylboryl group means a dialkylboryl group substituted with an alkyl group having 1 to 40 carbon atoms, and as non-limiting examples of the alkylboryl group, there are di-t-butylboryl group, diisobutylboryl group and the like.
Preferably, the aryl, heteroaryl or heteroaryl group is preferably selected from the group consisting of phenyl, naphthyl, anthracenyl, benzanthracenyl, phenanthryl, pyrenyl,A group, perylene group, fluoranthenyl group, naphthacene group, pentacene group, benzopyrene group, biphenyl group, terphenyl group, tripolyphenyl group, tetrabiphenyl group, fluorenyl group, spirobifluorenyl group, dihydrophenanthrene group, triphenylene group, dihydropyrenyl group, tetrahydropyrenyl group, cis-or trans-indenofluorenyl group, cis-or trans-indenocarbazolyl group, indolocarbazolyl group, benzofuranocarbazolyl group, benzothiophenocarbazolyl group, benzocarbazolyl group, azadibenzo [ g., iD ] naphtho [2,1,8-cde ] azulene, trimeric indenyl, heterotrimeric indenyl, spirotrimeric indenyl, spiroheterotrimeric indenyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, indolyl, isoindolyl, carbazolyl, pyridyl, quinolinyl, isoquinolinyl, acridinyl, phenanthridinyl, benzo [5,6] quinolinyl, benzo [6,7] quinolinyl, benzo [7,8] quinolinyl, phenothiazinyl, phenoxazinyl, pyrazolyl, indazolyl, imidazolyl benzimidazolyl, naphthylimidazolyl, phenanthroimidazolyl, pyridmethylimidazolyl, pyrazinoimidazolyl, quinoxalinoimidazolyl, oxazolyl, benzoxazolyl, naphthazolyl, anthracoxazolyl, phenanthrooxazolyl, isoxazolyl, 1, 2-thiazolyl, 1, 3-thiazolyl, benzothiazolyl, pyridazinyl, hexaazabenzophenanthryl, benzopyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1, 5-diazaanthryl, 2, 7-diazapyrenyl, 2, 3-diazapyrenyl, 1, 6-diazapyrenyl, 1, 8-diazapyrenyl, 4, 5-diazapyrenyl group, 4,5,9, 10-tetraazaperylene, pyrazinyl, phenazinyl, phenoxazinyl, phenothiazinyl, fluorogenic ring, naphthyridinyl, azacarbazolyl, benzocarboline, carboline, phenanthroline, 1,2, 3-triazolyl, 1,2, 4-triazolyl, benzotriazole, 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, indolizinyl, or combinations thereof.
In the fluorene derivative represented by formula (I) of the present invention, preferably, the fluorene derivative is selected from the group consisting of the structures shown below:
Wherein R 1～R12、x、L1、Ar1、Ar2 and n have the same meanings as defined above.
Preferably, each of the R 1、R2、R11、R12 is independently selected from the group consisting of substituted or unsubstituted C 1-C40 alkyl, substituted or unsubstituted C 6-C60 aryl, substituted or unsubstituted C 6-C60 arylamine.
Preferably, each R 3、R4、R5、R6、R7、R8、R9、R10 is independently selected from the group consisting of hydrogen, deuterium, fluorine, nitrile, substituted or unsubstituted C 1-C40 alkyl, substituted or unsubstituted C 1-C40 alkoxy, substituted or unsubstituted C 1-C40 heteroalkyl, substituted or unsubstituted C 3-C40 cycloalkyl, substituted or unsubstituted C 6-C60 aryl, substituted or unsubstituted C 6-C60 arylamine, substituted or unsubstituted C 2-C60 heteroaryl, or a group of formula (II), and at least one is a group of formula (II).
Further, each of the R 1、R2、R11、R12 is independently selected from the group consisting of hydrogen, deuterium, methyl, substituted or unsubstituted phenyl, substituted or unsubstituted fluorenyl.
Further, each of the R 3、R4、R5、R6、R7、R8、R9、R10 is independently selected from the group consisting of hydrogen, deuterium, fluorine, nitrile, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylene, substituted or unsubstituted carbazolyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophene, and at least one of them is a group represented by formula (II).
Further, each of the Ar 1、Ar2 is independently selected from the group consisting of a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted tetrabiphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted benzothienyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophene group.
Preferably, n represents 0, 1 or 2.
Further, each R 1、R2、R11、R12 is independently selected from methyl or phenyl.
Further, each of the R 3、R4、R5、R6、R7、R8、R9、R10 is independently selected from the group consisting of hydrogen, deuterium, nitrile, tert-butyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophene, or a group represented by formula (II), and at least one is a group represented by formula (II).
In the fluorene derivative represented by formula (I) of the present invention, L 1 is a functional group that connects the parent nucleus containing the substituents R 1 to R 10 with the NAr 1Ar2, and in this case, preferably, L 1 is selected from a single bond or a group consisting of groups represented by the following III-1 to III-23:
Wherein the dotted line represents the linking site of the group, and the binding site of the groups represented by the above formulas III-1 to III-23 is not limited, and may be any of ortho-, meta-, and para-ones. The above-mentioned L 1 may each independently be substituted with one or more selected from the group consisting of deuterium, a halogen atom, a nitrile group, a C 1-C40 alkyl group, a C 6-C60 aryl group and a C 2-C60 heterocyclic aryl group, and in this case, when the substituents are plural, it is preferable that the plural substituents are the same as or different from each other.
In the present invention, the term "substituted or unsubstituted" means that the compound is substituted or unsubstituted with 1 or more substituents selected from 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, a C 1-C40 alkyl group, a C 2-C40 alkenyl group, a C 2-C40 alkynyl group, a C 1-C40 alkoxy group, a C 3-C40 cycloalkyl group, a C 3-C40 cycloalkenyl group, a C 6-C60 aryl group, a C 6-C60 aryloxy group, a C 6-C60 arylene sulfide group, and a C 2-C60 heteroaryl group, or a substituent bonded with 2 or more substituents selected from the above-exemplified substituents.
Preferably, the fluorene derivative is selected from compounds represented by the following formulas D100 to D207:
wherein, -T-/are each independently selected from-O-, -S-/or one of the structures shown below:
* -X-each independently selected from-O-, S-, or one of the structures shown below:
* -and-represents a bond.
The invention also provides an organic electroluminescent material, which comprises the fluorene derivative; the organic electroluminescent material comprising the fluorene derivative according to the present invention has a carrier transporting ability.
The invention also provides application of the fluorene derivative in preparing an organic electroluminescent element.
The present invention also provides an organic electroluminescent element comprising: 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 or the capping layer includes the fluorene derivative described above.
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 further 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-generating layers. An intermediate layer having, for example, an exciton blocking function can likewise be introduced between the two light-emitting layers. It should be noted, however, that not every one of these layers need be present. The organic electroluminescent device described herein may comprise one light emitting layer, or it may comprise 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 is a system with three light-emitting layers, wherein the three layers can display blue, green and red light emission. If more than one light emitting layer is present, at least one of these layers comprises a fluorene derivative according to the present invention.
Further, the organic electroluminescent element according to the present 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 anode and/or the light emitting layer is directly adjacent to the electron transport layer or electron injection layer or cathode.
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 generally used according to the prior art. A person of ordinary skill in the art will thus be able to use all materials known in relation to organic electroluminescent elements in combination with the light-emitting layer according to the invention without inventive effort.
Furthermore, preference is given to organic electroluminescent elements in which one or more layers are applied by means of a sublimation process, wherein the material is applied by vapor deposition in a vacuum sublimation apparatus at an initial pressure of less than 10 -5 Pa, preferably less than 10 -6 Pa. However, the initial pressure may also be even lower, for example below 10 -7 Pa.
Also preferred are organic electroluminescent elements in which one or more layers are applied by means of an organic vapor deposition process or by means of sublimation of a carrier gas, wherein the material is applied at a pressure of between 10 -5 Pa and 1 Pa. A particular example of this method is an organic vapor jet printing method, wherein the material is applied directly through a nozzle and is thus structured.
Furthermore, organic electroluminescent elements are preferred, from which one or more layers are produced, for example by spin coating, or by means of any desired printing method, for example screen printing, flexography, lithography, photoinitiated thermal imaging, thermal transfer, inkjet 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, a hybrid method is possible, in which one or more layers are applied, for example from a solution, and one or more further layers are applied by vapor deposition.
These methods are generally known to those of ordinary skill in the art and they can be applied to the organic electroluminescent element comprising the compound according to the present invention without inventive effort.
The invention therefore also relates to a method for manufacturing an organic electroluminescent element according to the invention, at least one layer being applied by means of a sublimation method, and/or characterized in that at least one layer is applied by means of an organic vapour deposition method or by means of carrier gas sublimation, and/or in that at least one layer is applied from solution by spin coating or by means of a printing method.
Furthermore, the present invention relates to a fluorene derivative comprising at least one of the present invention as indicated above. The same preferable cases as indicated above with respect to the organic electroluminescent element apply to the compound of the present invention. In particular, the fluorene derivative may preferably contain other compounds in addition to the fluorene derivative. Treatment of fluorene derivatives of the present invention from the liquid phase, for example by spin coating or by printing methods, requires treatment of the formulation of the compounds of the present invention. These formulations may be, for example, solutions, dispersions or emulsions. For this purpose, it may be preferable to use a mixture of two or more solvents. Suitable and preferred solvents are, for example, toluene, anisole, o-, m-or p-xylene, methyl benzoate, mesitylene, tetralin, o-dimethoxybenzene, tetrahydrofuran, methyltetrahydrofuran, tetrahydropyran, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxytoluene, (-) -fenchyl ketone, 1,2,3, 5-tetramethylbenzene, 1,2,4, 5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methylanisole, 4-methylanisole, 3, 4-dimethylbenzene, 3, 5-dimethylbenzene, acetophenone, alpha-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, methyl benzoate, 1-methylpyrrolidone, p-cymene, phenetole, 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-bis (3, 4-dimethylphenyl) ethane, 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 hole transport layer, hole transport layer or electron blocking layer comprises the fluorene derivative of the present invention.
Still further, the electron blocking layer comprises the fluorene derivative of the present invention.
The invention also provides a consumer electronic device comprising the organic electroluminescent element.
In addition, unless otherwise specified, all raw materials used in the present invention are commercially available, and any ranges recited in the present invention include any numerical value between the end values and any sub-range constituted by any numerical value between the end values or any numerical value between the end values.
The beneficial effects obtained by the invention are as follows:
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 characteristics, and thus can be applied to an organic layer of an organic electroluminescent element. In particular, when the fluorene derivative represented by the formula (I) of the present invention is used for an electron blocking layer or a light emitting layer, an organic electroluminescent element having a lower driving voltage, higher efficiency and longer lifetime than conventional electron blocking materials can be produced, and further, a full-color display panel having improved performance and lifetime can be produced.
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 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 fabricated by sequentially depositing the layers described.
Fig. 2 shows a schematic diagram of an organic light emitting device 200 with 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 emissive layer 205, an electron transport layer 206, a charge generation layer 207, a hole injection layer 208, a hole transport layer 209, a second emissive layer 210, an electron transport layer 211, an electron injection layer 212, and a cathode 213. The device 200 may be prepared by sequentially depositing the layers described. Because the most common OLED device has one light emitting layer, and device 200 has a first light emitting layer and a second light emitting layer, the light emitting peaks of the first and second light emitting layers may be overlapping or cross-overlapping or non-overlapping. In the corresponding layers of device 200, materials similar to those described with respect to device 100 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 illustrative of the invention and are not intended to limit the scope of the invention.
In the description of the present invention, unless otherwise indicated, the meaning of "a plurality" is two or more; the orientation or positional relationship indicated by the terms "upper", "lower", etc. are based on the orientation or positional relationship shown in the drawings, are merely for convenience of description and to simplify the description, and are not indicative or implying that the apparatus or elements in question must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be construed as limiting the present invention.
The experimental methods used in the following examples are conventional methods unless otherwise specified. The experimental materials and related equipment used in the examples below, unless otherwise specified, are all commercially available, and the percentages, such as the percentages without otherwise specified, are all mass percentages.
The following examples are examples of the test apparatus and method for testing the performance of OLED materials and devices as follows:
OLED element performance detection conditions:
luminance and chromaticity coordinates: testing using a spectral scanner PhotoResearch PR-715;
current density and driving voltage: testing using a digital source table Keithley 2420;
power efficiency: the NEWPORT 1931-C test was used.
Example 1
A process for the preparation of compound D115, exemplified by x=o, comprising the steps of:
The first step: preparation of intermediate Int-1
Under the protection of nitrogen, 20.0mmol of 2-bromo-3, 5-dichlorobenzonitrile is dissolved in 60mL of toluene, 22.0mmol of (2 '-methoxy- [1,1' -biphenyl ] -2-yl) boric acid, 60.0mmol of anhydrous sodium carbonate, 0.2mmol of Pd (PPh 3)4 catalyst, 30mL of ethanol and 30mL of water are added, the mixture is heated to reflux and stirred for reaction for 12 hours, the temperature is reduced to room temperature, 50mL of water is added, an organic phase is separated, the aqueous phase is extracted by ethyl acetate, the organic phase is combined and dried, the filtration and the concentration of the filtrate under reduced pressure are carried out, and the separation and purification are carried out by using a silica gel column to obtain an intermediate Int-1, white solid, and the yield is 74%.
And a second step of: preparation of intermediate Int-2
Under the protection of nitrogen, 20.0mmol of Int-1 is dissolved in 60mL of dry THF, the temperature is reduced to 0 ℃, 24.0mmol of 1M methyl magnesium bromide THF solution is added dropwise, the temperature is raised to room temperature, stirring reaction is carried out for 1 hour, 50mL of 2M dilute hydrochloric acid aqueous solution is added, extraction is carried out by ethyl acetate, the organic phase is washed by saturated saline, drying and filtration are carried out, the filtrate is concentrated under reduced pressure, the residue is dissolved in 60mL of dry THF, the temperature is reduced to 0 ℃, 24.0mmol of 1M methyl magnesium bromide THF solution is added dropwise, the temperature is raised to room temperature, stirring reaction is carried out for 1 hour, 50mL of 2M dilute hydrochloric acid aqueous solution is added, extraction is carried out by ethyl acetate, the organic phase is washed by saturated saline, drying and filtration are carried out, the filtrate is concentrated under reduced pressure and purification is carried out by silica gel column separation, thus obtaining the compound Int-2 with a yellow solid with a yield of 76%.
And a third step of: preparation of intermediate Int-3
Under the protection of nitrogen, 20.0mmol of Int-2 is dissolved in 50mL of dichloromethane, 30.0mmol of boron trifluoride diethyl etherate is added dropwise, the reaction is stirred at room temperature for 15 hours, 50mL of aqueous sodium bicarbonate solution is added, the aqueous solution is extracted with dichloromethane, the organic phase is washed with water, dried, filtered, the filtrate is concentrated to dryness under reduced pressure, and the intermediate Int-3 is obtained by separation and purification by a silica gel column, and is a white solid with the yield of 89%.
Fourth step: preparation of intermediate Int-4
Under the protection of nitrogen, 20.0mmol of Int-3 is dissolved in 80mL of dry dichloromethane, the temperature is reduced to 0 ℃, 24.0mmol of boron tribromide is added dropwise, stirring reaction is carried out for 1 hour, 50mL of 1M dilute hydrochloric acid aqueous solution is added, an organic phase is separated, the aqueous phase is extracted by dichloromethane, the organic phases are combined and dried, filtration and filtrate decompression concentration are carried out, and silica gel column separation and purification are carried out, thus obtaining intermediate Int-4, yellow solid with the yield of 95%.
Fifth step: preparation of intermediate Int-5
Under the protection of nitrogen, 20.0mmol of Int-4 is dissolved in 60mL of DMF, 50.0mmol of anhydrous potassium carbonate is added, the temperature is raised to 120 ℃ and the mixture is stirred for reaction for 15 hours, the temperature is reduced to room temperature, the reaction solution is poured into 150mL of water and extracted by ethyl acetate, the organic phase is combined and washed by saturated brine, dried, filtered, and the filtrate is concentrated under reduced pressure to dryness, and is separated and purified by a silica gel column to obtain an intermediate Int-5, white solid with the yield of 87%.
Sixth step: preparation of Compound D115
Under the protection of nitrogen, 12.0mmol of intermediate Int-5, 10.0mmol of diarylamine, 15.0mmol of tertiary sodium butoxide, 0.01mmol of Pd 2(dba)3 catalyst, 0.04mmol of 10% tri-tertiary butyl phosphine toluene solution and 50mL of toluene are heated to 100 ℃ to react for 15 hours under stirring, cooled to room temperature, 50mL of water is added for dilution, toluene is used for extraction, an organic phase is collected, dried, filtered, the filtrate is concentrated to dryness under reduced pressure, and the compound D115 is obtained by separating and purifying by a silica gel column;
X=o, T is CMe 2, white solid, yield ：85％,MS(MALDI-TOF)：m/z＝644.2891[M+H]+;1HNMR(δ、CDCl3)：8.26～8.24(1H,d);7.87～7.84(2H,m);7.65～7.56(7H,m);7.50～7.41(5H,m);7.36～7.27(4H,m);7.24～7.20(3H,m);7.17～7.15(1H,d);7.02(1H,s);6.83～6.80(1H,m);1.69～1.68(12H,d).
X=o, T is 9, 9-fluorenyl, white solid, yield ：82％,MS(MALDI-TOF)：m/z＝766.3094[M+H]+;1HNMR(δ、CDCl3)：7.89～7.84(4H,m);7.65～7.54(5H,m);7.50～7.40(6H,m);7.38～7.35(1H,m);7.32～7.20(8H,m);7.18～7.11(5H,m);7.04(1H,s);6.98～6.96(2H,m);6.82(1H,s);1.69(6H,s).
X=s, T is CMe 2, white solid, yield ：81％,MS(MALDI-TOF)：m/z＝660.2709[M+H]+;1HNMR(δ、CDCl3)：8.27～8.25(1H,d);7.92～7.90(1H,d);7.67～7.58(6H,m);7.53～7.45(5H,m);7.41～7.33(5H,m);7.27～7.21(4H,m);7.19～7.14(2H,m);6.83～6.80(1H,m);1.68(12H,s).
X=s, T is 9, 9-fluorenyl, white solid, yield ：78％,MS(MALDI-TOF)：m/z＝782.2867[M+H]+;1HNMR(δ、CDCl3)：7.92～7.87(3H,m);7.65～7.56(4H,m);7.53～7.41(8H,m);7.39～7.35(2H,m);7.25～7.12(11H,m);6.99(1H,s);6.96～6.92(4H,m);1.68(6H,s).
X=cme 2, T is CMe 2, white solid, yield ：86％,MS(MALDI-TOF)：m/z＝670.3408[M+H]+;1HNMR(δ、CDCl3)：8.26～8.24(1H,m);8.01～7.96(2H,m);7.90～7.88(1H,d);7.81(1H,s);7.68～7.58(4H,m);7.56～7.44(5H,m);7.41～7.28(7H,m);7.25～7.20(2H,m);7.14～7.09(1H,m);6.85～6.82(1H,m);1.76(3H,s);1.68(6H,s);1.64(9H,s).
X=cme 2, T is 9, 9-fluorenyl, white solid, yield ：74％,Ms(MALDI-TOF)：m/z＝792.3566[M+H]+;1HNMR(δ、CDCl3)：7.92～7.85(4H,m);7.68～7.58(4H,m);7.56～7.48(5H,m);7.46～7.41(5H,m);7.39～7.32(4H,m);7.26～7.18(5H,m);7.15～7.09(2H,m);6.96(1H,s);6.85～6.80(3H,m);1.76(3H,s);1.65(9H,s).
Referring to the above synthetic method, the following compounds shown in table 1 were prepared:
TABLE 1
Example 2
A process for the preparation of compound D172, exemplified by x=cme 2, comprising the steps of:
the first step: preparation of intermediate Int-6
Under the protection of nitrogen, 20.0mmol of dimethyl 2-iodoisophthalate is dissolved in 60mL of toluene, 24.0mmol of 4-chloro-2-phenylphenylboronic acid, 60.0mmol of anhydrous sodium carbonate and 0.2mmol of Pd (PPh 3)4 catalyst, 30mL of ethanol and 30mL of water are added, the mixture is heated to reflux and stirred for reaction for 12 hours, the temperature is reduced to room temperature, 50mL of water is added, an organic phase is separated, the aqueous phase is extracted by ethyl acetate, the organic phase is combined and dried, the filtrate is filtered, the filtrate is concentrated to dryness under reduced pressure, and the intermediate Int-6 is obtained by separating and purifying by a silica gel column, and yellow solid is obtained, and the yield is 76%.
And a second step of: preparation of intermediate Int-7
Under the protection of nitrogen, 20.0mmol of Int-6 is dissolved in 80mL of dry THF, the temperature is reduced to 0 ℃, 0.1mmol of 1M methyl magnesium bromide THF solution is added dropwise, the temperature is raised to 45 ℃, the stirring reaction is carried out for 12 hours, 50mL of 2N diluted hydrochloric acid aqueous solution is added, the ethyl acetate is used for extraction, the organic phase is washed with saturated saline, the drying is carried out, the filtration is carried out, the filtrate is concentrated under reduced pressure to dryness, and the compound Int-7 is obtained by separating and purifying a silica gel column, and the yellow solid is obtained in 87 percent of yield.
And a third step of: preparation of intermediate Int-8
Under the protection of nitrogen, 20.0mmol of Int-7 is dissolved in 50mL of dichloromethane, 60.0mmol of boron trifluoride diethyl etherate is added dropwise, stirring is carried out at room temperature for reaction for 15 hours, 50mL of 2% aqueous sodium hydroxide solution is added, dichloromethane is used for extraction, an organic phase is washed with water, drying and filtration are carried out, filtrate is concentrated to dryness under reduced pressure, and silica gel column separation and purification are carried out to obtain an intermediate Int-8, white solid is obtained, and the yield is 92%.
Fourth step: preparation of Compound D172
Under the protection of nitrogen, 20.0mmol of Int-8 is dissolved in 60mL of toluene, then 24.0mmol of (3- (biphenyl anilino) phenyl) pinacol borate, 60.0mmol of anhydrous sodium carbonate, 0.01mmol of Pd132 catalyst, 30mL of ethanol and 30mL of water are added, the mixture is heated to reflux and stirred for reaction for 12 hours, the temperature is reduced to room temperature, 50mL of water is added, an organic phase is separated, the aqueous phase is extracted by ethyl acetate, the organic phase is combined and dried, the filtration is carried out, the filtrate is concentrated to dryness under reduced pressure, and the compound D172 is obtained by separating and purifying by a silica gel column;
X: CMe 2, white solid, yield ：78％,MS(MALDI-TOF)：m/z＝630.3169[M+H]+;1HNMR(δ、CDCl3)：8.05(1H,s);7.97(1H,s);7.75～7.71(3H,m);7.56～7.47(5H,m);7.45～7.35(7H,m);7.29～7.24(3H,m);7.22～7.16(4H,m);7.09～7.06(2H,m);7.01～6.97(1H,m);1.76(3H,s);1.69(6H,s);1.64(3H,s).
X: o, white solid, yield ：77％,MS(MALDI-TOF)：m/z＝604.2654[M+H]+;1HNMR(δ、CDCl3)：8.06(1H,s);7.97～7.94(2H,m);7.75～7.72(2H,m);7.56～7.48(5H,m);7.45～7.37(4H,m);7.29～7.22(5H,m);7.20～7.14(4H,m);7.08～7.03(3H,m);7.01～6.97(1H,m);1.73(6H,s).
X: s, white solid, yield ：73％,MS(MALDI-TOF)：m/z＝620.2352[M+H]+;1HNMR(δ、CDCl3)：8.05(1H,s);7.98(1H,s);7.76～7.73(2H,m);7.59～7.52(5H,m);7.50～7.38(5H,m);7.35～7.28(4H,m);7.26～7.17(5H,m);7.09～7.04(3H,m);7.02～6.98(1H,m);1.72(6H,s).
Referring to the above-described similar synthetic method, the following compounds shown in table 2 were prepared:
TABLE 2
In the above embodiments, each T-is independently selected from one of the following structures:
* -X-each independently selected from-O-, S-, or one of the structures shown below:
* -and-represents a bond.
Example 3
As shown in fig. 1, the OLED element of the present 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, wherein the method for preparing the OLED element excluding 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, rinsed in deionized water, subjected to ultrasonic treatment in an acetone/ethanol mixed solvent for 30 minutes, baked in a clean environment until completely dried, irradiated by an ultraviolet light cleaning machine for 10 minutes, and bombarded on the surface by a low-energy cation beam.
2) Placing the above ITO glass substrate in a vacuum chamber, vacuumizing to less than 1× -5 Pa, evaporating metallic silver as anode layer on the ITO film, and evaporating film thickness to beContinuing to vapor deposit the compounds HI01 and F4TCNQ respectively as hole injection layers, wherein F4TCNQ is 3% of HI01 by mass, and the vapor deposition film thickness is
3) Continuously evaporating compound HTM as hole transport layer on the hole injection layer to obtain an evaporating film with a thickness of
4) Continuing to vapor deposit the compound represented by the formula (I) of the present invention as an electron blocking layer on the hole transport layer, the vapor deposition film thickness being
5) Vapor deposition of the compound GH015 as a host material and GD040 as a dopant material were continued on the electron blocking layer, with GD040 being 3% by mass of GH015 as an organic light-emitting layer of the device, and the film thickness of the vapor-deposited organic light-emitting layer being
6) Continuously evaporating a layer of LiQ and a compound ET028 on the organic light-emitting layer as an electron transport layer of the element, wherein the compound ET028 is 50% of the mass of the LiQ, and the evaporating film thickness is
7) Continuously evaporating a LiF layer on the electron transport layer to form an electron injection layer with an evaporating film thickness of
8) Evaporating metal magnesium and silver on the electron injection layer to obtain a transparent cathode layer with a mass ratio of magnesium to silver of 1:10, and evaporating film thickness of
9) Evaporating CPD layer as CPL layer of the device on the transparent cathode layer to obtain an evaporated film thickness ofThe OLED element provided by the invention is obtained.
The structure of the compound used in example 3 above is as follows:
Example 4
An organic electroluminescent device 200, the structure of which is shown in fig. 2, 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.
Comparative example 1
By following the same procedure as in example 3, substituting the compound of the invention of formula (I) in step 4) with H01 gives comparative element 1;
The organic electroluminescent element prepared by the above process was subjected to the following performance test:
the driving voltage and current efficiency and the lifetime of the organic electroluminescent elements prepared in examples 3 and 4 and comparative example 1 were measured using a digital source meter and a luminance meter. Specifically, the voltage was increased at a rate of 0.1V per second, and the driving voltage, which is the voltage when the luminance of the organic electroluminescent element reached 1000cd/m2, was measured, while the current density at that time was measured; the ratio of brightness to current density is the current efficiency; LT95% life test is as follows: the time, in hours, for which the luminance decay of the organic electroluminescent element was 950cd/m 2 was measured using a luminance meter at a luminance of 1000cd/m2 with a constant current. The data listed in table 5 are relative data compared to comparative element 3.
TABLE 3 Table 3
In the above table, me is methyl, ph is phenyl, FR is 9, 9-fluorenyl, and Ad is adamantyl.
As is clear from Table 3, the fluorene derivative of the present invention has a lower driving voltage than H01, a significantly improved current efficiency up to as much as 1.2 times that of the comparative element, and a significantly improved LT95% lifetime of the element at the same luminance, indicating that the fluorene derivative of the present invention is an excellent electron blocking layer material.
The compound H01 of comparative example 1 is different from the compound of the present invention in that the planar conjugation ability of the fluorenyl indene is enhanced, the hole transport and charge blocking properties are lowered, resulting in high voltage and reduced efficiency. The fluorene derivative of the present invention has improved charge blocking performance after one indene plane is reduced, so that the fluorene derivative is more excellent in molecular film formation and charge blocking performance, and the charge transmission in the element is more balanced, so that the element performance is obviously improved.
While the invention has been described in detail in the foregoing general description and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.

Claims (6)

1. A fluorene derivative, wherein said fluorene derivative is selected from the group consisting of the structures shown below:
Wherein each X is independently selected from O, S;
Each R 1、R2 is independently selected from methyl;
each R 3、R4、R5、R6、R7、R8、R9、R10 is independently selected from hydrogen;
ar 1、Ar2 is each independently selected from the group consisting of biphenyl, terphenyl, tetrabiphenyl, naphthyl, phenanthryl, anthracenyl, dibenzofuranyl, phenyl, carbazolyl, fluorenyl, or spirobifluorenyl;
n represents 0, 1;
l 1 is selected from single bond or A group of groups;
Wherein the dotted line represents the attachment site of the group.
2. Fluorene derivative according to claim 1, characterized in that it is selected from compounds represented by the following formulae D100-D204:
Wherein each X is independently selected from O, S;
* -T-, each independently selected from one of the following structures:
* -and- (x) represents a bond.
3. Use of a fluorene derivative according to any one of claims 1-2 in the preparation of an organic electroluminescent element.
4. An organic electroluminescent element, characterized in that it 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; a material of at least one of the organic layer or the capping layer comprising a fluorene derivative as claimed in any one of claims 1-2.
5. The organic electroluminescent element according to claim 4, 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;
The hole transport layer or the electron blocking layer comprises the fluorene derivative according to any one of claims 1-2.
6. A consumer electronic device characterized in that it comprises the organic electroluminescent element as claimed in claim 4.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107353890A (en) * 2016-05-09 2017-11-17 三星显示有限公司 Polycyclic compound and the Organnic electroluminescent device including the polycyclic compound
CN111423453A (en) * 2019-11-18 2020-07-17 烟台九目化学股份有限公司 Organic electroluminescent material with seven-membered heterocycle as main body and application thereof

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US10490753B2 (en) * 2016-12-15 2019-11-26 Universal Display Corporation Organic electroluminescent materials and devices

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107353890A (en) * 2016-05-09 2017-11-17 三星显示有限公司 Polycyclic compound and the Organnic electroluminescent device including the polycyclic compound
CN111423453A (en) * 2019-11-18 2020-07-17 烟台九目化学股份有限公司 Organic electroluminescent material with seven-membered heterocycle as main body and application thereof

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