CN111056959A - Fluorene derivative and electronic device - Google Patents

Fluorene derivative and electronic device Download PDF

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Publication number
CN111056959A
CN111056959A CN201911066351.1A CN201911066351A CN111056959A CN 111056959 A CN111056959 A CN 111056959A CN 201911066351 A CN201911066351 A CN 201911066351A CN 111056959 A CN111056959 A CN 111056959A
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carbon atoms
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fluorene derivative
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崔林松
刘向阳
张业欣
陈华
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Suzhou Jiuxian New Material Co ltd
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Suzhou Jiuxian New Material Co ltd
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Abstract

The invention provides a fluorene derivative and an electronic device. The fluorene derivative obtained by introducing the fluorene rigid structure has excellent film forming property and thermal stability, and can be used for preparing organic electroluminescent devices, organic field effect transistors and organic solar cells. In addition, the fluorene derivative of the present invention can be used as a material constituting a hole injection layer, a hole transport layer, a light emitting layer, an electron blocking layer, a hole blocking layer, or an electron transport layer, and can reduce a driving voltage, improve efficiency, luminance, and lifetime. In addition, the preparation method of the fluorene derivative is simple, raw materials are easy to obtain, and the industrial development requirement can be met.

Description

Fluorene derivative and electronic device
Technical Field
The invention belongs to the technical field of organic photoelectric materials, and relates to a fluorene derivative and an electronic device containing the fluorene derivative. More particularly, the present invention relates to 1, 7-disubstituted fluorene derivatives suitable for electronic devices, particularly organic electroluminescent devices, organic field effect transistors and organic solar cells, and electronic devices using the fluorene derivatives.
Background
The organic electroluminescent device has a series of advantages of self-luminescence, low-voltage driving, full curing, wide viewing angle, simple composition and process and the like, and compared with a liquid crystal display, the organic electroluminescent device does not need a backlight source. Therefore, the organic electroluminescent device has wide application prospect.
Organic electroluminescent devices generally comprise an anode, a metal cathode and an organic layer sandwiched therebetween. The organic layer mainly comprises a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer. In addition, a host-guest structure is often used for the light-emitting layer. That is, the light emitting material is doped in the host material at a certain concentration to avoid concentration quenching and triplet-triplet annihilation, improving the light emitting efficiency. Therefore, the host material is generally required to have a higher triplet energy level and, at the same time, a higher stability.
At present, research on organic electroluminescent materials has been widely conducted in academia and industry, and a large number of organic electroluminescent materials with excellent performance have been developed. In view of the above, the future direction of organic electroluminescent devices is to develop high efficiency, long lifetime, low cost white light devices and full color display devices, but the industrialization of the technology still faces many key problems. Therefore, designing and searching a stable and efficient compound as a novel material of an organic electroluminescent device to overcome the defects of the organic electroluminescent device in the practical application process is a key point in the research work of the organic electroluminescent device material and the future research and development trend.
Disclosure of Invention
Problems to be solved by the invention
The invention aims to provide a fluorene derivative. The fluorene derivative has high thermal stability, good transmission performance, high triplet state and simple preparation method, and an organic light-emitting device prepared from the fluorene derivative has the advantages of high luminous efficiency, long service life and low driving voltage, and is an organic electroluminescent material with excellent performance.
It is another object of the present invention to provide an electronic device using the fluorene-based derivative, which has advantages of high efficiency, high durability and long life span.
Means for solving the problems
The fluorene compound has a special biphenyl structure, has high thermal stability, chemical stability and carrier transport property, and more importantly, has appropriate singlet state, triplet state and molecular orbital energy level. Therefore, the organic electroluminescent material is introduced into molecules with electroluminescent characteristics, so that the stability and the luminous efficiency of a device are improved, and the driving voltage of the device is reduced.
Namely, the present invention is as follows.
[1] A fluorene derivative represented by the following general formula (1):
Figure BDA0002259465060000021
wherein the content of the first and second substances,
L1and L2Each independently represents one or more of a single bond, a carbonyl group, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or an aromatic heterocyclic group having 5 to 18 carbon atoms;
A1～A4each independently represents Ar1、Ar2、Ar3、Ar4、
Figure BDA0002259465060000022
One or more of;
Ar1～Ar4each independently represents optionally substituted one or more R1Substituted, aromatic hydrocarbon radical having 6 to 30 carbon atoms or optionally substituted by one or more R1One or more substituted aromatic heterocyclic groups having 5 to 30 carbon atoms;
z represents CR1Or N;
m represents C (R)1)2Or a group represented by any one of the following structural formulae (a) to (F):
Figure BDA0002259465060000031
wherein the dotted line represents a bond;
x represents an alkylene group having 1 to 8 carbon atoms, a single bond, or an alkyl group having 1 to 8 carbon atoms;
y represents-C (R)1)2、-NR1、-O-、-S-、-S(O)2-、-P(＝O)R1、-Si(R1)2、-Ge(R1)2Or a single bond;
R1represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, NO2、-N(R2)2、-OR2、-SR2、-C(＝O)R2、-P(＝O)R2、-Si(R2)3One or more of a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 40 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 40 carbon atoms;
R2represents one or more of a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms;
z in the structural formulae (B) to (E) has the meaning as defined in the general formula (1).
[2] The fluorene derivative according to [1], which is represented by the following general formula (I):
Figure BDA0002259465060000032
L1and L2、Ar1～Ar4Z and M have a formula according to [1]]The meaning as defined.
[3] The fluorene derivative according to [1], which is represented by the following general formula (II):
Figure BDA0002259465060000041
L1and L2、Ar1～Ar2Z and M have a formula according to [1]]The meaning as defined.
[4]According to [1]The fluorene derivative wherein Ar is1、Ar2、Ar3And Ar4Each independently selected from the following groups:
Figure BDA0002259465060000051
Figure BDA0002259465060000061
Figure BDA0002259465060000071
wherein the dotted line represents and L1、L2Or a bond of an N-bond,
R1has the following formula [1]The meaning as defined.
[5] The fluorene derivative according to any one of [1] to [4], wherein,
L1and L2Each independently represents a single bond, a carbonyl group, a phenyl group or a triazinyl group;
R1and R2Each independently represents one or more of phenyl, biphenyl, terphenyl, quaterphenyl, pentabiphenyl, benzothienocarbazole, benzofurocarbazole, benzofluorenocarbazole, benzanthracene, triphenylene, fluorenyl, spirobifluorenyl, triazinyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, N-phenylcarbazolyl, indenocarbazolyl, benzimidazolyl, diphenyl-oxadiazolyl, diphenyl boron group, triphenyl phosphoxy, diphenyl phosphoxy, triphenyl silicon group, or tetraphenyl silicon group.
[6] The fluorene derivative according to any one of [1] to [4], wherein the fluorene derivative represented by the general formula (1) is selected from the following compounds:
Figure BDA0002259465060000091
Figure BDA0002259465060000101
Figure BDA0002259465060000111
Figure BDA0002259465060000121
Figure BDA0002259465060000131
Figure BDA0002259465060000141
Figure BDA0002259465060000151
Figure BDA0002259465060000161
Figure BDA0002259465060000171
Figure BDA0002259465060000181
Figure BDA0002259465060000191
Figure BDA0002259465060000201
Figure BDA0002259465060000211
Figure BDA0002259465060000221
Figure BDA0002259465060000231
Figure BDA0002259465060000241
Figure BDA0002259465060000251
Figure BDA0002259465060000261
Figure BDA0002259465060000271
Figure BDA0002259465060000281
Figure BDA0002259465060000291
Figure BDA0002259465060000301
Figure BDA0002259465060000311
Figure BDA0002259465060000321
Figure BDA0002259465060000331
[7] an electronic device comprising the fluorene derivative according to any one of [1] to [6 ].
[8] The electronic device according to [7], wherein the electronic device is an organic electroluminescent device, an organic field effect transistor, or an organic solar cell;
wherein the organic electroluminescent device comprises: a first electrode, a second electrode provided so as to face the first electrode, and at least one organic layer interposed between the first electrode and the second electrode, wherein the at least one organic layer contains the fluorene derivative according to any one of [1] to [6 ].
[9] The electronic device according to [8], wherein the at least one organic layer is a hole injection layer, a hole transport layer, a light emitting layer, an electron blocking layer, a hole blocking layer, or an electron transport layer.
ADVANTAGEOUS EFFECTS OF INVENTION
The fluorene derivative has good film forming property and thermal stability by introducing a fluorene rigid structure, can be used for preparing electronic devices such as organic electroluminescent devices, organic field effect transistors and organic solar cells, particularly used as a constituent material of a hole injection layer, a hole transport layer, a luminescent layer, an electron blocking layer, a hole blocking layer or an electron transport layer in the organic electroluminescent devices, can show the advantages of high luminous efficiency, long service life and low driving voltage, and is obviously superior to the existing organic electroluminescent devices.
In addition, the preparation method of the fluorene derivative is simple, raw materials are easy to obtain, and the industrial development requirement can be met.
The fluorene derivative has good application effect in electronic devices such as organic electroluminescent devices, organic field effect transistors, organic solar cells and the like, and has wide industrialization prospect.
The fluorene derivative of the present invention has high electron injection and movement rates. Therefore, with the organic electroluminescent device having an electron injection layer and/or an electron transport layer prepared using the fluorene-based derivative of the present invention, the electron transport efficiency from the electron transport layer to the light emitting layer is improved, thereby improving the light emitting efficiency. And, the driving voltage is reduced, thereby enhancing durability of the resulting organic electroluminescent device.
The fluorene derivative of the present invention has excellent hole blocking ability, excellent electron transporting property, and is stable in a thin film state. Therefore, the organic electroluminescent device having the hole blocking layer prepared using the fluorene-based derivative of the present invention has high luminous efficiency, a reduced driving voltage, and improved current resistance, so that the maximum luminous brightness of the organic electroluminescent device is increased.
The fluorene derivative can be used as a material for forming a hole injection layer, a hole transport layer, a luminescent layer, an electron blocking layer, a hole blocking layer or an electron transport layer of an organic electroluminescent device. With the organic electroluminescent device of the present invention, excitons generated in the light emitting layer can be confined, and the possibility of recombination of holes and electrons can be further increased to obtain high luminous efficiency. In addition, the driving voltage is so low that high durability can be achieved.
Drawings
FIG. 1 shows a hydrogen nuclear magnetic spectrum (C) of compound 19 of example 1 of the present invention1H NMR)。
FIG. 2 shows a hydrogen nuclear magnetic spectrum (C) of compound 20 of example 2 of the present invention1H NMR)。
Figure 3 is a thermogravimetric plot (TGA) of inventive examples 1 and 2 (compounds 19 and 20).
FIG. 4 shows organic electroluminescence spectra of organic electroluminescence devices 1 to 3 in examples 7 to 9 of the present invention.
FIG. 5 is a view showing the configurations of organic electroluminescent devices of examples 7 to 13 and organic electroluminescent devices of comparative examples 1 and 2.
Description of the reference numerals
1 substrate
2 anode
3 hole injection layer
4 hole transport layer
5 Electron blocking layer
6 light-emitting layer
7 hole blocking layer
8 electron transport layer
9 electron injection layer
10 cathode
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.
The fluorene derivative of the present invention is a novel compound having a fluorene ring structure, and is represented by the following general formula (1).
Figure BDA0002259465060000361
Specifically, the fluorene derivative of the present invention has the following general formulae (I) to (II):
Figure BDA0002259465060000362
in the above general formulae (1) and (II),
L1and L2Each independently represents one or more of a single bond, a carbonyl group, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or an aromatic heterocyclic group having 5 to 18 carbon atoms;
A1and A2Each independently represents Ar1、Ar2、Ar3、Ar4、
Figure BDA0002259465060000363
One or more of;
Ar1～Ar4each independently represents optionally substituted one or more R1Substituted, aromatic hydrocarbon radical having 6 to 30 carbon atoms or optionally substituted by one or more R1One or more substituted aromatic heterocyclic groups having 5 to 30 carbon atoms;
z represents CR1Or N;
m represents C (R)1)2Or a group represented by any one of the following structural formulae (a) to (F):
Figure BDA0002259465060000371
wherein the dotted line represents a bond;
x represents an alkylene group having 1 to 8 carbon atoms, a single bond, or an alkyl group having 1 to 8 carbon atoms;
y represents-C (R)1)2、-NR1、-O-、-S-、-S(O)2-、-P(＝O)R1、-Si(R1)2、-Ge(R1)2Or a single bond;
R1represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, NO2、-N(R2)2、-OR2、-SR2、-C(＝O)R2、-P(＝O)R2、-Si(R2)3One or more of a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 40 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 40 carbon atoms;
R2represents one or more of a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms;
z in the structural formulae (B) to (E) has the meaning as defined in the general formula (1).
<L1And L2>
L1And L2Each independently represents one or more of a single bond, a carbonyl group, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or an aromatic heterocyclic group having 5 to 18 carbon atoms.
In the present invention, the hetero atom in the aromatic heterocyclic group having 5 to 18 carbon atoms is preferably selected from N, O and/or S. In the present invention, the number of hetero atoms may be 1 to 5. An aromatic hydrocarbon group or aromatic heterocyclic group in the sense of the present invention means a system which does not necessarily contain only aryl or heteroaryl groups, but in which a plurality of aryl or heteroaryl groups may also be interrupted by non-aromatic units (preferably less than 10% of non-hydrogen atoms), which may be, for example, carbon atoms, nitrogen atoms, oxygen atoms or carbonyl groups. For example, systems of 9, 9' -spirobifluorenes, 9, 9-diarylfluorenes, triarylamines, diaryl ethers, etc., as well as systems in which two or more aryl groups are interrupted, for example by linear or cyclic alkyl groups or by silyl groups, are also intended to be considered aromatic hydrocarbon groups in the sense of the present invention. Furthermore, systems in which two or more aryl or heteroaryl groups are bonded directly to one another, such as biphenyl, terphenyl or quaterphenyl, are likewise intended to be regarded as aromatic hydrocarbon groups or aromatic heterocyclic groups.
From L1And L2The aromatic hydrocarbon group having 6 to 18 carbon atoms or the aromatic heterocyclic group having 5 to 18 carbon atoms represented may be exemplified by: phenyl, naphthyl, anthracenyl, benzanthracenyl, phenanthrenyl, benzophenanthrenyl, pyrenyl, perylenyl, fluoranthenyl, benzofluoranthenyl, tetracenyl, pentacenyl, benzopyrenyl, biphenyl, idophenyl, terphenyl, quaterphenyl, pentabiphenyl, terphenyl, fluorenyl, spirobifluorenyl, dihydrophenanthrenyl, hydropyranyl, cis-or trans-indenofluorenyl, cis-or trans-monobenzindenofluorenyl, cis-or trans-dibenzoindenofluorenyl, trimeric indenyl, isotridecyl, spirotrimeric indenyl, spiroisotridecyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, indolyl, isoindolyl, carbazolyl, indolocarbazolyl, indenocarbazolyl, pyridyl, quinolyl, isoquinolyl, acridinyl, perylenyl, anthryl, benzopyrenyl, terphenylenyl, terphenylindenyl, etc, Phenanthridinyl, benzo-5, 6-quinolinyl, benzo-6, 7-quinolinyl, benzo-7, 8-quinolinyl, phenothiazinyl, phenoxazinyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxalinylimidazolyl, oxazolyl, benzoxazolyl, naphthooxazolyl, anthraoxazolyl, phenanthrooxazolyl, isoxazolyl, 1, 2-thiazolyl, 1, 3-thiazolyl, benzothiazolyl, pyridazinyl, benzopyrazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1, 5-diazenanthranyl, 2, 7-diazapyrenyl, benzopyrenyl, quinoxalinyl, and a pharmaceutically acceptable salt thereof,2, 3-diazpyrenyl, 1, 6-diazpyrenyl, 1, 8-diazpyrenyl, 4,5,9, 10-tetraazaperylenyl, pyrazinyl, phenazinyl, phenoxazinyl, phenothiazinyl, fluoryl, naphthyridinyl, azacarbazolyl, benzocarbazinyl, phenanthrolinyl, 1,2, 3-triazolyl, 1,2, 4-triazolyl, benzotriazolyl, 1,2, 3-oxadiazolyl, 1,2, 4-oxadiazolyl, 1,2, 5-oxadiazolyl, 1,3, 4-oxadiazolyl, 1,2, 3-thiadiazolyl, 1,2, 4-thiadiazolyl, 1,2, 5-thiadiazolyl, 1,3, 4-thiadiazolyl, 1,3, 5-triazinyl, 1,2, 4-triazinyl, 1,2, 3-triazinyl, tetrazolyl, 1,2,4, 5-tetrazinyl, 1,2,3, 4-tetrazinyl, 1,2,3, 5-tetrazinyl, purinyl, pteridinyl, indolizinyl, benzothiadiazolyl, and the like.
In the present invention, preferably, L1And L2Each independently represents one or more of a single bond, a carbonyl group, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or an aromatic heterocyclic group having 5 to 12 carbon atoms. More preferably, L1And L2Each independently represents one or more of a single bond, a carbonyl group, a phenyl group, a triazinyl group or a biphenyl group.
From L1And L2The aromatic hydrocarbon group having 6 to 18 carbon atoms or the aromatic heterocyclic group having 5 to 18 carbon atoms represented may be unsubstituted, but may also have a substituent. The substituents may be exemplified by the following: a deuterium atom; a cyano group; a nitro group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; an alkyl group having 1 to 6 carbon atoms, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a n-pentyl group, an isopentyl group, a neopentyl group, or a n-hexyl group; alkoxy having 1 to 6 carbon atoms such as methoxy, ethoxy or propoxy; alkenyl, such as vinyl or allyl; aryloxy groups such as phenoxy or tolyloxy; arylalkoxy, such as benzyloxy or phenethyloxy; aromatic hydrocarbon radicals or condensed polycyclic aromatic radicals, e.g. phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, fluorenyl, indenyl, pyrenyl, perylenyl, fluoranthryl, benzo [9,10 ] benzo]Phenanthryl or spirobifluorenyl; aromatic heterocyclic radicals, e.g. pyridyl, thienyl, furyl, pyrrolyl, quinolylIsoquinolinyl, benzofuranyl, benzothienyl, indolyl, carbazolyl, benzoxazolyl, benzothiazolyl, quinoxalinyl, benzimidazolyl, pyrazolyl, dibenzofuranyl, dibenzothienyl, azafluorenyl, diazafluorenyl, carbolinyl, azaspirobifluorenyl or diazaspiro-bifluorenyl; arylethenyl, such as styryl or naphthylethenyl; and acyl groups such as acetyl or benzoyl and the like.
The alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms may be linear or branched. Any of the above substituents may be further substituted with the above exemplary substituents. The above substituents may be present independently of each other, but may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom to form a ring.
<A1And A2>
A1And A2Each independently represents Ar1、Ar2、Ar3、Ar4、
Figure BDA0002259465060000391
One or more of the above.
(Ar1To Ar4)
Ar1～Ar4Each independently represents optionally substituted one or more R1Substituted, aromatic hydrocarbon radical having 6 to 30 carbon atoms or optionally substituted by one or more R1One or more substituted aromatic heterocyclic groups having 5 to 30 carbon atoms.
From Ar1～Ar4The aromatic hydrocarbon group having 6 to 30 carbon atoms or the aromatic heterocyclic group having 5 to 30 carbon atoms represented may be exemplified by: phenyl, naphthyl, anthracenyl, benzanthracenyl, phenanthrenyl, benzophenanthrenyl, pyrenyl, perylenyl, fluoranthenyl, benzofluoranthenyl, tetracenyl, pentacenyl, benzopyrenyl, biphenyl, idophenyl, terphenyl, quaterphenyl, pentabiphenyl, terphenyl, fluorenyl, spirobifluorenyl, dihydrophenanthryl, dihydropyrenyl, tetrahydropyrenyl, cis-or trans-indenofluorenyl, cis-or trans-anthrylMonobenzindenofluorenyl, cis-or trans-dibenzoindenofluorenyl, trimeric indenyl, isotridendenyl, spirotrimeric indenyl, spiroisotridendenyl, furyl, benzofuryl, isobenzofuryl, dibenzofuryl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, benzothienocarbazolyl, pyrrolyl, indolyl, isoindolyl, carbazolyl, indolocarbazolyl, indenocarbazolyl, pyridyl, bipyridyl, terpyridyl, quinolyl, isoquinolyl, acridinyl, phenanthridinyl, benzo-5, 6-quinolyl, benzo-6, 7-quinolyl, benzo-7, 8-quinolyl, phenothiazinyl, phenoxazinyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, benzimidazolyl, etc, Quinoxalinylazolyl, oxazolyl, benzoxazolyl, benzoxadiazolyl, naphthooxazolyl, anthraoxazolyl, phenanthrooxazolyl, isoxazolyl, thiazolyl, isothiazolyl, benzothiazolyl, benzothiadiazolyl, pyridazinyl, benzpyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, quinazolinyl, azafluorenyl, diazenanthranyl, diazperylenyl, tetrazaperylenyl, naphthyridinyl, pyrazinyl, phenazinyl, phenoxazinyl, phenothiazinyl, fluoresceinyl, naphthyridinyl, azacarbazolyl, benzocarbazinyl, phenanthrolinyl, triazolyl, benzotriazolyl, oxadiazolyl, thiadiazolyl, triazinyl, tetrazolyl, tetrazinyl, purinyl, pteridinyl, indolizinyl, benzothiadiazolyl, pyridopyrrolyl, pyridotriazolyl, xanthenyl, benzofurocarbazyl, benzofluorenocarbazyl carbazolyl, benzoxazolyl, isothiazolyl, thiadiazolyl, and thiadiazolyl, N-phenylcarbazolyl, diphenyl-benzimidazolyl, diphenyl-oxadiazolyl, diphenyl boronyl, triphenyl phosphinyl, diphenyl phosphinyl, triphenyl silyl, tetraphenyl silyl and the like.
In the present invention, preferably, Ar1、Ar2、Ar3And Ar4Each independently selected from the following groups:
Figure BDA0002259465060000411
Figure BDA0002259465060000421
Figure BDA0002259465060000431
wherein the dotted line represents and L1、L2Or a N-bonded bond, R1Have the meaning defined above.
From Ar1～Ar4The aromatic hydrocarbon group having 6 to 30 carbon atoms or the aromatic heterocyclic group having 5 to 30 carbon atoms represented may be unsubstituted, but may also have a substituent. Preferably, from Ar1～Ar4The aromatic hydrocarbon group having 6 to 30 carbon atoms or the aromatic heterocyclic group having 5 to 30 carbon atoms represented by1Substituted, aromatic hydrocarbon radicals having 6 to 30 carbon atoms or substituted by one or more R1A substituted aromatic heterocyclic group having 5 to 30 carbon atoms.
(R1)
R1Represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, NO2、-N(R2)、-OR2、-SR2、-C(＝O)R2、-P(＝O)R2、-Si(R2)3One or more of a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 40 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 40 carbon atoms.
From R1The alkyl group having 1 to 20 carbon atoms represented may be exemplified by: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, 2-methylhexyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, 3-methylheptyl, n-nonyl, n-decyl, hexadecyl, neopentyl, or neopentyl,Octadecyl, eicosyl, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2, 3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2, 3-dimethylcyclohexyl, 3,4, 5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like. The alkyl group having 1 to 20 carbon atoms may be linear, branched or cyclic.
From R1The alkyl group having 1 to 20 carbon atoms represented may be unsubstituted, but may also have a substituent. Preferably, from R1Alkyl having 1 to 20 carbon atoms represented by one or more of the following R2And (4) substitution. In addition, one or more non-adjacent CH in the alkyl group2The group can be represented by R2C＝CR2、-C≡C-、-Si(R2)3、-C＝O、-C＝NR2、-P(＝O)R2、-SO-、-S(O)2-、-NR2-O-, -S-or-CONR2And wherein one or more hydrogen atoms may be replaced with deuterium atom, fluorine atom, chlorine atom, bromine atom, iodine atom, cyano group, nitro group.
From R1The alkenyl group having 2 to 20 carbon atoms represented may be exemplified by: vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, 2-ethylhexenyl, allyl, cyclohexenyl and the like. The alkenyl group having 2 to 20 carbon atoms may be linear, branched or cyclic.
From R1The alkenyl group having 2 to 20 carbon atoms represented may be unsubstituted or may have a substituent. The substituents can be exemplified by the group consisting of R1The alkyl group having 1 to 20 carbon atoms represented by (b) may have the same substituent as that represented by the substituent(s). The substituents may take the same pattern as that of the exemplary substituents.
From R1The alkynyl group having 2 to 20 carbon atoms represented may be exemplified by: ethynyl, isopropynyl, butynyl, pentynyl, hexynylAlkynyl, heptynyl, octynyl, nonynyl, decynyl and the like.
From R1The alkynyl group having 2 to 20 carbon atoms represented may be unsubstituted or may have a substituent. The substituents can be exemplified by the group consisting of R1The alkyl group having 1 to 20 carbon atoms represented by (b) may have the same substituent as that represented by the substituent(s). The substituents may take the same pattern as that of the exemplary substituents.
From R1The aromatic hydrocarbon group having 6 to 40 carbon atoms or the aromatic heterocyclic group having 5 to 40 carbon atoms represented by the formula are exemplified by the groups represented by the above formula Ar1～Ar4The aromatic hydrocarbon group having 6 to 30 carbon atoms or the aromatic heterocyclic group having 5 to 30 carbon atoms represented by the above formula represent the same groups.
From R1The aromatic hydrocarbon group having 6 to 40 carbon atoms or the aromatic heterocyclic group having 5 to 40 carbon atoms represented may be unsubstituted or may have a substituent. The substituents can be exemplified by the group consisting of R1The alkyl group having 1 to 20 carbon atoms represented by (b) may have the same substituent as that represented by the substituent(s). The substituents may take the same pattern as that of the exemplary substituents. In addition, two adjacent R1Substituents or two adjacent R2The substituents optionally may form a mono-or polycyclic aliphatic, aromatic or heteroaromatic ring system, which may be substituted by one or more R2Substitution; where two or more substituents R1May be connected to each other and may form a ring.
Preferably represented by R1The aromatic hydrocarbon group having 6 to 40 carbon atoms or the aromatic heterocyclic group having 5 to 40 carbon atoms represented by (a) may be exemplified by: phenyl, biphenyl, terphenyl, quaterphenyl, pentabiphenyl, benzothienocarbazolyl, benzofurocarbazolyl, benzofluorenocarbazolyl, benzanthracenyl, benzophenanthryl, fluorenyl, spirobifluorenyl, triazinyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, indenocarbazolyl, benzimidazolyl, diphenyl-oxadiazolyl, diphenyl-carbazolylBoron group, triphenyl phosphorus oxygen group, diphenyl phosphorus oxygen group, triphenyl silicon group, tetraphenyl silicon group, etc. The aromatic hydrocarbon group having 6 to 40 carbon atoms or the aromatic heterocyclic group having 5 to 40 carbon atoms may be substituted with one or more R2And (4) substitution.
(R2)
R2Represents one or more of a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms.
From R2The alkyl group having 1 to 20 carbon atoms represented by R1The alkyl groups represented by the formulae having 1 to 20 carbon atoms represent the same groups.
From R2The aromatic hydrocarbon group having 6 to 30 carbon atoms or the substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms represented by R1The same groups as those shown for the aromatic hydrocarbon group having 6 to 30 carbon atoms or the substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms.
From R2The alkyl group having 1 to 20 carbon atoms, the aromatic hydrocarbon group having 6 to 30 carbon atoms, or the substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms represented may be unsubstituted, or may also have a substituent. The substituents may be exemplified by: a deuterium atom; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; cyano, and the like.
(Z)
Z represents CR1Or N.
R1Have the meaning as defined above.
(M)
M represents C (R)1)2Or a group represented by any one of the following structural formulae (a) to (F):
Figure BDA0002259465060000471
wherein the dotted line represents a bond;
x represents an alkylene group having 1 to 8 carbon atoms, a single bond, or an alkyl group having 1 to 8 carbon atoms;
y represents-C (R)1)2、-NR1、-O-、-S-、-S(O)2-、-P(＝O)R1、-Si(R1)2、-Ge(R1)2Or a single bond;
Z、R1and R2Have the meaning as defined above.
The alkylene group having 1 to 8 carbon atoms represented by X may be exemplified by: methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, and the like.
The alkyl group having 1 to 8 carbon atoms represented by X may be exemplified by: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, 2-methylhexyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, 3-methylheptyl and the like. The alkyl group having 1 to 8 carbon atoms may be linear, branched or cyclic.
< production method >
The fluorene derivative of the present invention can be produced, for example, by the following method:
Figure BDA0002259465060000472
the obtained compound can be purified by, for example, purification by column chromatography, adsorption purification using silica gel, activated carbon, activated clay, or the like, recrystallization or crystallization using a solvent, sublimation purification, or the like. Identification of compounds can be carried out by mass spectrometry, elemental analysis.
Specific examples of preferred compounds among the fluorene derivatives of the present invention are shown below, but the present invention is by no means limited to these compounds.
Figure BDA0002259465060000491
Figure BDA0002259465060000501
Figure BDA0002259465060000511
Figure BDA0002259465060000521
Figure BDA0002259465060000531
Figure BDA0002259465060000541
Figure BDA0002259465060000551
Figure BDA0002259465060000561
Figure BDA0002259465060000571
Figure BDA0002259465060000581
Figure BDA0002259465060000591
Figure BDA0002259465060000601
Figure BDA0002259465060000611
Figure BDA0002259465060000621
Figure BDA0002259465060000631
Figure BDA0002259465060000641
Figure BDA0002259465060000651
Figure BDA0002259465060000661
Figure BDA0002259465060000671
Figure BDA0002259465060000681
Figure BDA0002259465060000691
Figure BDA0002259465060000701
Figure BDA0002259465060000711
Figure BDA0002259465060000721
Figure BDA0002259465060000731
< electronic device >
A variety of electronic devices containing the fluorene-based derivatives of the present invention may be produced by using the fluorene-based derivatives according to the present invention for producing organic materials which may be particularly configured in the form of layers. In particular, the fluorene derivative of the present invention can be used in organic electroluminescent devices, organic solar cells, organic diodes, and particularly organic field effect transistors. Particularly in the case of an organic electroluminescent device or a solar cell, the assembly may have a plug structure (the device has one or more p-doped hole transport layers and/or one or more n-doped electron transport layers) or an inverted structure (from the light emitting layer, the upper electrode and the hole transport layer are located on the same side while the substrate is on the opposite side), without being limited to these structures. The injection layer, the transport layer, the light-emitting layer, the barrier layer, and the like can be fabricated, for example, by forming a layer containing or consisting of the fluorene-based derivative according to the present invention between electrodes. However, the use of the fluorene-based derivative according to the present invention is not limited to the above exemplary embodiments.
< organic electroluminescent device >
The organic electroluminescent device of the present invention comprises: the organic electroluminescence device includes a first electrode, a second electrode provided so as to face the first electrode, and at least one organic layer interposed between the first electrode and the second electrode, wherein the at least one organic layer includes a fluorene derivative of the present invention.
Fig. 5 is a view showing the configuration of an organic electroluminescent device of the present invention. As shown in fig. 5, in the organic electroluminescent device of the present invention, for example, an anode 2, a hole injection layer 3, a hole transport layer 4, an electron blocking layer 5, a light emitting layer 6, a hole blocking layer 7, an electron transport layer 8, an electron injection layer 9, and a cathode 10 are sequentially disposed on a substrate 1.
The organic electroluminescent device of the present invention is not limited to such a structure, and for example, some organic layers may be omitted in the multi-layer structure. For example, it may be a configuration in which the hole injection layer 3 between the anode 2 and the hole transport layer 4, the hole blocking layer 7 between the light emitting layer 6 and the electron transport layer 8, and the electron injection layer 9 between the electron transport layer 8 and the cathode 10 are omitted, and the anode 2, the hole transport layer 4, the light emitting layer 6, the electron transport layer 8, and the cathode 10 are sequentially provided on the substrate 1.
The organic electroluminescent device according to the present invention may be manufactured by materials and methods well known in the art, except that the above organic layer contains the compound represented by the above general formula (1). In addition, in the case where the organic electroluminescent device includes a plurality of organic layers, the organic layers may be formed of the same substance or different substances.
For example, the organic electroluminescent device according to the present invention may be manufactured by sequentially laminating a first electrode, an organic layer, and a second electrode on a substrate. At this time, the following can be made: an anode is formed by depositing metal, a metal oxide having conductivity, or an alloy thereof on a substrate by a PVD (physical vapor deposition) method such as a sputtering method or an electron beam evaporation method, an organic layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer is formed on the anode, and a substance which can be used as a cathode is deposited on the organic layer. However, the production method is not limited thereto.
In one example, the first electrode is an anode and the second electrode is a cathode, or the first electrode is a cathode and the second electrode is an anode.
The anode of the organic electroluminescent device of the present invention may be made of a known electrode material. For example, an electrode material having a large work function, such as a metal of vanadium, chromium, copper, zinc, gold, or an alloy thereof; metal oxides such as zinc oxide, Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), and the like; such as ZnO, Al or SNO2A combination of a metal such as Sb and an oxide; poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxy) thiophene]And conductive polymers such as PEDOT, polypyrrole, and polyaniline. Among these, ITO is preferable.
As the hole injection layer of the organic electroluminescent device of the present invention, a known material having a hole injection property can be used. Examples thereof include: porphyrin compounds represented by copper phthalocyanine, naphthalenediamine derivatives, star-shaped triphenylamine derivatives, triphenylamine trimers such as arylamine compounds having a structure in which 3 or more triphenylamine structures are connected by a single bond or a divalent group containing no heteroatom in the molecule, tetramers, receptor-type heterocyclic compounds such as hexacyanoazatriphenylene, and coating-type polymer materials. These materials can be formed into a thin film by a known method such as a vapor deposition method, a spin coating method, and an ink jet method.
As the hole transport layer of the organic electroluminescent device of the present invention, the fluorene derivative of the present invention is preferably used. In addition, other known materials having a hole-transporting property can be used. Examples thereof include: a compound containing a m-carbazolylphenyl group; benzidine derivatives such as N, N ' -diphenyl-N, N ' -di (m-tolyl) benzidine (TPD), N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine (NPB), N ' -tetrakisbiphenylylbenzidine, and the like; 1, 1-bis [ (di-4-tolylamino) phenyl ] cyclohexane (TAPC); various triphenylamine trimers and tetramers; 9,9 ', 9 "-triphenyl-9H, 9' H, 9" H-3,3 ': 6', 3 "-tricarbazole (Tris-PCz), and the like. These may be used as a single layer formed by separately forming a film or by mixing them with other materials to form a film, or may be used as a laminated structure of layers formed by separately forming a film, a laminated structure of layers formed by mixing films, or a laminated structure of layers formed by separately forming a film and layers formed by mixing films. These materials can be formed into a thin film by a known method such as a vapor deposition method, a spin coating method, and an ink jet method.
In addition, in the hole injection layer or the hole transport layer, a material obtained by further P-doping tribromoaniline antimony hexachloride, an axial olefin derivative, or the like to a material generally used in the layer, a polymer compound having a structure of a benzidine derivative such as TPD in a partial structure thereof, or the like may be used.
As the electron blocking layer of the organic electroluminescent device of the present invention, the fluorene derivative of the present invention is preferably used. In addition, other known compounds having an electron blocking effect may be used. For example, there may be mentioned: carbazole derivatives such as 4,4', 4 ″ -tris (N-carbazolyl) triphenylamine (TCTA), 9-bis [4- (carbazol-9-yl) phenyl ] fluorene, 1, 3-bis (carbazol-9-yl) benzene (mCP), and 2, 2-bis (4-carbazol-9-ylphenyl) adamantane (Ad-Cz); a compound having a triphenylsilyl and triarylamine structure represented by 9- [4- (carbazol-9-yl) phenyl ] -9- [4- (triphenylsilyl) phenyl ] -9H-fluorene; and compounds having an electron-blocking effect, such as monoamine compounds having a high electron-blocking property and various triphenylamine dimers. These may be used as a single layer formed by film formation alone or by mixing with other materials to form a film, or may be used as a laminated structure of layers formed by film formation alone, a laminated structure of layers formed by mixing into a film, or a laminated structure of layers formed by film formation alone and layers formed by mixing into a film. These materials can be formed into a thin film by a known method such as a vapor deposition method, a spin coating method, and an ink jet method.
The fluorene derivative of the present invention is preferably used as the light-emitting layer of the organic electroluminescent device of the present invention. In addition to this, Alq can also be used3Various metal complexes such as metal complexes of a first hydroxyquinoline derivative, compounds having a pyrimidine ring structure, anthracene derivatives, bisstyrylbenzene derivatives, pyrene derivatives, oxazole derivatives, polyparaphenylene vinylene derivatives, and the like.
The light emitting layer may be composed of a host material and a dopant material. As the host material, the fluorene derivative of the present invention is preferably used. In addition to these, mCBP, mCP, thiazole derivatives, benzimidazole derivatives, polydialkylfluorene derivatives, heterocyclic compounds having a partial structure in which an indole ring is a condensed ring, and the like can be used.
As the doping material, an aromatic amine derivative, a styryl amine compound, a boron complex, a fluoranthene compound, a metal complex, or the like can be used. Examples thereof include pyrene derivatives, anthracene derivatives, quinacridones, coumarins, rubrenes, perylenes and their derivatives, benzopyran derivatives, rhodamine derivatives, aminostyryl derivatives, spirobifluorene derivatives, and the like. These may be used as a single layer formed by film formation alone or by mixing with other materials to form a film, or may be used as a laminated structure of layers formed by film formation alone, a laminated structure of layers formed by mixing into a film, or a laminated structure of layers formed by film formation alone and layers formed by mixing into a film. These materials can be formed into a thin film by a known method such as a vapor deposition method, a spin coating method, and an ink jet method.
As the hole blocking layer of the organic electroluminescent device of the present invention, the fluorene derivative of the present invention is preferably used. In addition, the hole-blocking layer may be formed using another compound having a hole-blocking property. For example, a phenanthroline derivative such as 2,4, 6-tris (3-phenyl) -1,3, 5-triazine (T2T), 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBi), Bathocuproine (BCP), a metal complex of a quinolyl derivative such as aluminum (III) bis (2-methyl-8-hydroxyquinoline) -4-phenylphenate (BAlq), and a compound having a hole-blocking effect such as various rare earth complexes, oxazole derivatives, triazole derivatives, and triazine derivatives can be used. These may be used as a single layer formed by separately forming a film or by mixing them with other materials to form a film, or may be used as a laminated structure of layers formed by separately forming a film, a laminated structure of layers formed by mixing films, or a laminated structure of layers formed by separately forming a film and layers formed by mixing films. These materials can be formed into a thin film by a known method such as a vapor deposition method, a spin coating method, and an ink jet method.
The above-described material having a hole-blocking property can also be used for formation of an electron transport layer described below. That is, by using the known material having a hole-blocking property, a layer which serves as both a hole-blocking layer and an electron-transporting layer can be formed.
As the electron transport layer of the organic electroluminescent device of the present invention, the fluorene derivative of the present invention is preferably used. In addition, the compound may be formed using other compounds having an electron-transporting property. For example, Alq can be used3Metal complexes of quinolinol derivatives including BAlq; various metal complexes; a triazole derivative; a triazine derivative; an oxadiazole derivative; a pyridine derivative; bis (10-hydroxybenzo [ H ]]Quinoline) beryllium (Be (bq)2) (ii) a Such as 2- [4- (9, 10-dinaphthalen-2-anthracen-2-yl) phenyl]Benzimidazole derivatives such as-1-phenyl-1H-benzimidazole (ZADN); a thiadiazole derivative; anthracene derivativesAn agent; a carbodiimide derivative; quinoxaline derivatives; pyridoindole derivatives; phenanthroline derivatives; silole derivatives and the like. These may be used as a single layer formed by separately forming a film or by mixing them with other materials to form a film, or may be used as a laminated structure of layers formed by separately forming a film, a laminated structure of layers formed by mixing films, or a laminated structure of layers formed by separately forming a film and layers formed by mixing films. These materials can be formed into a thin film by a known method such as a vapor deposition method, a spin coating method, and an ink jet method.
As the electron injection layer of the organic electroluminescent device of the present invention, a material known per se can be used. For example, alkali metal salts such as lithium fluoride and cesium fluoride; alkaline earth metal salts such as magnesium fluoride; metal complexes of quinolinol derivatives such as lithium quinolinol; and metal oxides such as alumina.
In the electron injection layer or the electron transport layer, a material obtained by further N-doping a metal such as cesium, a triarylphosphine oxide derivative, or the like can be used as a material generally used for the layer.
As the cathode of the organic electroluminescent device of the present invention, an electrode material having a low work function such as aluminum, magnesium, or an alloy having a low work function such as magnesium-silver alloy, magnesium-indium alloy, aluminum-magnesium alloy is preferably used as the electrode material.
As the substrate of the present invention, a substrate in a conventional organic light emitting device, such as glass or plastic, can be used. In the present invention, a glass substrate is selected.
Examples
The production of the compound represented by the above general formula (1) and the organic electroluminescent device comprising the same is specifically described in the following examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.
Example 1: synthesis of Compound 19
(Synthesis of intermediate 1)
The synthetic route for intermediate 1 is shown below:
Figure BDA0002259465060000781
to a clean 250mL three-necked flask, 6.7g (47.8mmol) of 4-fluorobenzeneboronic acid, 8.4g (79.6mmol) of anhydrous sodium carbonate, 9.3g (39.8mmol) of methyl 2-bromo-6-fluorobenzoate, 470.8mg (4.8mmol) of tetrakis (triphenylphosphine palladium), and 100mL of a mixed solvent (toluene: water: ethanol ═ 5: 1: 1(V/V)) were sequentially added under nitrogen. The system was gradually warmed to reflux and reacted under reflux overnight. After the reaction is finished, stopping heating, and automatically cooling the reaction system to room temperature. The reaction solution was poured into about 200mL of water and extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane 15: 1(V/V)) to obtain 8.2g of a pale yellow oily liquid in 83% yield. Ms (ei): m/z: 248.26[ M ]+]。Anal.calcd for C14H10F2O2(％)：C 67.74，H 4.06；found：C 67.73，H 4.10。
(Synthesis of intermediate 2)
The synthetic route for intermediate 2 is shown below:
Figure BDA0002259465060000791
10g (40mmol) of intermediate 1 and 100mL (3.2g, 80mmol) of aqueous sodium hydroxide were added sequentially to a clean 250mL single-neck flask, gradually warmed to reflux and reacted under reflux overnight. After the reaction is finished, stopping heating, and automatically cooling the system. The reaction solution was poured into a 1L beaker, 2N hydrochloric acid was added dropwise to neutralize the system until the system became acidic (pH 1.0), during which time a large amount of white solid was formed, collected by suction filtration, compacted and drained, and washed with water until the eluate became neutral. The filter cake dried overnight at 80 ℃ was a white solid weighing about 9.0g with a 96% yield.
The white solid was placed in a 250mL two-necked flask equipped with a mechanical stirring device, and about 80g of polyphosphoric acid was added, gradually warmed to 160 ℃ and reacted at this temperature for 4 h. After the reaction is finished, stopping heating, pouring the system into the container 1 while the system is hot under continuous stirringIn a large beaker of kg ice, the system was neutralized to basic with 1N sodium hydroxide solution. The yellow solid was collected by suction filtration and washed with copious amounts of water until the eluate was neutral. The filter cake weighed about 7.5g after drying overnight at 80 ℃ with a yield of 90%. Ms (ei): m/z: 216.08[ M ]+]。Anal.calcd for C13H6F2O(％)：C 72.23，H 2.80；found：C 72.21，H 2.83。
(Synthesis of intermediate 19A)
The synthetic route for intermediate 19A is shown below:
Figure BDA0002259465060000801
a dry, clean 250mL three-necked flask was charged with 5g (23mmol) of intermediate 2, 8.5g (50.6mmol) of carbazole, and 12.7g (92mmol) of anhydrous potassium carbonate in that order. The system was back and forth replaced with nitrogen three times to remove air therefrom. 150ml of LN-methylpyrrolidone was added, the temperature was gradually raised to 180 ℃ and the reaction was allowed to proceed at this temperature overnight. After the reaction is cooled, inorganic salt is removed by suction filtration, and the filtrate is distilled under reduced pressure to obtain reddish brown residue. The crude product was further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane 4: 1(V/V)) to give 11.0g of an orange-red solid with a yield of 95%. Ms (ei): m/z: 510.58[ M ]+]。Anal.calcd for C37H22N2O(％)：C 87.04，H 4.34，N 5.49；found：C 87.01，H 4.36，N 5.47。
(Synthesis of intermediate 19B)
The synthetic route for intermediate 19B is shown below:
Figure BDA0002259465060000802
adding 1g (5.9mmol) of iodine simple substance and 100mL of glacial acetic acid into a 250mL three-neck flask provided with a reflux condenser tube and a dropping funnel under the protection of nitrogen, stirring for dissolving, adding about 3.9g (29.6mmol) of hypophosphorous acid, and heating to 120 ℃ for reacting until the system color is faded. Then 7.5g (14.8mmol) of intermediate 19A was added in one portion, heated and refluxed for 4 hours, cooled to room temperature, poured into water and precipitatedA large amount of white solid was filtered, washed with water and dried to give 6.0g of white crystalline solid in 82% yield. Ms (ei): m/z: 496.48[ M ]+]。Anal.calcd for C27H24N2(％)：C 89.49，H 4.87，N 5.64；found：C 89.46，H 4.89，N 5.63。
(Synthesis of Compound 19)
The synthetic route for compound 19 is shown below:
Figure BDA0002259465060000811
6.9g (13.9mmol) of the above intermediate 19B solid was transferred to a 250mL three-necked flask equipped with a dropping funnel, 100mL of tetrahydrofuran was added under nitrogen, dissolved with stirring, and cooled with an ice-water bath. 4.0g (41.7mmol) of sodium tert-butoxide was added while cooling on ice, and after stirring for 10min while maintaining the temperature, 5.9g (41.7mmol) of methyl iodide were added. The system was stirred for 30min and then the ice bath was removed, the system allowed to warm to room temperature and the reaction continued overnight at room temperature. After the reaction, insoluble matter was removed by suction filtration, and the filtrate was concentrated and purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane 10: 1(V/V)) to obtain 6.0g of white crystals, with a yield of 82%. Ms (ei): m/z: 524.48[ M ]+]。Anal.calcd for C39H28N2(％)：C 89.28，H5.38，N 5.34；found：C 89.25，H 5.43；N 5.31。
Example 2: synthesis of Compound 20
(Synthesis of intermediate 20A)
The synthetic route for intermediate 20A is shown below:
Figure BDA0002259465060000821
a dry, clean 250mL three-necked flask was charged with 5g (23mmol) of intermediate 2, 14.1g (50.6mmol) of 3, 6-di-tert-butylcarbazole, and 12.7g (92mmol) of anhydrous potassium carbonate in that order. The system was back and forth replaced with nitrogen three times to remove air therefrom. Adding 150ml of N-methyl pyrrolidone, and gradually heating to 180 DEG℃And reacted at that temperature overnight. After the reaction is cooled, inorganic salt is removed by suction filtration, and the filtrate is distilled under reduced pressure to obtain reddish brown residue. The crude product was further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane 4: 1(V/V)) to give 15.3g of an orange-red solid in 88% yield. Ms (ei): m/z: 735.03[ M ]+]。Anal.calcd for C53H54N2O(％)：C 86.61，H 7.41，N 3.81；found：C 86.57，H7.45，N 3.76。
(Synthesis of intermediate 20B)
The synthetic route for intermediate 20B is shown below:
Figure BDA0002259465060000822
adding 1g (5.9mmol) of iodine simple substance and 100mL of glacial acetic acid into a 250mL three-neck flask provided with a reflux condenser tube and a dropping funnel under the protection of nitrogen, stirring for dissolving, adding about 3.9g (29.6mmol) of hypophosphorous acid, and heating to 120 ℃ for reacting until the system color is faded. 10.9g (14.8mmol) of intermediate 20A were then added in one portion and after further heating under reflux for 4h, cooled to room temperature, poured into water to precipitate a large amount of white solid, filtered, washed with water and dried to give 9.0g of white crystalline solid in 84% yield. Ms (ei): m/z: 721.04[ M ]+]。Anal.calcd for C53H56N2(％)：C 88.29，H 7.83，N 3.89；found：C88.24，H 7.86，N 3.87。
(Synthesis of Compound 20)
The synthetic route for compound 20 is shown below:
Figure BDA0002259465060000831
10.0g (13.9mmol) of the above intermediate 20B solid was transferred to a 250mL three-necked flask equipped with a dropping funnel, 100mL of tetrahydrofuran was added under nitrogen, dissolved with stirring, and cooled with an ice-water bath. 4.0g (41.7mmol) of sodium tert-butoxide was added while cooling on ice, and after stirring for 10min while maintaining the temperature, 5.9g (41.7mmol) of methyl iodide were added. Stirring the system for 30min, removing ice bath, allowing the system to warm to room temperature, and continuously reacting at room temperatureShould be allowed to stand overnight. After the reaction, insoluble matter was removed by suction filtration, and the filtrate was concentrated and purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane 10: 1(V/V)) to obtain 8.7g of white crystals with a yield of 84%. Ms (ei): m/z: 749.08[ M ]+]。Anal.calcd for C55H60N2(％)：C88.19，H 8.07，N 3.74；found：C 88.16，H 8.11；N 3.72。
Example 3: synthesis of Compound 353
(Synthesis of Compound 353)
The synthetic route for compound 353 is shown below:
to a dry, clean, 250mL three-necked flask, 2.0g (8.9mmol) of 2-bromobiphenyl and 150mL of anhydrous tetrahydrofuran are added under nitrogen and dissolved with stirring at room temperature. The system was cooled to-78 ℃ and 3.9mL (2.5M, 9.8mmol) of n-butyllithium were added dropwise at this temperature and stirring continued at this temperature for 1.5 h. 4.1g (8.1mmol) of intermediate 19A were then added in one portion, the cold bath was removed after addition, the reaction warmed to room temperature by itself and stirring was continued overnight. And after the reaction is finished, washing with water, drying and spin-drying to obtain a white solid.
The white solid was transferred to a 250mL single-neck flask equipped with a reflux condenser, 100mL glacial acetic acid was added and heated to reflux, 3mL concentrated HCl was added dropwise, and the reaction was continued under reflux overnight. After the reaction, the heating was turned off, the reaction mixture was cooled to room temperature, poured into ice water, and filtered to obtain a white solid. The crude product was further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane: 5: 1(V/V)) to give 4.5g of white crystals in 85% yield. Ms (ei): m/z: 646.78[ M ]+]。Anal.calcdfor C49H30N2(％)：C 90.99，H 4.68，N 4.33；found：C 90.96，H 4.72，N 4.30。
Example 4: synthesis of Compound 360
(Synthesis of Compound 360)
The synthetic route for compound 360 is shown below:
Figure BDA0002259465060000841
to a dry, clean, 250mL three-necked flask, 2.0g (8.9mmol) of 2-bromobiphenyl and 150mL of anhydrous tetrahydrofuran are added under nitrogen and dissolved with stirring at room temperature. The system was cooled to-78 ℃ and 3.9mL (2.5M, 9.8mmol) of n-butyllithium were added dropwise at this temperature and stirring continued at this temperature for 1.5 h. 6.1g (8.1mmol) of intermediate 20A were then added in one portion, the cold bath was removed after addition, the reaction warmed to room temperature by itself and stirring was continued overnight. And after the reaction is finished, washing with water, drying and spin-drying to obtain a white solid.
The white solid was transferred to a 250mL single-neck flask equipped with a reflux condenser, 100mL glacial acetic acid was added and heated to reflux, 3mL concentrated HCl was added dropwise, and the reaction was continued under reflux overnight. After the reaction, the heating was turned off, the reaction mixture was cooled to room temperature, poured into ice water, and filtered to obtain a white solid. The crude product was further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane: 5: 1(V/V)) to give 6.0g of white crystals in 84% yield. MS (EI) M/z 871.20[ M ]+]。Anal.calcdfor C65H52N2(％)：C 89.61，H 7.17，N 3.22；found：C 89.57，H 7.22，N 3.19。
Example 5: synthesis of Compound 52
(Synthesis of intermediate 3)
The synthetic route for intermediate 3 is shown below:
Figure BDA0002259465060000851
in a clean 250mL three-necked flask, 7.5g (47.8mmol) of 4-chlorobenzeneboronic acid, 0.46g (0.4mmol) of tetrakis (triphenylphosphine) palladium and 8.4g of anhydrous sodium carbonate (79.6mmol) were sequentially added, and the system was purged with nitrogen back and forth three times to remove air. 100mL of a mixed solvent (toluene: water: ethanol ═ 5: 1: 1(V/V)) and 8.2g (39.8mmol) of methyl 2, 6-dichlorobenzoate were added, and the mixture was stirred at room temperature for 10 min. The system was transferred to an oil bath and gradually increasedWarmed to reflux and reacted at reflux overnight. After the reaction is finished, stopping heating, and automatically cooling the reaction system to room temperature. The reaction solution was poured into about 200mL of water and extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane: 20: 1(V/V)) to obtain 10.3g of a pale yellow oily liquid in 92% yield. Ms (ei): m/z: 281.10[ M ]+]。Anal.calcd for C14H10Cl2O2(％)：C 59.81，H 3.59；found：C 59.77，H 3.62。
(Synthesis of intermediate 4)
The synthetic route for intermediate 4 is shown below:
Figure BDA0002259465060000852
10g (35.6mmol) of intermediate 3 and 100mL (2.8g, 71.2mmol) of aqueous sodium hydroxide were added sequentially to a clean 250mL single-neck flask, gradually warmed to reflux and reacted under reflux overnight. After the reaction is finished, stopping heating, and automatically cooling the system. The reaction solution was poured into a 1L beaker, 2N hydrochloric acid was added dropwise to neutralize the system until the system became acidic (pH 1.0), during which time a large amount of white solid was formed, collected by suction filtration, compacted and drained, and washed with water until the eluate became neutral. The filter cake dried overnight at 80 ℃ was a white solid weighing about 8.0g, 84% yield.
The white solid was placed in a 250mL two-necked flask equipped with a mechanical stirring device, and about 80g of polyphosphoric acid was added, gradually warmed to 160 ℃ and reacted at this temperature for 4 h. After the reaction, the heating was stopped, the system was poured into a large beaker containing 1kg of ice while hot under constant stirring, and the system was neutralized to alkaline with 1N sodium hydroxide solution. The yellow solid was collected by suction filtration and washed with copious amounts of water until the eluate was neutral. The filter cake weighed about 6.5g after drying overnight at 80 ℃ with 87% yield. Ms (ei): m/z: 249.13[ M ]+]。Anal.calcd for C13H6Cl2O(％)：C 62.69，H 2.43；found：C 62.66，H 2.45。
(Synthesis of intermediate 52A)
The synthetic route for intermediate 52A is shown below:
Figure BDA0002259465060000861
to a 250mL three-necked flask equipped with a reflux condenser, under nitrogen protection, were added 2.49g (10.0mmol) of intermediate 4, 10.2g (40.0mmol) of pinacol diboron diboride, 823.5mg (0.9mmol) of tris (dibenzylideneacetone) dipalladium, 858.6mg (1.8mmol) of 2-dicyclohexylphosphorus-2, 4, 6-triisopropylbiphenyl, 5.8g (60.0mmol) of potassium acetate, and 100mL of anhydrous dioxane, in that order. The system was warmed to reflux and reacted overnight. After the reaction, the reaction mixture was filtered, and the filtrate was spin-dried and separated by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane 4: 1(V/V)) to obtain 2.4g of a yellow foamy solid with a yield of 56%. Ms (ei): m/z: 432.12[ M ]+]。Anal.calcd for C25H30B2O5(％)：C 69.49，H 7.00；found：C69.45，H 7.04。
(Synthesis of intermediate 52B)
The synthetic route for intermediate 52B is shown below:
Figure BDA0002259465060000871
to a clean 250mL three-necked flask, 4.3g (10mmol) of intermediate 52A, 4.2g (40mmol) of anhydrous sodium carbonate, 6.7g (25mmol) of 2-chloro-4, 6-diphenyl-1, 3, 5-triazine, 115.4mg (0.1mmol) of tetrakis (triphenylphosphine) palladium, and 100mL of a mixed solvent (toluene: water: ethanol ═ 5: 1: 1(V/V)) were sequentially added under nitrogen, and the system was heated to reflux and reacted overnight under reflux. After the reaction is finished, stopping heating, and automatically cooling the reaction system to room temperature. The reaction solution was poured into about 200mL of water and extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane 4: 1(V/V)) to obtain 5.5g of an orange solid with a yield of 85%. Ms (ei): m/z: 642.59[ M ]+]。Anal.calcd for C43H26N6O(％)：C 80.36，H 4.08，N 13.08；found：C80.34，H 4.11，N 13.06。
(Synthesis of intermediate 52C)
The synthetic route for intermediate 52C is shown below:
Figure BDA0002259465060000872
adding 1g (5.9mmol) of iodine simple substance and 100mL of glacial acetic acid into a 250mL three-neck flask provided with a reflux condenser tube and a dropping funnel under the protection of nitrogen, stirring for dissolving, adding about 3.9g (29.6mmol) of hypophosphorous acid, and heating to 120 ℃ for reacting until the system color is faded. Then 9.5g (14.8mmol) of intermediate 52B were added in one portion, heated under reflux for 4h, cooled to room temperature, poured into water to precipitate a large amount of white solid, filtered, washed with water and dried to give 7.6g of white crystalline solid with a yield of 82%. Ms (ei): m/z: 628.68[ M ]+]。Anal.calcd for C43H28N6(％)：C 82.14，H 4.49，N 13.37；found：C82.10，H 4.51，N 13.34。
(Synthesis of Compound 52)
The synthetic route for compound 52 is shown below:
Figure BDA0002259465060000881
8.7g (13.9mmol) of the above intermediate 52C solid was transferred to a 250mL three-necked flask equipped with a dropping funnel, 100mL of tetrahydrofuran was added under nitrogen, dissolved with stirring, and cooled with an ice-water bath. 4.0g (41.7mmol) of sodium tert-butoxide was added while cooling on ice, and after stirring for 10min while maintaining the temperature, 5.9g (41.7mmol) of methyl iodide were added. The system was stirred for 30min and then the ice bath was removed, the system allowed to warm to room temperature and the reaction continued overnight at room temperature. After the reaction, insoluble matter was removed by suction filtration, and the filtrate was concentrated and purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane 5: 1(V/V)) to obtain 7.2g of white crystals, which was obtained in 77% yield. Ms (ei): m/z: 656.74[ M ]+]。Anal.calcd for C45H32N6(％)：C 82.29，H4.91，N 12.80；found：C 82.25，H 4.93；N 12.77。
Example 6: synthesis of Compound 393
The synthetic route for compound 393 is shown below:
Figure BDA0002259465060000882
to a dry, clean, 250mL three-necked flask, 2.0g (8.9mmol) of 2-bromobiphenyl and 150mL of anhydrous tetrahydrofuran are added under nitrogen and dissolved with stirring at room temperature. The system was cooled to-78 ℃ and 3.9mL (2.5M, 9.8mmol) of n-butyllithium were added dropwise at this temperature and stirring continued at this temperature for 1.5 h. 5.2g (8.1mmol) of intermediate 52B were then added in one portion, the cold bath was removed after addition, the reaction warmed to room temperature by itself and stirring was continued overnight. And after the reaction is finished, washing with water, drying and spin-drying to obtain a white solid.
The white solid was transferred to a 250mL single-neck flask equipped with a reflux condenser, 100mL glacial acetic acid was added and heated to reflux, 3mL concentrated HCl was added dropwise, and the reaction was continued under reflux overnight. After the reaction, the heating was turned off, the reaction mixture was cooled to room temperature, poured into ice water, and filtered to obtain a white solid. The crude product was further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane: 5: 1(V/V)) to give 5.0g of white crystals in 79% yield. MS (EI) M/z 778.56[ M ]+]。Anal.calcdfor C55H34N6(％)：C 84.81，H 4.40，N 10.79；found：C 84.79，H 4.43，N 10.76。
Example 7: preparation of organic electroluminescent device 1 (organic EL device 1)
A hole injection layer 3, a hole transport layer 4, an electron blocking layer 5, a light emitting layer 6, a hole blocking layer 7, an electron transport layer 8, an electron injection layer 9 and a cathode 10 were sequentially formed on a transparent anode 2 previously formed on a glass substrate 1 to prepare an organic electroluminescent device as shown in fig. 5.
Specifically, a glass substrate on which an ITO film having a film thickness of 100nm was formed was subjected to ultrasonic treatment in Decon 90 alkaline cleaning solution, rinsed in deionized water, and washed in acetone and ethanol for three times, respectivelyNext, baking is performed in a clean environment to completely remove moisture, washing with ultraviolet light and ozone, and bombarding the surface with a low-energy cation beam. Placing the glass substrate with ITO electrode into a vacuum chamber, and vacuumizing to 4 × 10-4-2×10-5Pa. Then, 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazatriphenylene (HAT-CN) was deposited on the ITO electrode-equipped glass substrate at a deposition rate of 0.2 nm/sec to form a layer having a film thickness of 10nm as a hole injection layer. The compound (compound 20) of example 2 was vapor-deposited on the hole injection layer at a vapor deposition rate of 0.2nm/s to form a layer having a film thickness of 30nm as a hole transport layer. The compound (compound 19) of example 1 was vapor-deposited on the hole-transporting layer at a vapor deposition rate of 0.2nm/s to form a layer having a thickness of 10nm as an electron-blocking layer. On the electron-blocking layer, double-source co-evaporation was performed at a deposition rate of 0.2nm/s for the compound of example 1 (compound 19) as a host material and 0.016nm/s for GD1 as a dopant material to form a layer with a thickness of 20nm as a light-emitting layer, and the proportion by weight of the dopant of GD1 was 8 wt%. The compound (compound 393) of example 6 was vapor-deposited on the light-emitting layer at a vapor deposition rate of 0.2nm/s to form a layer having a thickness of 10nm as a hole-blocking layer. The compound (compound 393) of example 6 was vapor-deposited on the hole-blocking layer at a vapor deposition rate of 0.2nm/s to form a layer having a thickness of 40nm as an electron-transporting layer. On the electron transport layer, 8-hydroxyquinoline-lithium (Liq) was vapor-deposited at a vapor deposition rate of 0.2nm/s to form a layer having a film thickness of 2nm as an electron injection layer. Finally, aluminum was deposited at a deposition rate of 3.0nm/s or more to form a cathode having a film thickness of 100 nm.
Examples 8 to 13: preparation of organic EL devices 2 to 7
An organic EL device was produced under the same conditions as the organic EL device 1 except that the compounds in table 1 below were used instead of the compounds in each layer of example 7, respectively.
Comparative examples 1 to 2: preparation of organic EL device comparative examples 1 to 2
Comparative examples of organic EL devices were prepared under the same conditions as the organic EL device 1 except that the compounds in table 1 below were used instead of the compounds in each layer of example 7, respectively.
The examples and comparative examples relate to the following structures of compounds:
Figure BDA0002259465060000901
TABLE 1
Figure BDA0002259465060000911
The light emission characteristics of the organic EL devices 1 to 7 produced in examples 7 to 13 and the organic EL devices produced in comparative examples 1 to 2 were measured at normal temperature under the application of a direct current voltage in the atmosphere. The measurement results are shown in table 2.
The current-luminance-voltage characteristics of the device were obtained from a Keithley source measuring system (Keithley 2400Sourcemeter, Keithley 2000Currentmeter) with calibrated silicon photodiodes, the electroluminescence spectra were measured by a Photo research PR655 spectrometer, and the external quantum efficiencies of the devices were calculated by the method of the documents adv.mater, 2003,15, 1043-.
The lifetime of the device was measured as: the emission luminance (initial luminance) at the start of light emission was set to 10000cd/m2Constant current driving is performed until the light emission luminance decays to 9000cd/m2(corresponding to 90%, where the initial brightness is taken as 100%: 90% decay). Device lifetime with GD1 as dopant is in the order of 10000cd/m2For initial luminance, attenuation is to 9000cd/m2(corresponding to 90%, where the initial brightness is taken as 100%: 90% decay). The lifetime of the device with BD1 as dopant is 1000cd/m2For initial luminance, attenuation to 900cd/m2(corresponding to 90%, where the initial brightness is taken as 100%: 90% decay). All devices were encapsulated in a nitrogen atmosphere.
TABLE 2
Figure BDA0002259465060000921
As can be seen from table 2, the fluorene derivatives of the present invention obtained excellent performance data.
Organic EL device comparative example 1 and organic EL device 3 each used BD1 as a dopant, and the constituent materials of the hole transport layer, host material, and electron transport layer of organic EL device 3 were compound 20, compound 19, and compound 393 of the present invention. As can be seen from the comparison of the device performance data, the organic EL device 3 has a lower working voltage, the external quantum efficiency is relatively improved by more than 40%, and the device life (90%) is also remarkably improved from 280h to 440 h.
In addition, in both of comparative example 2 and organic EL device 4 of the organic EL device, GD1 was used as a dopant, and the hole transport material, host material and electron transport material of the organic EL device 4 were compound 353, compound 19 and compound 393 of the present invention, and it was found from a comparison of the device performance data that the organic EL device 4 had a longer device life.
FIG. 4 shows an organic electroluminescence spectrum of the organic EL devices 1 to 3 of the present invention. As can be seen from fig. 4, it has a strong emission intensity, in which the organic EL device 3 employs the blue fluorescent material BD1 as a guest, and its blue light peak is at 455nm and has a very narrow half-peak width, demonstrating that the color purity of its blue light is high.
Compared with the common materials in the prior art, the fluorene derivative can effectively reduce the working voltage, improve the external quantum efficiency and prolong the service life of devices.
Industrial applicability
The fluorene derivative of the present invention has excellent light-emitting efficiency and life characteristics, and a low driving voltage. Therefore, an organic electroluminescent device having an excellent lifetime can be prepared from the compound.

Claims (9)

1. A fluorene derivative represented by the following general formula (1):
Figure FDA0002259465050000011
wherein the content of the first and second substances,
L1and L2Each independently represents one or more of a single bond, a carbonyl group, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or an aromatic heterocyclic group having 5 to 18 carbon atoms;
A1and A2Each independently represents Ar1、Ar2、Ar3、Ar4、
Figure FDA0002259465050000012
One or more of;
Ar1～Ar4each independently represents optionally substituted one or more R1Substituted, aromatic hydrocarbon radical having 6 to 30 carbon atoms or optionally substituted by one or more R1One or more substituted aromatic heterocyclic groups having 5 to 30 carbon atoms;
z represents CR1Or N;
m represents C (R)1)2Or a group represented by any one of the following structural formulae (a) to (F):
Figure FDA0002259465050000013
wherein the dotted line represents a bond;
x represents an alkylene group having 1 to 8 carbon atoms, a single bond, or an alkylene group having 1 to 8 carbon atoms;
y represents-C (R)1)2、-NR1、-O-、-S-、-S(O)2-、-P(＝O)R1、-Si(R1)2、-Ge(R1)2Or a single bond;
R1represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, NO2、-N(R2)2、-OR2、-SR2、-C(＝O)R2、-P(＝O)R2、-Si(R2)3Substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, substituted or unsubstituted alkenyl group havingOne or more of an alkynyl group of 2 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 40 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 40 carbon atoms;
R2represents one or more of a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms;
z in the structural formulae (B) to (E) has the meaning as defined in the general formula (1).
2. The fluorene derivative according to claim 1, which is represented by the following general formula (I):
Figure FDA0002259465050000021
L1and L2、Ar1～Ar4Z and M have the meanings defined in claim 1.
3. The fluorene derivative according to claim 1, which is represented by the following general formula (II):
Figure FDA0002259465050000022
L1and L2、Ar1～Ar2Z and M have the meanings defined in claim 1.
4. The fluorene derivative according to claim 1, wherein Ar is Ar1、Ar2、Ar3And Ar4Each independently selected from the following groups:
Figure FDA0002259465050000031
Figure FDA0002259465050000041
Figure FDA0002259465050000051
wherein the dotted line represents and L1、L2Or a bond of an N-bond,
R1have the meaning as defined in claim 1.
5. The fluorene derivative according to any one of claims 1 to 4,
L1and L2Each independently represents a single bond, a carbonyl group, a phenyl group or a triazinyl group;
R1and R2Each independently represents one or more of phenyl, biphenyl, terphenyl, quaterphenyl, pentabiphenyl, benzothienocarbazole, benzofurocarbazole, benzofluorenocarbazole, benzanthracene, triphenylene, fluorenyl, spirobifluorenyl, triazinyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, N-phenylcarbazolyl, indenocarbazolyl, benzimidazolyl, diphenyl-oxadiazolyl, diphenyl boron group, triphenyl phosphoxy, diphenyl phosphoxy, triphenyl silicon group, or tetraphenyl silicon group.
6. The fluorene derivative according to any one of claims 1 to 4, wherein the fluorene derivative represented by the general formula (1) is selected from the following compounds:
Figure FDA0002259465050000071
Figure FDA0002259465050000081
Figure FDA0002259465050000091
Figure FDA0002259465050000101
Figure FDA0002259465050000111
Figure FDA0002259465050000121
Figure FDA0002259465050000131
Figure FDA0002259465050000141
Figure FDA0002259465050000151
Figure FDA0002259465050000161
Figure FDA0002259465050000171
Figure FDA0002259465050000181
Figure FDA0002259465050000191
Figure FDA0002259465050000201
Figure FDA0002259465050000211
Figure FDA0002259465050000221
Figure FDA0002259465050000231
Figure FDA0002259465050000241
Figure FDA0002259465050000251
Figure FDA0002259465050000261
Figure FDA0002259465050000271
Figure FDA0002259465050000281
Figure FDA0002259465050000291
Figure FDA0002259465050000301
Figure FDA0002259465050000311
7. an electronic device comprising the fluorene derivative according to any one of claims 1 to 6.
8. The electronic device according to claim 7, wherein the electronic device is an organic electroluminescent device, an organic field effect transistor, or an organic solar cell;
wherein the organic electroluminescent device comprises: a first electrode, a second electrode provided so as to face the first electrode, and at least one organic layer interposed between the first electrode and the second electrode, wherein the at least one organic layer contains the fluorene derivative according to any one of claims 1 to 6.
9. The electronic device of claim 8, wherein the at least one organic layer is a hole injection layer, a hole transport layer, a light emitting layer, an electron blocking layer, a hole blocking layer, or an electron transport layer.
CN201911066351.1A 2019-11-04 2019-11-04 Fluorene derivative and electronic device Pending CN111056959A (en)

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