CN115536535A - Fluorene derivative and organic light-emitting element containing same - Google Patents

Fluorene derivative and organic light-emitting element containing same Download PDF

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CN115536535A
CN115536535A CN202211211985.3A CN202211211985A CN115536535A CN 115536535 A CN115536535 A CN 115536535A CN 202211211985 A CN202211211985 A CN 202211211985A CN 115536535 A CN115536535 A CN 115536535A
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unsubstituted
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fluorene derivative
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CN115536535B (en
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张海威
李程辉
邸庆童
张昊
边坤
刘殿君
郭文龙
王振宇
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Beijing Bayi Space LCD Technology 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 an organic light-emitting element containing the fluorene derivative. The structure of the fluorene derivative is shown as a formula (I), the plane conjugation capacity of the fluorene derivative is increased, and the thermal stability and the carrier transport capacity of the material are improved; when the fluorene derivative is applied to an organic electroluminescent element, the driving voltage can be obviously reduced, the luminous efficiency can be improved, and the service life can be prolonged;
Figure DDA0003875543680000011

Description

Fluorene derivative and organic light-emitting element containing same
Technical Field
The invention relates to the technical field of organic electroluminescent materials, in particular to a fluorene derivative, an organic material and application thereof in an organic electroluminescent element.
Background
In recent years, optoelectronic devices based on organic materials are becoming more popular, and compared with inorganic materials, the inherent flexibility of organic materials makes them suitable for manufacturing on flexible substrates, and various optoelectronic products can be designed and produced according to requirements. Currently known organic optoelectronic devices include Organic Light Emitting Diodes (OLEDs), organic field effect transistors, organic photovoltaic cells, organic sensors, and the like; among them, OLEDs have advantages of self-luminescence, high contrast, wide color gamut, flexibility, low power consumption, etc., have been developed particularly rapidly, have been commercially successful, and are widely used in various fields such as flexible display, flat panel display, and solid state lighting.
The OLED element comprises a cathode, an anode and an organic thin film structure arranged between the two electrodes, the core of the OLED element is a thin film structure containing various organic functional materials, and the common organic functional materials comprise: a hole injection material, a hole transport material, a hole blocking material, an electron injection material, an electron transport material, an electron blocking material, a light emitting host material, a light emitting guest (dopant material), and the like. When electricity is applied, electrons and holes are injected, transported to the light emitting region, and recombined therein, respectively, to generate excitons and emit light. In OLED elements, organic functional materials directly affect the light emitting properties of the device.
The hole transport material is used as a universal layer material of the OLED element, and the core indexes of the element, such as voltage, efficiency, service life and the like, are influenced by adjusting the injection and transport performance of holes. At present, hole transport materials for commercial mass production are mainly arylamine materials, and due to different material collocation of devices, the problems of OLED product efficiency, service life, cost and the like cannot be completely solved by the currently used materials and element structures.
In order to overcome the above-described problems and to further improve the characteristics of the organic electroluminescent element, development of a more stable and effective substance that can be used as 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 has good photoelectric characteristics, and an organic electroluminescent element prepared by using the fluorene derivative, particularly an element used as a hole transport material and/or an electron blocking material, can obviously reduce the driving voltage, improve the luminous efficiency and prolong the service life; another object of the present invention is to provide use of the fluorene derivative in an organic electroluminescent device.
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 BDA0003875543660000011
wherein two adjacent radicals W 1 And W 2 Represents a group of the formula (II) and "^" indicates the adjacent group W in the formula (I) 1 And W 2 ；
Figure BDA0003875543660000021
R 1 、R 2 、R 3 、R 4 、R 5 Each independently selected from hydrogen, deuterium, C 1 -C 40 Alkyl of (C) 3 -C 40 Cycloalkyl, 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, substituted or unsubstituted C 2 -C 60 Heterocyclic aryl groups;
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;
m is an integer of 0 to 5;
L 1 selected from single bond, substituted or unsubstituted C 6 -C 60 Or substituted or unsubstituted C 2 -C 60 A heteroarylene group.
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.
Preferably, R is 3 、R 4 、R 5 Each is hydrogen or deuterium; r 1 、R 2 Each independently selected from C 1 -C 40 Alkyl, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 2 -C 60 Heterocyclic aryl groups.
Preferably, ar is 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 Arylamino, or substituted or unsubstituted C 2 -C 60 Heterocyclic aryl groups.
Preferably, m is 0, 1 or 2.
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 also being optionally substituted; alkenyl or alkynyl groups contain at least two carbon atoms, and as non-limiting examples, alkyl, alkenyl or alkynyl groups are preferably considered to refer to 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 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-pentyloxy, sec-pentyloxy, 2-methylbutoxy, n-hexyloxy, cyclohexyloxy, n-heptyloxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy and 2, 2-trifluoroethoxy.
Heteroalkyl is preferably alkyl having 1 to 40 carbon atoms, meaning that the individual hydrogen atoms or-CH 2 The radicals are substituted by oxygen, sulfur or halogen atoms, by way of non-limiting examples, alkoxy, alkylthio, fluorinated alkoxy, fluorinated alkylthio, in particular methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, trifluoromethylthio, trifluoromethoxy, pentafluoroethoxy, pentafluoroethylthio, 2-trifluoroethoxy, 2-trifluoroethylthio, vinyloxy, vinylthio, propenyloxy, propenylthio, butenylthio, butenyloxy, pentenyloxy, pentenylthio, cyclopentenyloxy, cyclopentenylthio, hexenyloxy, hexenylthio, cyclohexenyloxy, cyclohexenylthio, ethynyloxy, ethynylthio, propynyloxy, propynylthio, butynyloxy, butynylthio, pentynyloxy, pentynylthio, hexynyloxy, hexynylthio.
In general, the cycloalkyl, cycloalkenyl groups according to the invention may be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptyl, cycloheptenyl, where one or more-CH may be present 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 an atomic number of 3 to 40. In this case, 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.
Fused cyclophane used in the inventionThe group is a monovalent functional group obtained by combining two or more aromatic hydrocarbons having 6 to 60 carbon atoms in a ring and removing one hydrogen atom. 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 BDA0003875543660000031
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 non-limiting examples of the heteroarylamine group include an N-phenylpyridine-3-amine group, an N- ([ 1,1 '-biphenyl ] -4-yl) dibenzo [ b, d ] furan-2-amine group, an N- ([ 1,1' -biphenyl ] -4-yl) -9, 9-dimethyl-9H-fluorene-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. As non-limiting examples of such alkoxy groups, there may be mentioned 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 aryl phosphorus group used in the present invention means a diaryl phosphorus group substituted with an aryl group having 6 to 60 carbon atoms, and non-limiting examples of the aryl phosphorus group include a diphenyl phosphorus group, a bis (4-trimethylsilylphenyl) phosphorus group and the like. The aryloxyphosphoryl group is a group in which the phosphorus atom of the diarylphosphorus group is oxidized to the maximum 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 as non-limiting examples of the arylboron group, there are a diphenylboron group, a bis (2, 4, 6-trimethylphenyl) 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, said aryl, heterocyclic aryl, in particular refers to groups derived from: phenyl, naphthyl, anthryl, benzanthryl, phenanthryl, pyrenyl,
Figure BDA0003875543660000032
A phenyl group, a peryleneyl group, a fluoranthenyl group, a tetracenyl group, a pentacenyl group, a benzopyrenyl group, a biphenyl group, an idophenyl group, a terphenyl group, a quaterphenyl group, a fluorenyl group, a spirobifluorenyl group, a phenanthrenyl group, a triphenylenyl group, a dihydropyrenyl group, a tetrahydropyrenyl group, a cis-or trans-indenofluorenyl group, a cis-or trans-indenocarbazolyl group, a cis-or trans-indolocarbazolyl group, a triindenylgroup, an isotridecylindenyl group, a spiroisotridecylindenyl group, a furanyl group, a benzofuranyl group, an isobenzofuranyl group, a dibenzofuranyl group, a thienyl group, a benzothienyl group, an isobenzothienyl group, a dibenzothienyl group, a pyrrolyl group, an indolyl group, an isoindolyl group, a carbazolyl group, a pyridyl group, a quinolyl group, an isoquinolyl group, an acridinyl group, a phenanthridinyl group, a benzo [5,6 ] group]Quinolyl, benzo [6,7 ]]Quinolyl, benzo [7,8 ]]Quinolyl, phenothiazinyl, phenoxazinyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxaloimidazolyl, oxazolyl, benzoxazolyl, naphthooxazolyl, anthraoxazolyl, phenanthrooxazolyl, isoxazolyl, 1, 2-thiazolyl, 1, 3-thiazolyl, benzothiazolyl, pyridazinyl, hexaazabenzophenanthrenyl, benzopyrazinyl, pyrimidinyl, benzopyrimidinylA group selected from the group consisting of a phenyl group, a quinoxalinyl group, a 1, 5-diazanthryl group, a 2, 7-diazpyrenyl group, a 2, 3-diazpyrenyl group, a 1, 6-diazpyrenyl group, a 1, 8-diazpyrenyl group, a 4,5,9, 10-tetraazaperylenyl group, a pyrazinyl group, a phenazinyl group, a phenoxazinyl group, a phenothiazinyl group, a fluoryl group, a naphthyridinyl group, an azacarbazolyl group, a benzocarbazinyl group, a carbolinyl group, a phenanthrolinyl group, a 1,2, 3-triazolyl group, a 1,2, 4-triazolyl group, a benzotriazolyl group, a 1,2, 3-oxadiazolyl group, a 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, 1,3,5-triazinyl, 1,2,4-triazinyl, 1,2,3-triazinyl, tetrazolyl, 1,2,4,5-tetrazinyl, 1,2,3,4-tetrazinyl, 1,2,3,5-tetrazinyl, purinyl, pteridinyl, indolizinyl, quinazolinyl, benzothiadiazolyl, or groups derived from a combination of these systems.
Further, said R 1 、R 2 Each independently selected from the group consisting of a methyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted quaterphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted fluorenyl group, and a substituted or unsubstituted carbazolyl group.
Further, said Ar 1 、Ar 2 Each independently selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted quaterphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylene, substituted or unsubstituted anthryl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted fluorenyl, and substituted or unsubstituted carbazolyl.
Preferably, L is 1 Selected from a single bond or a group consisting of the following groups III-1 to III-23:
Figure BDA0003875543660000041
wherein the dotted line represents the attachment site of the group.
In the present invention, the term "substituted or unsubstituted" means a compound selected from the group consisting of hydrogen, deuterium, fluorine, hydroxyl, nitrile, nitro, amino, amidino, hydrazine, hydrazone, carboxyl or carboxylate thereof, sulfonic acid or sulfonate thereof, phosphoric acid or phosphate thereof, and C 1 -C 40 Alkyl of (C) 2 -C 40 Alkenyl of, C 2 -C 40 Alkynyl of, C 1 -C 40 Alkoxy group of (C) 3 -C 40 Cycloalkyl of, C 3 -C 40 Cycloalkenyl group of (1), C 6 -C 60 Aryl of (C) 6 -C 60 Aryloxy group of (A), C 6 -C 60 And C is an aryl sulfide group 2 -C 60 The heterocyclic aryl group of (1) is substituted or unsubstituted or substituted or unsubstituted with a substituent in which 2 or more substituents among the above-exemplified substituents are bonded.
Preferably, the structural formula of the fluorene derivative is selected from the group consisting of D01 to D201 below:
Figure BDA0003875543660000042
Figure BDA0003875543660000051
Figure BDA0003875543660000061
Figure BDA0003875543660000071
Figure BDA0003875543660000081
Figure BDA0003875543660000091
Figure BDA0003875543660000101
Figure BDA0003875543660000111
Figure BDA0003875543660000121
Figure BDA0003875543660000131
wherein T is selected from O, S, or one of the following structures:
Figure BDA0003875543660000141
preferably, said T-is selected from O-, S-, or one of the following structures:
Figure BDA0003875543660000142
further, the T is selected from O, S or one of the following structures:
Figure BDA0003875543660000143
the foregoing represents a bond.
The invention provides a synthetic route of a compound shown as a formula (I), which is shown as follows:
Figure BDA0003875543660000144
wherein, X 1 、X 2 Represents I, br, cl, OTf, CO 2 H. Boronic acid or boronic acid pinacol ester; the other symbols used are as defined above.
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.
In particular, the compounds of formula (I) are represented by X 1 The substituted I-0 is subjected to SUZUKI coupling reaction, substitution reaction, condensation reaction, buchwald-Hartwig coupling reaction and the like to prepare a compound shown in the formula (I). Intermediate Ar 1 Ar 2 N-(L 1 ) m B(OH) 2 Or Ar 1 Ar 2 The NH is prepared by a palladium-catalyzed or base-catalyzed coupling reaction.
As palladium catalysts which may be used in 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 solvents such as benzene, toluene, or xylene, chlorobenzene, dichlorobenzene, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, or sulfolane, and one or a mixture of two or more thereof may 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 carrier transporting ability or light extracting ability.
Preferably, the organic electroluminescent material is a hole injection layer material, a hole transport layer material, a hole blocking layer material, a light emitting layer material, an electron transport layer material, an electron injection layer material, a light extraction layer material, or an electron blocking layer material.
The present invention also provides an organic electroluminescent element comprising: a first electrode, a second electrode, a light extraction layer, and one or more organic layers disposed between the first electrode and the second electrode; at least one of the organic layer and the light extraction layer includes the fluorene derivative described above.
The organic electroluminescent element includes a first electrode, a second electrode, a light extraction layer, and at least one light emitting layer. In addition to these layers, it may also comprise further layers, for example in each case one or more hole-injecting layers, hole-transporting layers, electron-blocking layers, electron-transporting layers, electron-injecting layers, hole-blocking layers 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 element 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 compounds of the invention according to the 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 hole injection 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 transport layer and the light-emitting layer and in the light extraction 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 can be applied by means of a sublimation process in which the temperature is below 10 ℃ in a vacuum sublimation apparatus -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 can also be applied by means of organic vapor deposition methods or by means of carrier gas sublimation, where 10 is -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 of a compound of formula (I). 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 of manufacturing an organic electroluminescent element according to the invention, comprising applying at least one layer by means of a sublimation method, and/or applying at least one layer by means of an organic vapour deposition method or by means of carrier gas sublimation, and/or applying at least one layer from solution by spin coating or by means of a printing method.
Furthermore, the present invention relates to pharmaceutical compositions comprising at least one compound of the invention as indicated above. The same preferences as indicated above for the organic electroluminescent elements apply to the compounds according to the invention. In particular, the compounds may furthermore preferably comprise further compounds. Processing the compounds of the invention from the liquid phase, for example by spin coating or by printing methods, requires processing preparations of the compounds of the invention, which may be, for example, solutions, dispersions or emulsions. For this purpose, it may be preferred to use a mixture of two or more solvents. Suitable and preferred solvents are, for example, toluene, anisole, o-xylene, m-or p-xylene, methyl benzoate, mesitylene, tetralin, o-dimethoxybenzene, tetrahydrofuran, methyltetrahydrofuran, tetrahydropyran, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxytoluene, (-) -fenchytone, 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, 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 dibutyl glycol methyl ether, triethyl glycol, tripropyl glycol, 1, 2-dimethyl benzyl ether, 1, 2-octylbenzene glycol, 1, 2-dimethyl-octylbenzene ether, 1, octylbenzene glycol, or mixtures of these solvents.
The present invention also provides an application of an organic electroluminescent element used in any one device selected from the following devices:
a flat panel display device;
a flexible display device;
a monochromatic or white flat panel lighting device; or
A monochromatic or white flexible lighting device.
The invention has the following beneficial effects:
the fluorene derivative has a structure shown in a formula (I), and a mother nucleus group can effectively regulate and control the three-dimensional structure of molecules, so that the stacking density of the molecules is improved; meanwhile, the triarylamine structure and the fluorene structure act together, so that the compound has excellent hole transport performance, the HOMO energy level of the compound is regulated and improved, the HOMO energy level of the compound is more matched with the energy level of an anode, the hole injection and transport capacity of the compound are improved, the low voltage acquisition is facilitated, and the stability of the compound for transporting carriers in an electric field environment is obviously improved. Moreover, the special tetrahedral conjugated structure of the organic compound enables the preparation of a good amorphous film, so that the organic compound can be applied to an organic electroluminescent element to remarkably reduce the driving voltage, improve the luminous efficiency and prolong the service life.
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 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 the 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 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 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 all conventional procedures 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.
In addition, unless otherwise specified, any range recited herein includes any value between the endpoints and any sub-range defined by any value between the endpoints or any value between the endpoints.
The following test instruments and methods for performance testing of OLED materials and devices were used in the examples as follows:
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: NEWPORT 1931-C was used for testing.
Example 1
A process for the preparation of compound D31 comprising the steps of:
the first step is as follows: preparation of intermediate Int-1
Figure BDA0003875543660000171
Under the protection of nitrogen, 22.0mmol of SM-1 (CAS: 2667606-44-0), 20.0mmol of 5-chloro-2-bromo-benzoate, 60.0mmol of potassium phosphate hydrate, 0.1mmol of Pd0132, 80mL of 1, 4-dioxane and 25mL of water are mixed, heated to reflux, stirred and reacted for 12 hours, cooled to room temperature, 100mL of saturated aqueous ammonium chloride solution is added, extracted by ethyl acetate, the organic phase is collected, dried, concentrated under reduced pressure, and separated and purified by silica gel column to obtain the compound Int-1, white solid, yield: and 75 percent.
The second step is that: preparation of Compound Int-2
Figure BDA0003875543660000172
Under the protection of nitrogen, 20.0mmol of intermediate Int-1 is dissolved in 60mL of dry THF, the temperature is reduced to 0 ℃, 60.0mmol of 1M methyl magnesium bromide THF solution is dropwise added, the temperature is raised to room temperature, the reaction is stirred for 1 hour, 20mL of 3N dilute hydrochloric acid aqueous solution is added, an organic phase is separated, the aqueous phase is extracted by ethyl acetate, the organic phase is collected, dried, decompressed and concentrated, and separated and purified by a silica gel column to obtain a compound Int-2, namely a white solid, the yield: 83 percent.
The third step: preparation of Compound Int-3
Figure BDA0003875543660000181
Under the protection of nitrogen, 20.0mmol of intermediate Int-2 is dissolved in 60mL of dry dichloromethane, the temperature is reduced to 0 ℃, 30.0mmol of boron trifluoride diethyl etherate solution is added dropwise, the mixture is heated to room temperature and stirred for reaction for 12 hours, 20mL of water is added, an organic phase is separated, the aqueous phase is extracted by dichloromethane, the organic phase is collected and washed by 5% of sodium hydroxide aqueous solution, the organic phase is dried, decompressed and concentrated, and is separated and purified by silica gel column to obtain a compound Int-3, a white solid, and the yield: 87 percent.
The fourth step: preparation of Compound D31
Figure BDA0003875543660000182
Under the protection of nitrogen, 22.0mmol of intermediate Int-3 is dissolved in 60mL of dry toluene, and 20.0mmol of diarylamine, 30.0mmol of sodium tert-butoxide and 0.2mmol of Pd are added 2 (dba) 3 Heating to 110 ℃ with 0.4mmol of 10% tri-tert-butylphosphonium toluene solution, stirring for 12 hours, cooling to room temperature, adding 50mL of water, separating out an organic phase, extracting a water phase with toluene, combining and drying the organic phase, filtering, concentrating the filtrate under reduced pressure, and separating and purifying by using a silica gel column to obtain a compound D31;
t = O, white solid, yield: 80%, MS (MALDI-TOF): m/z =728.2889[ 2 ] M + H] + ； 1 HNMR(δ、CDCl 3 )：8.83(1H,s)；8.44～8.36(5H,m)；8.11～8.09(1H,d)；7.98～7.90(5H,m)；7.79～7.72(5H,m)；7.65～7.63(1H,m)；7.61～7.52(4H,m)；7.50～7.45(2H,m)；7.40～7.33(6H,m)；6.91～6.88(1H,m)；1.79(6H,s)。
T＝CMe 2 White solid, yield: 76%, MS (MALDI-TOF): m/z =754.3414[ m ] +H ]] + ； 1 HNMR(δ、CDCl 3 )：8.83(1H,s)；8.44～8.36(5H,m)；8.19～8.17(1H,d)；8.11～8.06(4H,m)；7.91～7.85(2H,m)；7.78(1H,s)；7.74～7.72(2H,m)；7.61～7.59(1H,m)；7.56～7.52(4H,m)；7.50～7.45(2H,m)；7.40～7.32(5H,m)；7.30～7.26(2H,m)；7.15～7.13(1H,d)；1.73(6H,s)；1.68(6H,s)。
T = NPh, white solid, yield: 72%, MS (MALDI-TOF): m/z =803.3394[ M ] +H] + ； 1 HNMR(δ、CDCl 3 )：8.83(1H,s)；8.53(1H,s)；8.42～8.36(5H,m)；8.23～8.20(2H,d)；8.11～8.06(4H,m)；7.93～7.90(1H,m)；7.79(1H,s)；7.74～7.72(2H,m)；7.63～7.57(4H,m)；7.55～7.51(3H,m)；7.48～7.43(4H,m)；7.40～7.32(5H,m)；7.24～7.21(2H,m)；7.15～7.12(1H,m)；1.74(6H,s)。
T = FR (9,9-fluorenyl), white solid, yield: 72%, MS (MALDI-TOF): m/z =876.3616[ M + H ]] + ； 1 HNMR(δ、CDCl 3 )：8.83(1H,s)；8.42～8.36(5H,m)；8.19～8.17(1H,d)；8.11～8.06(4H,m)；7.92～7.86(4H,m)；7.78(1H,s)；7.74～7.71(2H,m)；7.62～7.58(1H,m)；7.55～7.50(4H,m)；7.48～7.43(4H,m)；7.40～7.32(6H,m)；7.29～7.21(5H,m)；7.15～7.12(1H,m)；1.74(6H,s)。
With reference to the analogous synthetic procedures described above, the following compounds shown in table 1 were prepared:
TABLE 1
Figure BDA0003875543660000183
Figure BDA0003875543660000191
Figure BDA0003875543660000201
Figure BDA0003875543660000211
Figure BDA0003875543660000221
Figure BDA0003875543660000231
Example 2
A process for the preparation of compound D89, comprising the steps of:
the first step is as follows: preparation of intermediate Int-4
Figure BDA0003875543660000232
Referring to the synthetic procedure of example 1, the compound Int-4 was prepared as a white solid in yield by replacing only methyl 5-chloro-2-bromobenzoate in the first step of example 1 with 4-chloro-2-bromoiodobenzene: 76 percent.
The second step: preparation of Compound Int-5
Figure BDA0003875543660000233
Under the protection of nitrogen, dissolving 20.0mmol of intermediate Int-4 in 60mL of dry THF, cooling to-78 ℃ with liquid nitrogen, dropwise adding 22.0mmol of 2.5M N-butyllithium N-hexane solution, stirring for reaction for 30 minutes, dropwise adding 22.0mmol of fluorenone solution in THF, heating to warm temperature, stirring for reaction for 2 hours, adding 20mL of 3N dilute hydrochloric acid aqueous solution, separating out an organic phase, extracting an aqueous phase with ethyl acetate, combining and drying the organic phase, filtering, concentrating the filtrate under reduced pressure to dryness to obtain a yellow solid, dissolving the yellow solid in 50mL of dichloromethane, cooling to 0 ℃ and dropwise adding 30.0mmol of boron ethyl ether solution, heating to room temperature, stirring for reaction for 12 hours, adding 20mL of 25% sodium hydroxide aqueous solution, separating out the organic phase, drying, concentrating to dryness under reduced pressure, separating and purifying by using a silica gel column to obtain compound Int-5, a white solid, wherein the yield is as follows: 74 percent.
The third step: preparation of Compound D89
Figure BDA0003875543660000241
Under the protection of nitrogen, 22.0mmol of intermediate Int-5 is dissolved in 80mL of dry toluene, and 20.0mmol of diphenylamine, 30.0mmol of sodium tert-butoxide, and 0.2mmol of Pd are added 2 (dba) 3 And 0.4mmol of 10% tri-tert-butylphosphonium toluene solution, heating to 110 ℃, stirring for reaction for 12 hours, cooling to room temperature, adding 50mL of water, separating an organic phase, extracting an aqueous phase with toluene, combining and drying the organic phase, filtering, concentrating the filtrate under reduced pressure to dryness, and separating and purifying by using a silica gel column to obtain a compound D89, namely a white solid, wherein the yield is as follows: 84%, MS (MALDI-TOF): m/z =836.3257[ M ] +H] + ； 1 HNMR(δ、CDCl 3 )：8.89(1H,s)；8.42～8.36(4H,m)；8.18～8.16(1H,d)；8.11～8.06(4H,m)；7.92～7.89(2H,m)；7.78(1H,s)；7.74～7.70(4H,m)；7.64～7.62(1H,m)；7.55～7.50(5H,m)；7.48～7.42(5H,m)；7.40～7.32(6H,m)；7.29～7.21(5H,m)；7.18～7.15(2H,m)。
With reference to the analogous synthetic procedures described above, the following compounds shown in table 2 were prepared:
TABLE 2
Figure BDA0003875543660000242
Figure BDA0003875543660000251
Figure BDA0003875543660000261
Example 3
A process for the preparation of compound D126 comprising the steps of:
the first step is as follows: preparation of Compound Int-6
Figure BDA0003875543660000262
Under the protection of nitrogen, 20.0mmol of SM-2 is dissolved in 80mL of dimethylbenzene, 50.0mmol of bis (p-bromophenyl) iodotrifluoromethanesulfonate, 2.0mmol of palladium acetate and 20.0mmol of sodium tert-butoxide are added, the temperature is raised to 110 ℃, the mixture is stirred and reacted for 24 hours, the mixture is cooled to room temperature, 50mL of water is added, an organic phase is separated out, the aqueous phase is extracted by toluene, the organic phase is combined and dried, the filtration is carried out, the filtrate is concentrated under reduced pressure to dryness, and the filtrate is separated and purified by a silica gel column to obtain a compound Int-6, a yellow solid and the yield: 83 percent.
The second step is that: preparation of Compound Int-7
Figure BDA0003875543660000271
Under the protection of nitrogen, dissolving 24.4mmol of iodine in 200mL of glacial acetic acid, dropwise adding 24.4mmol of 50% hypophosphorous acid, heating to 100 ℃, stirring to react until red color disappears, adding 20.0mmol of Int-6, heating to reflux for 6 hours, concentrating under reduced pressure until about 50mL of residual, adding 200mL of ice water, filtering, washing a filter cake with water and ethanol, and separating and purifying a yellow solid by using a silica gel column to obtain a compound Int-7, namely a white solid, wherein the yield is as follows: and 90 percent.
The third step: preparation of Compound Int-8
Figure BDA0003875543660000272
Under the protection of nitrogen, 20.0mmol of Int-7 is dissolved in 200mL of THF, 118.0mmol of potassium tert-butoxide is added, 79.0mmol of iodomethane is added dropwise, the mixture is stirred at room temperature for 12 hours, 150mL of ice water is added, an organic phase is separated, a dichloromethane is used for extraction of an aqueous phase, the organic phase is combined and dried, filtration is carried out, a filtrate is concentrated under reduced pressure and dried, and a silica gel column is used for separation and purification to obtain a compound Int-8, a white solid, and the yield: 85.5 percent.
The fourth step: preparation of Compound D126
Figure BDA0003875543660000273
Under the protection of nitrogen, 22.0mmol of intermediate Int-8 is dissolved in 120mL of dry toluene, and 20.0mmol of biphenylnaphthylamine, 30.0mmol of sodium tert-butoxide and 0.2mmol of Pd are added 2 (dba) 3 And 0.4mmol of Xantphos, heating to 110 ℃, stirring for reaction for 12 hours, cooling to room temperature, adding 50mL of water, separating an organic phase, extracting the aqueous phase with toluene, combining and drying the organic phase, filtering, concentrating the filtrate under reduced pressure to dryness, and separating and purifying by using a silica gel column to obtain a compound D126, a white solid, and the yield: 86%, MS (MALDI-TOF): m/z =688.3012[ m + H ]] + ； 1 HNMR(δ、CDCl 3 )：8.71(1H,s)；8.55～8.48(3H,m)；8.29～8.27(1H,d)；8.13～8.06(2H,m)；7.89～7.86(1H,m)；7.72～7.62(5H,m)；7.60～7.45(4H,m)；7.41～7.36(2H,m)；7.25～7.21(2H,m)；7.18～7.07(7H,m)；7.04(1H,s)；7.01～6.98(2H,m)；1.82(6H,s)。
With reference to the analogous synthetic procedures described above, the following compounds shown in table 3 were prepared:
TABLE 3
Figure BDA0003875543660000274
Figure BDA0003875543660000281
Figure BDA0003875543660000291
Figure BDA0003875543660000301
Example 4
A process for the preparation of compound D166, comprising the steps of:
the first step is as follows: preparation of Compound Int-9
Figure BDA0003875543660000302
Under the protection of nitrogen, 20.0mmol of Int-6 is dissolved in 60mL of dry THF, the temperature is reduced to 0 ℃,22.0mmol of phenylmagnesium bromide THF solution is added dropwise, the mixture is heated to room temperature and stirred for reaction for 2 hours, 20mL of 2N dilute hydrochloric acid aqueous solution 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 under reduced pressure, and the separation and purification are carried out by a silica gel column, so that a compound Int-9, yellow solid, yield: 88 percent.
The second step is that: preparation of Compound Int-10
Figure BDA0003875543660000311
Under the protection of nitrogen, dissolving 20.0mmol of Int-9 in 80mL of benzene, dropwise adding 40.0mmol of concentrated sulfuric acid, heating to reflux reaction for 12 hours, cooling to room temperature, dropwise adding 50mL of ice water, separating an organic phase, extracting a water phase with benzene, drying the organic phase, filtering, concentrating a filtrate under reduced pressure, and separating and purifying an obtained green solid by using a silica gel column to obtain a compound Int-10, namely a white solid, wherein the yield is as follows: 82 percent.
The third step: preparation of Compound D166
Figure BDA0003875543660000312
Referring to the synthesis of the fourth step of example 3, replacing only Int-8 in the fourth step of example 3 with Int-10 and replacing biphenylnaphthylamine with biphenylnaphthylamine for biphenylnaphthylamine, compound D166 was prepared as a white solid in yield: 85 percent. MS (MALDI-TOF): m/z =838.3478[ m ] +H] + ； 1 HNMR(δ、CDCl 3 )：8.55～8.51(2H,m)；8.29～8.22(2H,m)；8.11(1H,s)；7.64～7.59(3H,m)；7.55～7.45(7H,m)；7.40～7.32(6H,m)；7.25～7.21(2H,m)；7.15～7.07(8H,m)；7.05～6.98(7H,m)；6.95(1H,s)；6.93～6.84(4H,m)。
With reference to the analogous synthetic procedures described above, the following compounds shown in table 4 were prepared:
TABLE 4
Figure BDA0003875543660000313
Figure BDA0003875543660000321
Figure BDA0003875543660000331
Figure BDA0003875543660000341
Figure BDA0003875543660000351
In the above embodiments, T-is selected from O-, S-, or one of the following structures:
Figure BDA0003875543660000352
example 5
An organic electroluminescent device 100, the structure of which is shown in fig. 1, comprises 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, and the preparation method of the element without the hole blocking layer 107 comprises 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, evaporating silver on the ITO film to form an anode layer with a thickness of
Figure BDA0003875543660000353
Evaporating compounds HI01 and HI102 as hole injection layer, wherein HI102 is 3% of HI01 mass, and the thickness of the evaporated film is
Figure BDA0003875543660000354
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 BDA0003875543660000355
4) The compound represented by the formula (I) of the invention is continuously evaporated on the hole transport layer to form an electron blocking layer, and the thickness of the evaporated film is
Figure BDA0003875543660000356
5) The electron blocking layer is continuously evaporated with BH012 as a main material and BD022 as a doping material, the BD022 is 3% of the mass of the BH012, and the electron blocking layer is used as an organic light-emitting layer with the thickness of the evaporation film
Figure BDA0003875543660000357
6) And continuously evaporating a layer of LiQ and ET015 on the organic light-emitting layer to form an electron transport layer, wherein the mass ratio of LiQ to ET015 is 50
Figure BDA0003875543660000358
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 BDA0003875543660000359
8) And evaporating metal magnesium and silver on the electron injection layer to form a transparent cathode layer, wherein the mass ratio of magnesium to silver is 1
Figure BDA00038755436600003510
9) Depositing a CPL layer as an element on the transparent cathode layer by vapor deposition to a thickness of
Figure BDA00038755436600003511
The OLED element provided by the invention is obtained.
The structures of the compounds HI01, HI102, HTM, BH012, BD022, ET015 and LiQ used in example 5 are as follows:
Figure BDA00038755436600003512
Figure BDA0003875543660000361
example 6
An organic electroluminescent device 200, as shown in fig. 2, includes 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 corresponding layers of the device 200, materials similar to those described with respect to the device 100 may be used.
Comparative example 1
Following the same procedure as in example 5, the compound represented by the formula (I) in step 4) was replaced with B-1 to give comparative element 1; b-1 has the following structural formula:
Figure BDA0003875543660000362
comparative example 2
Following the same procedure as in example 4, the compound represented by formula (I) in step 4) was replaced with B-2 to give comparative element 2; b-2 has the following structural formula:
Figure BDA0003875543660000363
comparative example 3
Following the same procedure as in example 4, the compound represented by formula (I) in step 4) was replaced with B-3 to give comparative element 3; b-3 has the following structural formula:
Figure BDA0003875543660000364
the performance test data of the obtained element was normalized with reference to comparative element 1, and the results are shown in Table 5, in which the driving voltage and the luminous efficiency were such that the current density of the element was 10mA/cm 2 Under the conditions, the LT95% lifetime of the element was found to be at a current density of 50mA/cm 2 Is measured under the starting conditions of (1).
TABLE 5 test results of the performance of each element
Figure BDA0003875543660000365
Figure BDA0003875543660000371
Figure BDA0003875543660000381
Figure BDA0003875543660000391
Figure BDA0003875543660000401
Figure BDA0003875543660000411
In the table, me is methyl; ph is phenyl; phPhPh is biphenyl; nap is naphthyl; FR is 9,9-fluorenyl.
As is clear from Table 5, the light-emitting element produced by using the fluorene derivative of the present invention as an electron blocking material was also 10mA/cm 2 Under the condition, the driving voltage is obviously reduced compared with B-1, B-2 and B-3, the luminous efficiency and LT95% service life performance are greatly improved, the luminous efficiency can reach 1.4 times of that of a comparison element at most, and particularly the LT95% service life exceeds 3 times of that of the comparison element at most, which shows that the compound parent nucleus of the invention has improved stability and is an electron barrier layer material with excellent performance.
Compared with the compound B-1 of the comparative example, the fluorene derivative disclosed by the invention has the difference that the molecular plane of the B-1 is too large and the steric hindrance is very large, while the fluorene derivative disclosed by the invention is a tetrahedron conjugated plane and has small steric hindrance, the performance of the fluorene derivative in molecular film formation and charge transmission is excellent, and the charge transmission in an element is more balanced, so that the performance of the element is improved, and the performance of the compound disclosed by the invention in a light-emitting element is more excellent.
Compared with the compounds B-2 and B-3 of the comparative examples, the fluorene derivative disclosed by the invention has the difference that B-2 and B-3 are conjugated planar molecules, have no triarylamine groups and have deeper HOMO energy level, so that the imbalance of exciton transmission in an element and a larger carrier injection barrier are caused, the imbalance causes the driving voltage of the element to be increased, and the efficiency is reduced. The fluorene derivative has a triarylamine group, so that the carrier transmission performance is enhanced, the carrier injection barrier is reduced, the performance of the fluorene derivative on molecular film formation and charge transmission is excellent, and the exciton transmission in the element is more balanced, so that the element performance is improved, and the performance of the fluorene derivative on a light-emitting element is more excellent.
Although the invention has been described in detail with respect to the general description and the specific embodiments thereof, it will be apparent to those skilled in the art that modifications and improvements can be made 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 is characterized in that the structural formula is shown as a formula (I):
Figure FDA0003875543650000011
wherein two radicals W adjacent to each other 1 And W 2 Represents a group of the following formula (II), and "^" indicates adjacent group W in the formula (I) 1 And W 2 ；
Figure FDA0003875543650000012
R 1 、R 2 、R 3 、R 4 、R 5 Each independently selected from hydrogen, deuterium, C 1 -C 40 Alkyl of (C) 3 -C 40 Cycloalkyl, 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, substituted or unsubstituted C 2 -C 60 Heterocyclic aryl groups;
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;
m is an integer of 0 to 5;
L 1 selected from single bond, substituted or unsubstituted C 6 -C 60 Or substituted or unsubstituted C 2 -C 60 A heteroarylene group.
2. Fluorene derivative according to claim 1, wherein R is 3 、R 4 、R 5 Each is hydrogen or deuterium; r is 1 、R 2 Each independently selected from the group consisting of C 1 -C 40 Alkyl, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 2 -C 60 Heterocyclic aryl groups;
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 Arylamino, or substituted or unsubstituted C 2 -C 60 Heterocyclic aryl groups;
m is 0, 1 or 2.
3. Fluorene derivative according to claim 1, wherein R is 1 、R 2 Each independently selected from the group consisting of methyl, substituted or unsubstituted phenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted quaterphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylene, substituted or unsubstituted anthracenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted fluorenyl, and substituted or unsubstituted carbazolyl;
Ar 1 、Ar 2 each independently selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted biphenylA tetrakisbiphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted fluorenyl group, or a substituted or unsubstituted carbazolyl group.
4. Fluorene derivative according to any one of claims 1 to 3, wherein L is 1 Selected from a single bond or a group consisting of the following groups III-1 to III-23:
Figure FDA0003875543650000021
Figure FDA0003875543650000031
wherein the dotted line represents the attachment site of the group.
5. The fluorene derivative according to any one of claims 1 to 4, wherein the fluorene derivative is selected from the group consisting of D01 to D201:
Figure FDA0003875543650000032
Figure FDA0003875543650000041
Figure FDA0003875543650000051
Figure FDA0003875543650000061
Figure FDA0003875543650000071
Figure FDA0003875543650000081
Figure FDA0003875543650000091
Figure FDA0003875543650000101
Figure FDA0003875543650000111
Figure FDA0003875543650000121
wherein T is selected from O, S, or one of the following structures:
Figure FDA0003875543650000122
preferably, said T-is selected from O-, S-, or one of the following structures:
Figure FDA0003875543650000123
* -and-represent a bond.
6. The fluorene derivative according to claim 5, wherein the fluorene derivative is
* -T-is selected from-O-, S-, or one of the following structures:
Figure FDA0003875543650000131
* -and-represent a connecting bond.
7. An organic electroluminescent material characterized in that its raw material comprises the fluorene derivative according to any one of claims 1 to 6.
8. An organic electroluminescent element, characterized by comprising: a first electrode, a second electrode, a light extraction layer, and one or more organic layers disposed between the first electrode and the second electrode; at least one of the organic layer and the light extraction layer comprises the 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 at least one of: a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, an electron transport layer, an electron injection layer, and a hole blocking layer; the selected one or more layers of the respective layers are formed through a deposition process or a solution process.
10. The organic electroluminescent element according to claim 8 or 9, wherein the organic electroluminescent element is used in any one of the following devices:
a flat panel display device;
a flexible display device;
a monochromatic or white flat panel lighting device; or
A monochromatic or white flexible lighting device.
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CN112794856A (en) * 2019-11-14 2021-05-14 广州华睿光电材料有限公司 Organic compounds, mixtures, compositions and uses thereof
CN112794842A (en) * 2019-11-14 2021-05-14 广州华睿光电材料有限公司 Polycyclic compound and use thereof
CN115073501A (en) * 2021-03-10 2022-09-20 北京夏禾科技有限公司 Organic electroluminescent material and device thereof

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CN112794856A (en) * 2019-11-14 2021-05-14 广州华睿光电材料有限公司 Organic compounds, mixtures, compositions and uses thereof
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