CN115724750A - Spirofluorene derivative and application thereof - Google Patents

Spirofluorene derivative and application thereof Download PDF

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CN115724750A
CN115724750A CN202211434762.3A CN202211434762A CN115724750A CN 115724750 A CN115724750 A CN 115724750A CN 202211434762 A CN202211434762 A CN 202211434762A CN 115724750 A CN115724750 A CN 115724750A
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spirofluorene derivative
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CN115724750B (en
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张海威
姜坤
何连贞
唐怡杰
邸庆童
张昊
边坤
刘殿君
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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 spirofluorene derivative and application thereof. The structural formula of the spirofluorene derivative is shown as a formula (I); the compound shown in the formula (I) has a spirofluorene structure substituted by arylamine groups. 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.
Figure DDA0003946359370000011

Description

Spirofluorene derivative and application thereof
Technical Field
The invention relates to the technical field of organic electroluminescent materials, in particular to a spirofluorene derivative and application thereof in an organic light-emitting element.
Background
In general, the organic light emitting phenomenon refers to a phenomenon in which light is emitted when electric energy is applied to an organic substance; that is, when an organic layer is disposed between an anode and a cathode, if a voltage is applied between the two electrodes, holes are injected from the anode into the organic layer, and electrons are injected from the cathode into the organic layer; when the injected holes and electrons meet, excitons are formed, and when the excitons transition to a ground state, light and heat are emitted.
In recent years, organic electroluminescent display technology has become mature, and some products have entered the market, but in the process of industrialization, many problems still need to be solved. In particular, various organic materials used for manufacturing elements have many problems which are not solved, such as carrier injection and transmission performance, electroluminescent performance of the materials, service life, color purity, matching between various materials and between various electrodes, and the like; especially, the luminous efficiency and the service life of the light-emitting element are not practical, which greatly limits the development of the OLED technology. The metal complex phosphorescent material utilizing triplet state luminescence has high luminescence efficiency, and green and red materials of the metal complex phosphorescent material meet the use requirements, but the metal complex phosphorescent material requires a phosphorescent material or a hole material with a high triplet state energy level to be matched with the metal complex phosphorescent material, so that the development of the phosphorescent material or the hole material with the high triplet state energy level is an urgent need of the current development of the OLED.
Under the current technological development, improvements are also needed, both for fluorescent materials and for phosphorescent materials, in particular in terms of operating voltage, efficiency and lifetime for use in organic electroluminescent elements and thermal stability during sublimation.
In order to overcome the above-described problems and further improve the characteristics of the organic electroluminescent element, development of a more stable and effective substance that can be used as a phosphorescent material or a hole-forming material in the organic electroluminescent element is continuously required.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a spirofluorene derivative which can improve the thermal stability of materials and the capability of transporting carriers, and an organic electroluminescent element prepared by the spirofluorene derivative can obviously reduce the driving voltage, improve the luminous efficiency and prolong the service life; another object of the present invention is to provide the use of the compound.
Specifically, the invention provides the following technical scheme:
the invention provides a spirofluorene derivative, the structural formula of which is shown as the formula (I):
Figure BDA0003946359350000011
wherein the content of the first and second substances,
R 1 、R 2 each independently selected from hydrogen, deuterium, fluorine, substituted or unsubstituted C 1 -C 40 Alkyl, substituted or unsubstituted C 1 -C 40 Alkoxy, substituted or unsubstituted C 2 -C 40 Alkenyl, substituted or unsubstituted C 1 -C 40 Alkylthio, substituted or unsubstituted C 1 -C 40 Heteroalkyl, substituted or unsubstituted C 3 -C 40 Cycloalkyl, substituted or unsubstituted C 3 -C 40 Cycloalkenyl, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Aryloxy, substituted or unsubstituted C 6 -C 60 Arylthio, substituted or unsubstituted C 3 -C 40 Silyl, or substituted or unsubstituted C 2 -C 60 Heterocyclic aryl groups; r is 1 And R 2 Optionally joined or cyclized to form a substituted or unsubstituted ring; r is 1 And R 2 Optionally joined or cyclized to form a substituted or unsubstituted ring;
R 3 、R 4 、R 5 、R 6 each independently selected from the group consisting of hydrogen, deuterium, fluorine, hydroxyl, nitrile, nitro, carboxyl or carboxylate thereof, sulfonic acid or sulfonate thereof, phosphoric acid or phosphate thereof, boric acid or borate thereof, and substituted or unsubstituted C 1 -C 40 Alkyl, substituted or unsubstituted C 1 -C 40 Alkoxy, substituted or unsubstituted C 2 -C 40 Alkenyl, substituted or unsubstituted C 1 -C 40 Alkylthio, substituted or unsubstituted C 1 -C 40 Heteroalkyl, substituted or unsubstituted C 3 -C 40 Cycloalkyl, substituted or unsubstituted C 3 -C 40 Cycloalkenyl, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Aryloxy, substituted or unsubstituted C 6 -C 60 Arylthio, substituted or unsubstituted C 3 -C 40 Silyl, substituted or unsubstituted C 2 -C 60 A heterocyclic aryl group, or a group represented by formula (II);
Figure BDA0003946359350000021
L 1 selected from the group consisting of single bonds, substituted or unsubstituted C 6 -C 60 Arylene, or substituted or unsubstituted C 2 -C 60 Heteroarylene;
R 3 、R 4 、R 5 、R 6 one or more to saturated substitutions;
Ar 1 、Ar 2 each independently selected from the group consisting of substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Condensed ring aryl, substituted or unsubstituted C 6 -C 60 Arylamino, or substituted or unsubstituted C 2 -C 60 Heterocyclic aryl groups; wherein Ar is 1 、Ar 2 、L 1 Optionally joined or cyclized to form a substituted or unsubstituted ring with or without the heteroatom O, S, N or Si in the resulting ring;
* -represents R 3 、R 4 、R 5 、R 6 And L 1 The connecting bond of (1).
In the present invention, the "ring" refers to a substituted or unsubstituted hydrocarbon ring or a substituted or unsubstituted heterocyclic ring in which adjacent groups are bonded to each other to form a substituted or unsubstituted ring. The condensed ring is a condensed aliphatic ring, a condensed aromatic ring, a condensed aliphatic heterocyclic ring, a condensed aromatic heterocyclic ring, or a combination thereof.
Preferably, the spirofluorene derivative is selected from any one of the structures shown as follows:
Figure BDA0003946359350000022
Figure BDA0003946359350000031
wherein the symbols used are as defined above.
The spirofluorene derivative according to the present invention is electrochemically stable and has excellent hole mobility, and has a high glass transition temperature and excellent thermal stability, as compared to the conventionally known B-1 to B-4 structures.
Figure BDA0003946359350000032
Accordingly, the spirofluorene derivative of the present invention has excellent hole transport ability and light emitting characteristics, and thus can be used as a material for any one of a hole injection layer, a hole transport layer, a light emitting layer, and an electron blocking layer of an organic electroluminescent device. The material that can be used as either one of the light-emitting layer and the electron-blocking layer is preferable, and the material that can be used as the electron-blocking layer is more preferable.
Specifically, the compound represented by formula (I) of the present invention has stronger hole transporting ability and electron blocking ability than oxa or substituted fluorene derivatives, such as B-1 to B-4, and can exhibit relatively high luminous efficiency and high glass transition temperature, by means of a substituted or unsubstituted triarylamine spirofluorene derivative. Accordingly, when the spirofluorene derivative represented by formula (I) of the present invention is used in an organic electroluminescent device, not only excellent thermal stability and carrier transport ability, particularly electron blocking ability and light emitting ability, can be expected, but also driving voltage of the device can be reduced, efficiency and lifetime can be improved, and an excellent increase in efficiency due to a triplet-triplet fusion effect can be exhibited as a new electron blocking layer material because of a high triplet level.
Further, the spirofluorene derivative represented by formula (I) of the present invention is prepared by reacting a spirofluorene derivative containing a triarylamine with a substituent R 1 、R 2 、R 3 、R 4 、R 5 And R 6 By adjusting HOMO and LUMO levels according to the kind of the substituent, the organic electroluminescent element can have a wide band gap, and can exhibit the highest hole-transporting property and electron-blocking property in the organic electroluminescent element using such a compound.
Further, the spirofluorene derivative represented by the formula (I) of the present invention is obtained by introducing a polyfluorene compound into the above-mentioned basic skeletonSubstituent L 1 And Ar 1 、Ar 2 Particularly, aryl and/or heteroaryl, the molecular weight of the compound is significantly increased, and the glass transition temperature is increased, thereby having higher thermal stability than the conventional light-emitting material. Therefore, the performance and life characteristics of an organic electroluminescent element comprising the compound according to the present invention can be greatly improved. The organic electroluminescent element with improved performance and life characteristics can finally maximize the performance of a full-color organic light-emitting panel.
Aryl in the sense of the present invention contains 6 to 60 carbon atoms and heteroaryl contains 2 to 60 carbon atoms and at least one heteroatom, with the proviso that the sum of carbon atoms and heteroatoms is at least 5; the heteroatom is preferably selected from N, O or S. In this case, two or more rings of the heteroaryl group may be attached to each other simply or in a condensed form, and further, may include a form condensed with the aryl group. As non-limiting examples of such heteroaryl groups, six-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl; polycyclic rings such as phenoxathiyl, indolizinyl, indolyl, purinyl, quinolinyl, benzothiazolyl, carbazolyl, and the like; and 2-furyl, N-imidazolyl, 2-isoxazolyl, 2-pyridyl, 2-pyrimidyl and the like.
Alkyl in the sense of the present invention contains 1 to 40 carbon atoms and where the individual hydrogen atoms or-CH 2 -a linear alkyl group or an alkyl group with a branched chain, the groups of which may also be substituted; alkenyl or alkynyl groups contain at least two carbon atoms, 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 is preferably alkoxy having from 1 to 40 carbon atoms, and is understood 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, cycloheptoxy, n-octoxy, cyclooctoxy, 2-ethylhexoxy, 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 of the present invention can be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptyl, cycloheptenyl groups, wherein one or more-CH groups 2 The radicals may be replaced by the radicals mentioned above; furthermore, one or more hydrogen atoms may also be replaced by deuterium atoms, halogen atoms or nitrile groups.
The heterocycloalkyl group used in the present invention refers to a monovalent functional group obtained by removing one hydrogen atom from a non-aromatic hydrocarbon having a nuclear number of 3 to 40. 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, tetrahydrofuran, tetrahydrothiophene, morpholine, piperazine, and the like are given.
The fused ring aryl group used in the present invention is a monovalent functional group obtained by combining two or more rings and removing one hydrogen atom from an aromatic hydrocarbon having 6 to 60 carbon atoms. In this case, two or more rings may be attached to each other simply or in a condensed form. As non-limiting examples thereof, may be mentioned phenanthryl, anthracyl, fluoranthyl, pyrenyl, triphenylenyl, perylenyl, perylene, etc,
Figure BDA0003946359350000041
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.
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 diphenylboron group, bis (2, 4, 6-trimethylphenyl) boron group and the like. The alkyl boron group means a dialkyl boron group substituted with an alkyl group having 1 to 40 carbon atoms, and non-limiting examples of the alkyl boron group include a di-t-butyl boron group, a diisobutyl boron group and the like.
Preferably, the aryl, heteroaryl or heteroaryl is selected from the group consisting of phenyl, naphthyl, anthryl, benzanthryl, phenanthryl, pyrenyl,
Figure BDA0003946359350000053
A phenyl group, a perylene group, a fluoranthenyl group, a tetracenyl group, a pentacenyl group, a benzopyrenyl group, a biphenyl group, an idophenyl group, a terphenyl group, a fluorenyl group, a spirobifluorenyl group, a dihydrophenanthryl group, a triphenylene group, a dihydropyrenyl group, a tetrahydropyrenyl group, a cis-or trans-indenofluorenyl group, a cis-or trans-indenocarbazolyl group, an indolocarbazolyl group, a benzofurocarbazolyl group, a benzothienocarbazolyl group, a benzocarbazolyl group, a dibenzocarbazolyl group, an azadibenzo [ g, iD ]]Naphtho [2,1,8-cde]Azulene, trimeric indenyl, isotridecyl, spirotrimeric indenyl, spiroisotridecyl, furyl, benzofuryl, isobenzofuryl, dibenzofuryl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, indolyl, isoindolyl, carbazolyl, pyridyl, quinolyl, isoquinolyl, acridinyl, phenanthridinyl, benzo [5,6 ] benzo]Quinolyl, benzo [6,7 ]]Quinolyl, benzo [7,8 ]]Quinolyl, phenothiazinyl, phenoxazinyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxalinyl, oxazolyl, benzoxazolyl, naphthooxazolyl, anthraoxazolyl, phenanthrooxazolyl, isoxazolyl, 1, 2-thiazolyl, 1, 3-thiazolyl, benzothiazolyl, pyridazinyl, hexaazabenzophenanthryl, benzopyrazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1, 5-diazenanthrenyl, 2, 7-diazapynyl, 2, 3-diazapynyl, 1, 6-diazapynyl, 1, 8-diazapynyl, 4,5,9, 10-tetraazaperylenyl, pyrazinyl,Phenazinyl, phenoxazinyl, phenothiazinyl, fluorerynyl, naphthyridinyl, azacarbazolyl, benzocarbazinyl, carbolinyl, phenanthrolinyl, 1,2, 3-triazolyl, 1,2, 4-triazolyl, benzotriazolyl, 1,2, 3-oxadiazolyl, 1,2, 4-oxadiazolyl, 1,2, 5-oxadiazolyl, 1,3, 4-oxadiazolyl, 1,2, 3-thiadiazolyl, 1,2, 4-thiadiazolyl, 1,2, 5-thiadiazolyl, 1,3, 4-thiadiazolyl, 1,3, 5-triazinyl, 1,2, 4-triazinyl, 1,2, 3-triazinyl, tetrazolyl, 1,2,4, 5-tetrazinyl, 1,2,3, 4-tetrazinyl, 1,2,3, 5-tetrazinyl, purinyl, pteridinyl, phenothiazinyl, benzoquinazolinyl, benzothiadiazolyl, or a combination of these groups derived from a group or a combination of these systems.
In the spirofluorene derivative represented by formula (I) of the present invention, preferably, R is 1 、R 2 Each independently selected from the group consisting of hydrogen, deuterium, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, substituted or unsubstituted phenyl.
Preferably, R is 3 、R 4 、R 5 、R 6 Each independently selected from the group consisting of hydrogen, deuterium, fluorine, nitrile group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, substituted or unsubstituted phenyl group, substituted or unsubstituted biphenyl group, substituted or unsubstituted terphenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted phenanthryl group, substituted or unsubstituted triphenylene group, substituted or unsubstituted carbazolyl group, substituted or unsubstituted fluorenyl group, substituted or unsubstituted dibenzofuranyl group, and substituted or unsubstituted dibenzothiophene.
According to an embodiment of the invention, said R 1 、R 2 Each independently selected from the group consisting of hydrogen, deuterium, methyl, phenyl.
According to an embodiment of the invention, said R 3 、R 4 、R 5 、R 6 Each independently selected from hydrogen, deuterium, isopropyl, tert-butyl or substituted or unsubstituted phenyl.
According to an embodiment of the invention, said R 3 、R 4 、R 5 、R 6 At least one of them is selected from the group consisting of formula (II)A group shown;
Figure BDA0003946359350000051
preferably, ar is 1 、Ar 2 Each independently selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted biphenylyl, substituted or unsubstituted terphenylyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted dibenzofuranyl, or substituted or unsubstituted dibenzothiophene.
Preferably, said L 1 Selected from a single bond or a group consisting of the following groups III-1 to III-23:
Figure BDA0003946359350000052
Figure BDA0003946359350000061
wherein the dotted line represents the linking site of the group, and in this case, the binding site of the group represented by the above formulas III-1 to III-23 is not limited, and may be ortho, meta, or para. L mentioned above 1 Can be independently selected from deuterium, halogen atom, nitrile group and C 1 -C 40 Alkyl radical, C 6 -C 60 Aryl and C 2 -C 60 When the substituent is plural, it is preferable that plural substituents are the same as or different from each other.
The term "substituted or unsubstituted" as used herein means a group selected from the group consisting of hydrogen, deuterium, a halogen atom, a hydroxyl group, a nitrile group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxyl group or a carboxylate thereof, a sulfonic acid group or a sulfonate thereof, a phosphoric acid group or a phosphate thereof, and C 1 -C 40 Alkyl radical, C 2 -C 40 Alkenyl radical, C 2 -C 40 Alkynyl, C 1 -C 40 Alkoxy radical, C 3 -C 40 Cycloalkyl, C 3 -C 40 Cycloalkenyl radical, C 6 -C 60 Aryl radical, C 6 -C 60 Aryloxy group, C 6 -C 60 An arylthioether group and C 2 -C 60 The heterocyclic aryl group may be substituted or unsubstituted with 1 or more substituents, or may be substituted or unsubstituted with substituents formed by connecting 2 or more substituents among the above-exemplified substituents.
Preferably, the spirofluorene derivative is selected from compounds represented by the following formula D475 to D621:
Figure BDA0003946359350000062
Figure BDA0003946359350000071
Figure BDA0003946359350000081
Figure BDA0003946359350000091
Figure BDA0003946359350000101
Figure BDA0003946359350000111
Figure BDA0003946359350000121
Figure BDA0003946359350000131
Figure BDA0003946359350000141
wherein, T 1 -is selected from-O-, -S-, or one of the following structures:
Figure BDA0003946359350000142
Figure BDA0003946359350000151
* -and-represent a connecting bond.
The present invention also provides a method for preparing the spirofluorene derivative described above, as shown in scheme 1:
in the case of the scheme 1,
Figure BDA0003946359350000152
in scheme 1, the symbols used are as defined in formula (I), and R is 3 、R 4 、R 5 、R 6 May each independently be Cl, br, I or OTf.
The raw materials for synthesizing the compound shown in the formula (I) can be purchased from commercial sources, and the method principle, the operation process, the conventional post treatment, the column purification, the recrystallization purification and other means are well known to the synthesizers in the field, so that the synthesis process can be completely realized to obtain the target product.
Specifically, the compound of the formula (I) is prepared by carrying out addition reaction on a 9-fluorenone derivative S0 and a benzyl Grignard reagent S1 to prepare an intermediate S2; the intermediate S2 is subjected to dehydration condensation reaction under the catalysis of acid to prepare a compound shown in the formula (I); at R 3 、R 4 、R 5 、R 6 In the presence of halogen atoms or OTf with Ar 1 Ar 2 NL 1 Carrying out SUZUKI coupling reaction on the boric acid or the boric acid pinacol ester to prepare a compound shown as a formula (I) or reacting the compound with Ar 1 Ar 2 Buchwald-Hartwig coupling with NH to prepare the compound of formula (I) of the present invention. Intermediate Ar 1 Ar 2 NL 1 Boronic acid or boronic acid pinacol ester of (A) and Ar 1 Ar 2 The NH is prepared by a palladium-catalyzed or base-catalyzed coupling reaction.
As palladium catalysts which 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 hydrocarbon solvents such as benzene, toluene, or xylene, chlorobenzene, dichlorobenzene, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, and 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 spirofluorene derivative; the organic electroluminescent material comprising the spirofluorene derivative of the present invention has carrier transport ability.
The invention also provides application of the spirofluorene derivative in preparation of organic electroluminescent elements.
The present invention also provides an organic electroluminescent element comprising: the organic light-emitting diode comprises a first electrode, a second electrode, a capping layer and more than one organic layer arranged between the first electrode and the second electrode; the material of at least one of the organic layer or the capping layer includes the spirofluorene derivative described above.
The organic electroluminescent element includes a cathode, an anode, and at least one light-emitting layer. In addition to these layers, it may also comprise further layers, for example in each case one or more hole-injecting layers, hole-transporting layers, hole-blocking layers, electron-transporting layers, electron-injecting layers, exciton-blocking layers, electron-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 device described herein may include one light-emitting layer, or it may include a plurality of light-emitting layers. That is, a plurality of light-emitting compounds capable of emitting light are used in the light-emitting layer. Particular preference is given to systems having three light-emitting layers, where the three layers can exhibit blue, green and red emission. If more than one light-emitting layer is present, at least one of these layers comprises the spirofluorene derivative of the present invention according to the present invention.
Further, the organic electroluminescent element according to the invention does not comprise a separate hole injection layer and/or hole transport layer and/or hole blocking layer and/or electron transport layer, i.e. the light-emitting layer is directly adjacent to the electron blocking layer or hole transport layer or the anode and/or the light-emitting layer is directly adjacent to the electron transport layer or electron injection layer or the cathode.
In the other layers of the organic electroluminescent element according to the invention, in particular in the hole-injecting and hole-transporting layer and in the electron-injecting and electron-transporting layer, all materials can be used in the manner conventionally used according to the prior art. The person skilled in the art will thus be able to use all materials known for organic electroluminescent elements in combination for the light-emitting layer according to the invention without inventive effort.
Preference is furthermore given to organic electroluminescent elements in which one or more layers are applied by means of a sublimation process in which the temperature in a vacuum sublimation apparatus is below 10 -5 Pa, preferably less than 10 -6 Pa is applied by vapor deposition. However, the initial pressure may also be even lower, e.g. below 10 -7 Pa。
Preference is likewise given to organic electroluminescent elements in which one or more layers are applied by means of an organic vapor deposition method or by means of carrier gas sublimation, where 10 -5 The material is applied under a pressure between Pa and 1 Pa. A particular example of this method is the organic vapour jet printing method, in which the material is applied directly through a nozzle and is therefore structured.
Preference is furthermore given to organic electroluminescent elements in which one or more layers are produced from solution, for example by spin coating, or by means of any desired printing method, for example screen printing, flexographic printing, offset printing, photoinitiated thermal imaging, thermal transfer, ink-jet printing or nozzle printing. Soluble compounds, for example obtained by appropriate substitution. These methods are also particularly suitable for oligomers, dendrimers and polymers. Furthermore, hybrid methods are possible, in which, for example, one or more layers are applied from solution and one or more further layers are applied by vapor deposition.
These methods are generally known to those skilled in the art, and they can be applied to an organic electroluminescent element comprising the compound according to the present invention without inventive labor.
The invention therefore also relates to a method for producing an organic electroluminescent element according to the invention, at least one layer being applied by means of a sublimation method, and/or at least one layer being applied by means of an organic vapour deposition method or by means of carrier gas sublimation, and/or at least one layer being applied from solution by spin coating or by means of a printing method.
Furthermore, the present invention relates to spirofluorene derivatives comprising at least one of the above indicated present invention. The same preferences as indicated above for the organic electroluminescent elements apply to the compounds according to the invention. In particular, the spirofluorene derivative may preferably contain other compounds in addition thereto. Processing of the spirofluorene derivatives of the invention from the liquid phase, for example by spin coating or by printing methods, requires the processing of formulations of the compounds of the invention. These formulations may be, for example, solutions, dispersions or emulsions. For this purpose, a mixture of two or more solvents may preferably be used. Suitable and preferred solvents are, for example, toluene, anisole, o-xylene, m-xylene or p-xylene, methyl benzoate, mesitylene, tetralin, o-dimethoxybenzene, tetrahydrofuran, methyltetrahydrofuran, tetrahydropyran, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxytoluene, (-) -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 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 a mixture of these solvents.
Preferably, the organic layer includes a hole injection layer, a hole transport layer, a hole blocking layer, a light emitting layer, an electron transport layer, an electron injection layer, or an electron blocking layer.
Further, the light emitting layer or the electron blocking layer comprises the spirofluorene derivative of the present invention.
Further, the electron blocking layer comprises the spirofluorene derivative of the present invention.
The invention also provides a consumer product comprising the organic electroluminescent element.
In addition, unless otherwise specified, all starting materials for use in the present invention are commercially available, and any range recited herein includes any value between the endpoints and any subrange between the endpoints and any value between the endpoints or any subrange between the endpoints.
The invention has the following beneficial effects:
the spirofluorene derivative represented by formula (I) provided by the present invention is excellent in hole mobility, electron blocking property, thermal stability and light emitting property, and thus can be applied to an organic layer of an organic electroluminescent device. In particular, when the spirofluorene derivative represented by formula (I) of the present invention is used in an electron blocking layer or a light emitting layer, an organic electroluminescent element having a lower driving voltage, higher efficiency, and a longer lifetime than those of conventional electron blocking materials can be manufactured, and furthermore, a full-color display panel having improved performance and lifetime can be manufactured.
Drawings
Fig. 1 shows a schematic diagram of an organic light emitting device 100. The illustrations are not necessarily drawn to scale. The device 100 may include a substrate 101, an anode layer 102, a hole injection layer 103, a hole transport layer 104, an electron blocking layer 105, a light emitting layer 106, a hole blocking layer 107, an electron transport layer 108, an electron injection layer 109, a cathode layer 110, and a capping layer (CPL) 111. The device 100 may be fabricated by sequentially depositing the described layers.
Fig. 2 shows a schematic diagram of an organic light emitting device 200 with two light emitting layers. The device 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 213. The device 200 may be prepared by sequentially depositing the described layers. Since the most common OLED devices have one light emitting layer, while device 200 has a first light emitting layer and a second light emitting layer, the light emitting peak shapes of the first light emitting layer and the second light emitting layer may be overlapping or cross-overlapping or non-overlapping. In the corresponding layers of 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 that are based on the orientations or positional relationships shown in the drawings, are merely for convenience in describing the present invention and to simplify the description, and do not indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and thus, are not to be construed as limiting the present invention.
The experimental procedures used in the following examples are conventional unless otherwise specified. The experimental raw materials and the related equipments used in the following examples are commercially available unless otherwise specified, and the percentages are by mass unless otherwise specified.
The following examples are provided for testing the performance of OLED materials and devices using the following test apparatus and method:
OLED element performance detection conditions:
luminance and chromaticity coordinates: testing by using a spectrum scanner Photoresearch PR-715;
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 method for preparing compound D476, comprising the steps of:
the first step is as follows: preparation of intermediate Int-1
Figure BDA0003946359350000181
Under the protection of nitrogen, 48.0mmol of magnesium chips are dispersed in 40mL of dry THF, 2 iodine particles are added, the temperature is raised for reflux reaction until red color disappears, 40.0mmol of 2-benzyl chloride solution dissolved in THF is dropwise added, after the dropwise addition, the reflux reaction is continued for 30 minutes, the temperature is lowered to 0 ℃, 40.0mmol of 2-bromo-9-fluorenone THF solution is dropwise added, the stirring reaction is carried out for 30 minutes, the temperature is raised to room temperature, the stirring reaction is carried out for 1 hour, 50mL of saturated aqueous ammonium chloride solution is dropwise added, an organic phase is separated out, an aqueous phase is extracted by ethyl acetate, the organic phase is combined and dried, the filtrate is concentrated and dried under reduced pressure, and is separated and purified by a silica gel column to obtain an intermediate Int-1 which is colorless oily matter with the yield of 78%.
The second step is that: preparation of intermediate Int-2
Figure BDA0003946359350000182
Under the protection of nitrogen, 20.0mmol of Int-1 is dissolved in 60mL of dichloromethane, 20mL of formic acid is added, the mixture is stirred and reacted for 15 hours, the mixture is concentrated under reduced pressure and dried, and the mixture is separated and purified by a silica gel column to obtain an intermediate Int-2 which is a white solid and has the yield of 90%.
With reference to the analogous synthetic procedures described above, the following intermediates were prepared:
Figure BDA0003946359350000183
Figure BDA0003946359350000191
the third step: preparation of Compound D476
Figure BDA0003946359350000201
Under the protection of nitrogen, 12.0mmol of intermediate Int-2, 10.0mmol of diarylamine, 15.0mmol of sodium tert-butoxide and 0.01mmol of Pd 2 (dba) 3 Catalyst, 0.02mmol of Xantphos and 50mL of toluene, heating to 100 ℃, stirring for reaction for 15 hours, cooling to room temperature, adding 50mL of tolueneDiluting with water, extracting with toluene, collecting organic phase, drying, filtering, concentrating the filtrate under reduced pressure, drying, and separating and purifying with silica gel column to obtain compound D476;
T 1 is CMe 2 White solid, yield: 76%, MS (MALDI-TOF): m/z =690.3175[ m ] +H] + ； 1 HNMR(δ、CDCl 3 )：7.92～7.86(3H,m)；7.65～7.57(4H,m)；7.50～7.45(2H,m)；7.41～7.30(7H,m)；7.26～7.16(8H,m)；7.09～7.02(5H,m)；6.85～6.81(1H,m)；6.78～6.76(1H,m)；4.29～4.25(1H,d)；4.18～4.14(1H,d)；1.03(6H,s)。
T 1 As O, white solid, yield: 78%, MS (MALDI-TOF): m/z =664.2648[ m ] +H] + ； 1 HNMR(δ、CDCl 3 )：7.88～7.86(2H,m)；7.65～7.57(5H,m)；7.54～7.48(3H,m)；7.46～7.37(5H,m)；7.26～7.18(7H,m)；7.09～7.02(3H,m)；6.95～6.92(2H,m)；6.89～6.85(3H,m)；6.69～6.66(1H,d)；4.29～4.25(1H,d)；4.18～4.14(1H,d)。
T 1 Is CPh 2 White solid, yield: 75%, MS (MALDI-TOF): m/z =814.3488[ M + H ]] + ； 1 HNMR(δ、CDCl 3 )：7.94～7.92(1H,d)；7.89～7.87(1H,d)；7.65～7.57(4H,m)；7.50～7.44(3H,m)；7.41～7.32(9H,m)；7.28～7.15(8H,m)；7.10～6.97(9H,m)；6.84～6.79(2H,m)；6.77～6.73(2H,m)；6.68～6.66(2H,m)；4.29～4.25(1H,d)；4.18～4.14(1H,d)。
With reference to the above synthetic methods, the compounds shown in table 1 were prepared:
TABLE 1
Figure BDA0003946359350000202
Figure BDA0003946359350000211
Figure BDA0003946359350000221
Figure BDA0003946359350000231
Figure BDA0003946359350000241
Figure BDA0003946359350000251
Figure BDA0003946359350000261
Figure BDA0003946359350000271
Figure BDA0003946359350000281
Figure BDA0003946359350000291
Figure BDA0003946359350000301
Figure BDA0003946359350000311
In the above examples, — T 1 -is selected from-O-, -S-, or one of the following structures:
Figure BDA0003946359350000312
* -and-represent a bond.
Example 2
An OLED element, as shown in fig. 1, the OLED element of this embodiment is a top emission light element, and includes a substrate 101, an anode layer 102 disposed on the substrate 101, a hole injection layer 103 disposed on the anode layer 102, a hole transport layer 104 disposed on the hole injection layer 103, an electron blocking layer 105 disposed on the hole transport layer 104, an organic light emitting layer 106 disposed on the electron blocking layer 105, a hole blocking layer 107 disposed on the organic light emitting layer 106, an electron transport layer 108 disposed on the hole blocking layer 107, an electron injection layer 109 disposed on the electron transport layer 108, and a cathode layer 110 disposed on the electron injection layer 109 and a capping layer 111 disposed on the cathode layer, and the method for manufacturing the OLED element without the hole blocking layer 107 includes the following steps:
1) The glass substrate coated with the ITO conductive layer is subjected to ultrasonic treatment in a cleaning agent for 30 minutes, washed in deionized water, subjected to ultrasonic treatment in an acetone/ethanol mixed solvent for 30 minutes, baked to be completely dry in a clean environment, irradiated by an ultraviolet light cleaning machine for 10 minutes, and bombarded on the surface by a low-energy cation beam.
2) Placing the processed ITO glass substrate in a vacuum chamber, and vacuumizing to less than 1 × 10 -5 Pa, depositing silver on the ITO film as anode layer to obtain a deposited film with a thickness of
Figure BDA0003946359350000313
Continuing to respectively evaporate compounds HI01 and F4TCNQ as hole injection layers, wherein F4TCNQ is 3% of HI01 by mass, and the thickness of the evaporated film is
Figure BDA0003946359350000314
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 BDA0003946359350000315
4) In the above-mentioned blankThe compound shown in the formula (I) of the invention is continuously evaporated on the hole transport layer to be used as an electron blocking layer, and the thickness of the evaporated film is
Figure BDA0003946359350000316
5) Continuing to vapor-deposit a compound BH018 as a host material and BD044 as a dopant material on the electron blocking layer, wherein BD044 is 8% by mass of BH018, and is used as an organic light-emitting layer of the element, and the film thickness of the organic light-emitting layer obtained by vapor deposition is set to be
Figure BDA0003946359350000317
6) Continuously evaporating a layer of LiQ and a compound ET028 on the organic light-emitting layer to be used as an electron transport layer of the element, wherein the mass of the compound ET028 is 50 percent of that of the LiQ, and the thickness of the evaporated film is equal to that of the element
Figure BDA0003946359350000321
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 BDA0003946359350000322
8) And depositing metal magnesium and silver on the electron injection layer to form a transparent cathode layer of the element, wherein the mass ratio of magnesium to silver is 1
Figure BDA0003946359350000323
9) A CPL layer as element is evaporated on the transparent cathode layer with a thickness of
Figure BDA0003946359350000324
The OLED element provided by the invention is obtained.
The compound used in example 2 above has the following structure:
Figure BDA0003946359350000325
example 3
An organic electroluminescent device 200, which is structured as shown in fig. 2, includes a substrate 201, an anode layer 202, a hole injection layer 203, a hole transport layer 204, a first light-emitting layer 205, an electron transport layer 206, a charge generation layer 207, a hole injection layer 208, a hole transport layer 209, a second light-emitting layer 210, an electron transport layer 211, an electron injection layer 212, and a cathode layer 213.
Comparative example 1
Following the same procedure as in example 2, substituting the compound of the present invention of formula (I) in step 4) with H01 gave comparative element 1;
Figure BDA0003946359350000326
comparative example 2
Following the same procedure as in example 2, the compound of the present invention of formula (I) in step 4) was replaced with H02 to give comparative element 2;
Figure BDA0003946359350000331
comparative example 3
Following the same procedure as in example 2, the compound of the present invention of formula (I) in step 4) was replaced with H03 to give comparative element 3;
Figure BDA0003946359350000332
comparative example 4
Following the same procedure as in example 2, the compound of the present invention of formula (I) in step 4) was replaced with H04 to give comparative element 4;
Figure BDA0003946359350000333
the organic electroluminescent element prepared by the above process was subjected to the following performance tests:
the driving voltage and current efficiency of the organic electroluminescent elements prepared in examples 2 and 3 and comparative examples 1 to 4 and the lifetime of the elements were measured using a digital source meter and a luminance meter. Specifically, the voltage was raised at a rate of 0.1V per second, and it was determined that the luminance of the organic electroluminescent element reached 1000cd/m 2 The current density is measured at the same time as the driving voltage; the ratio of the brightness to the current density is the current efficiency; the LT95% lifetime test is as follows: using a luminance meter at 1000cd/m 2 The luminance degradation of the organic electroluminescent element was measured to 950cd/m while maintaining a constant current at luminance 2 Time in hours. The data listed in table 2 are relative data compared to comparative element 1.
TABLE 2
Figure BDA0003946359350000334
Figure BDA0003946359350000341
Figure BDA0003946359350000351
Figure BDA0003946359350000361
Figure BDA0003946359350000371
In the above tables, me is methyl, ph is phenyl, phPh is biphenyl, FR is 9,9-fluorenyl, and Ad is adamantyl.
As shown in table 2, the device prepared from the spirofluorene derivative of the present invention has a lower driving voltage than H01 under the same brightness, the current efficiency is improved significantly, which is up to 1.3 times that of the comparative device, and the LT95% lifetime of the device is greatly improved.
Compared with the compound of the present invention, the compounds H01 and H02 in comparative examples 1 and 2 are different in that spirofluorene is connected to two phenyl groups through oxygen, and the compound of the present invention introduces an alkyl group on the central carbon of spirofluorene, so that the conjugation ability is reduced, the performance of the compound on molecular film formation and charge blocking is more excellent, and the transport of carriers in the element is more balanced, and therefore, the element performance is significantly improved.
The compound H03 in comparative example 3 is different from the compound of the present invention in that the fluorene is weak in planar conjugation ability, large in steric hindrance, and results in high voltage. The compound of the invention introduces alkyl on the central carbon atom of spirobifluorene, thus greatly reducing steric hindrance and improving hole transmission performance, therefore, the compound is more excellent in molecular film formation and charge blocking performance, and the charge transmission in the element is more balanced, thus the element performance is obviously improved.
Compared with the compound of the invention, the compound H04 in the comparative example 4 is different in that a condensed electron donating group is introduced on the basis of fluorene, so that the planar conjugation capability is enhanced, the charge transport performance is improved, the transfer of excitons in the element is unbalanced, the voltage is increased, and the efficiency is reduced. The compound of the invention blocks excitons from moving towards the anode after introducing alkyl, so that the charge transmission in the element is more balanced, and the element performance is obviously improved.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, it is intended that all such modifications and alterations be included within the scope of this invention as defined in the appended claims.

Claims (10)

1. A spirofluorene derivative is characterized in that the structural formula is shown as the formula (I):
Figure FDA0003946359340000011
wherein the content of the first and second substances,
R 1 、R 2 each independently selected from hydrogen, deuterium, fluorine, substituted or unsubstituted C 1 -C 40 Alkyl, substituted or unsubstituted C 1 -C 40 Alkoxy, substituted or unsubstituted C 2 -C 40 Alkenyl, substituted or unsubstituted C 1 -C 40 Alkylthio, substituted or unsubstituted C 1 -C 40 Heteroalkyl, substituted or unsubstituted C 3 -C 40 Cycloalkyl, substituted or unsubstituted C 3 -C 40 Cycloalkenyl, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Aryloxy, substituted or unsubstituted C 6 -C 60 Arylthio, substituted or unsubstituted C 3 -C 40 Silyl, or substituted or unsubstituted C 2 -C 60 Heterocyclic aryl groups; r 1 And R 2 Optionally joined or cyclized to form a substituted or unsubstituted ring; r 1 And R 2 Optionally joined or cyclized to form a substituted or unsubstituted ring;
R 3 、R 4 、R 5 、R 6 each independently selected from hydrogen, deuterium, fluorine, hydroxyl, nitrile, nitro, carboxyl or carboxylate thereof, sulfonic acid or sulfonate thereof, phosphoric acid or phosphate thereof, boric acid or borate thereof, and substituted or unsubstituted C 1 -C 40 Alkyl, substituted or unsubstituted C 1 -C 40 Alkoxy, substituted or unsubstituted C 2 -C 40 Alkenyl, substituted or unsubstituted C 1 -C 40 Alkylthio, substituted or unsubstituted C 1 -C 40 Heteroalkyl, substituted or unsubstituted C 3 -C 40 Cycloalkyl, substituted or unsubstituted C 3 -C 40 Cycloalkenyl, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Aryloxy, substituted or unsubstituted C 6 -C 60 Arylthio, substituted or unsubstituted C 3 -C 40 First siliconAlkyl, substituted or unsubstituted C 2 -C 60 Heterocyclic aryl, or a group represented by formula (II);
Figure FDA0003946359340000021
L 1 selected from the group consisting of single bonds, substituted or unsubstituted C 6 -C 60 Arylene, or substituted or unsubstituted C 2 -C 60 Heteroarylene;
R 3 、R 4 、R 5 、R 6 is one or more, up to saturated substitution;
Ar 1 、Ar 2 each independently selected from the group consisting of substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Condensed ring aryl, substituted or unsubstituted C 6 -C 60 Arylamino, or substituted or unsubstituted C 2 -C 60 Heterocyclic aryl groups; wherein Ar 1 、Ar 2 、L 1 Optionally joined or cyclized to form a substituted or unsubstituted ring with or without the heteroatom O, S, N or Si in the resulting ring;
* -represents R 3 、R 4 、R 5 、R 6 And L 1 The connecting bond of (1).
2. The spirofluorene derivative according to claim 1, wherein the spirofluorene derivative is selected from any one of the following structures:
Figure FDA0003946359340000022
Figure FDA0003946359340000031
3. the spirofluorene derivative of claim 1, wherein R is 1 、R 2 Each independently selected from the group consisting of hydrogen, deuterium, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, substituted or unsubstituted phenyl;
R 3 、R 4 、R 5 、R 6 each independently selected from the group consisting of hydrogen, deuterium, fluorine, nitrile group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, substituted or unsubstituted phenyl group, substituted or unsubstituted biphenyl group, substituted or unsubstituted terphenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted phenanthryl group, substituted or unsubstituted triphenylene group, substituted or unsubstituted carbazolyl group, substituted or unsubstituted fluorenyl group, substituted or unsubstituted dibenzofuranyl group, and substituted or unsubstituted dibenzothiophene.
4. The spirofluorene derivative according to claim 1, wherein R is 1 、R 2 Each independently selected from the group consisting of hydrogen, deuterium, methyl, phenyl; r 3 、R 4 、R 5 、R 6 Each independently selected from hydrogen, deuterium, isopropyl, tert-butyl or substituted or unsubstituted phenyl.
5. The spirofluorene derivative according to claim 1 or 2, wherein R is 3 、R 4 、R 5 、R 6 At least one of them is selected from the group represented by formula (II); ar (Ar) 1 、Ar 2 Each independently selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted biphenylyl, substituted or unsubstituted terphenylyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted dibenzofuranyl, or substituted or unsubstituted dibenzothiophene.
6. According toThe spirofluorene derivative according to claim 1 or 2, wherein L is 1 Selected from a single bond or a group consisting of the following groups III-1 to III-23:
Figure FDA0003946359340000041
wherein the dotted line represents the attachment site of the group.
7. The spirofluorene derivative according to any one of claims 1-6, wherein the spirofluorene derivative is selected from compounds represented by the following formulae D475-D621:
Figure FDA0003946359340000042
Figure FDA0003946359340000051
Figure FDA0003946359340000061
Figure FDA0003946359340000071
Figure FDA0003946359340000081
Figure FDA0003946359340000091
Figure FDA0003946359340000101
Figure FDA0003946359340000111
Figure FDA0003946359340000121
wherein, T 1 -is selected from-O-, -S-, or one of the following structures:
Figure FDA0003946359340000122
Figure FDA0003946359340000131
* -and-represent a bond.
8. An organic electroluminescence element, comprising: the organic light-emitting diode comprises a first electrode, a second electrode, a capping layer and more than one organic layer arranged between the first electrode and the second electrode; the material of at least one of the organic layer or the capping layer includes the spirofluorene derivative according to any one of claims 1 to 7.
9. Use of the spirofluorene derivative according to any one of claims 1 to 7 for the preparation of an organic electroluminescent device.
10. The organic electroluminescent element according to claim 8, wherein the organic layer comprises a hole injection layer, a hole transport layer, a hole blocking layer, a light emitting layer, an electron transport layer, an electron injection layer, or an electron blocking layer.
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