CN109761822B - Fluorene derivative and electronic device - Google Patents

Fluorene derivative and electronic device Download PDF

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Publication number
CN109761822B
CN109761822B CN201910064265.0A CN201910064265A CN109761822B CN 109761822 B CN109761822 B CN 109761822B CN 201910064265 A CN201910064265 A CN 201910064265A CN 109761822 B CN109761822 B CN 109761822B
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organic
carbon atoms
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fluorene
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CN109761822A (en
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崔林松
张业欣
林久栋
陈华
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Weisipu New Material Suzhou Co ltd
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Suzhou Jiuxian New Material Co ltd
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Priority to CN201910064265.0A priority Critical patent/CN109761822B/en
Priority to CN202110579011.XA priority patent/CN113233988B/en
Publication of CN109761822A publication Critical patent/CN109761822A/en
Priority to PCT/CN2020/071129 priority patent/WO2020151499A1/en
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Abstract

The present invention relates to fluorene derivatives and electronic devices. 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 2, 6-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 the organic light-emitting device prepared from the fluorene derivative has the advantages of high light-emitting 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 BDA0001955167850000021
wherein the content of the first and second substances,
L1and L2Each independently represents 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、
Figure BDA0001955167850000022
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 R1A substituted aromatic heterocyclic group 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 (C):
Figure BDA0001955167850000031
wherein the dotted line represents a bond;
x represents C (R)1)2、N(R1)2、O、S、BR1、P(＝O)R2、Si(R1)3Or 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)3A 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 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 (A) to (C) 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 BDA0001955167850000032
wherein L is1、L2、M、Z、Ar1～Ar4Has the meaning as defined for the general formula (1).
[3] The fluorene derivative according to [1], which is represented by the following general formula (II):
Figure BDA0001955167850000033
wherein L is1、L2、M、Z、Ar1～Ar3Has the meaning as defined for the general formula (1).
[4] The fluorene derivative according to [1], which is represented by the following general formula (III):
Figure BDA0001955167850000041
wherein L is1、L2、M、Z、Ar1And Ar2Has the meaning as defined for the general formula (1).
[5]According to [1]The fluorene derivative wherein Ar is1、Ar2、Ar3And Ar4Each independently selected from the following groups:
Figure BDA0001955167850000051
Figure BDA0001955167850000061
Figure BDA0001955167850000071
wherein the dotted line represents and L1、L2Or a bond of an N-bond,
R1has the meaning as defined for the general formula (1).
[6] The fluorene derivative according to any one of [1] to [5], wherein,
L1and L2Each independently represents a single bond, a carbonyl group, a phenyl group or a triazinyl group;
R1and R2Each independently represents phenyl, biphenyl, terphenyl, quaterphenyl, pentabiphenyl, benzothienocarbazole, benzofurocarbazole, benzofluorenocarbazole, benzanthracene, triphenylene, fluorenyl, spirobifluorenyl, triazinyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, indenocarbazolyl, benzimidazolyl, diphenyl-oxadiazolyl, diphenyl boronyl, triphenyl phosphoroxy, diphenyl phosphoroxy, triphenyl silyl, or tetraphenyl silyl.
[7] The fluorene derivative according to any one of [1] to [5], wherein the fluorene derivative represented by the general formula (1) is selected from the following compounds:
Figure BDA0001955167850000081
Figure BDA0001955167850000091
Figure BDA0001955167850000101
[8] an electronic device comprising the fluorene derivative according to any one of [1] to [7 ].
[9] The electronic device according to [8], 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 [7 ].
[10] The electronic device according to [9], 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 of the present invention has excellent electron transport properties and a wide band gap. Therefore, the fluorene-based derivative of the present invention is used as a host material on which a fluorescent emitting substance, a phosphorescent emitting substance, or a delayed fluorescent emitting substance called a dopant is carried so as to form a light emitting layer. This makes it possible to realize an organic electroluminescent device that is driven at a reduced voltage and that is characterized by improved luminous efficiency.
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 ultraviolet absorption spectra (UV-Vis) of compounds of examples 1 to 5 of the present invention (compounds 10, 5, 17, 18 and 36).
FIG. 2 shows the room temperature fluorescence spectra (PL) of the compounds of examples 1 to 5 of the present invention (compounds 10, 5, 17, 18 and 36).
FIG. 3 shows low-temperature phosphorescence spectra (Phos) of the compounds of examples 1 to 5 of the present invention (compounds 10, 5, 17, 18 and 36).
FIG. 4 shows organic electroluminescence spectra of the organic electroluminescent devices 1 to 3 in examples 9 to 11 of the present invention.
FIG. 5 is a view showing the configurations of organic electroluminescent devices of examples 9 to 19 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 BDA0001955167850000131
Specifically, the fluorene derivative of the present invention has the following general formulae (I) to (III):
Figure BDA0001955167850000132
Figure BDA0001955167850000141
in the above general formulae (1), (I) to (III),
L1and L2Each independently represents 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、
Figure BDA0001955167850000142
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 R1A substituted aromatic heterocyclic group 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 (C):
Figure BDA0001955167850000143
wherein the dotted line represents a bond;
x represents C (R)1)2、N(R1)2、O、S、BR1、P(＝O)R2、Si(R1)3Or 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)、OR2、SR2、C(＝O)R2、P(＝O)R2、Si(R2)3A 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 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 (A) to (C) has the meaning as defined in the general formula (1).
<L1And L2>
L1And L2Each independently represents 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-diazenanthrayl, 2, 7-diazapyranyl, 2, 3-diazapyranyl, 1, 6-diazapyranyl, 1, 8-diazapyranyl, 4, 5-diazapyranyl, 4,5,9, 10-tetraazaperylenyl, pyrazinyl, phenazinyl, phenoxazinyl, phenothiazinyl, fluorerynyl, 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 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 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; an aromatic heterocyclic group such as pyridyl, thienyl, furyl, pyrrolyl, quinolyl, isoquinolyl, benzofuryl, benzothienyl, indolyl, carbazolyl, benzoxazolyl, benzothiazolyl, quinoxalyl, benzimidazolyl, pyrazolyl, dibenzofuryl, 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、
Figure BDA0001955167850000171
(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 R1A substituted aromatic heterocyclic group 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, biphenylyl, 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, benzothienyl, benzothiophenocarbazolyl, pyrrolyl, indolyl, isoindolyl, carbazolyl, indolocarbazolyl, indenocarbazolyl, pyridyl, bipyridyl, perylenyl, pyranthrylyl, benzopyrenyl, pentacenyl, benzopyrenyl, terphenyl, Terpyridyl, quinolyl, isoquinolyl, acridinyl, phenanthridinyl, benzo-5, 6-quinolyl, benzo-6, 7-quinolyl, benzo-7, 8-quinolyl, phenothiazinyl, phenoxazinylPyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxalinylimidazolyl, oxazolyl, benzoxazolyl, benzooxadiazolyl, naphthooxazolyl, anthraoxazolyl, phenanthrooxazolyl, isoxazolyl, thiazolyl, isothiazolyl, benzothiazolyl, benzothiadiazolyl, pyridazinyl, benzopyrazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, quinazolinyl, azafluorenyl, diazahrenyl, diazapyranyl, tetraazaperylyl, naphthyridinyl, pyrazinyl, phenazinyl, phenoxazinyl, phenothiazinyl, fluorescenzyl, naphthyridinyl, azacarbazolyl, benzocarbazinyl, phenanthrolinyl, triazolyl, benzotriazolyl, oxadiazolyl, thiadiazolyl, triazinyl, tetrazolyl, tetrazinyl, purinyl, pteridinyl, Indolizinyl, benzothiadiazolyl, pyridopyrrolyl, pyridotriazolyl, xanthenyl, benzofurocarbazolyl, benzofluorenocarbazolyl, N-phenylcarbazolyl, diphenyl-benzimidazolyl, diphenyl-oxadiazolyl, diphenyl boron, triphenylphosporoxy, diphenylphosphinyloxy, triphenylsilicon, tetraphenylsilyl and the like.
In the present invention, preferably, Ar1、Ar2、Ar3And Ar4Each independently selected from the following groups:
Figure BDA0001955167850000191
Figure BDA0001955167850000201
Figure BDA0001955167850000211
wherein the dotted line represents and L1、L2Or a N-bonded bond, R1Has the meaning as defined for the general formula (1).
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 5 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)3A 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, 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 R1Having 1 to 20 carbon atomsBy 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、SO2、NR2O, 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, hexynyl, 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 R1An aromatic hydrocarbon group having 6 to 40 carbon atoms or an aromatic hetero group having 5 to 40 carbon atomsExamples of cyclic groups are given above for 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 boron, triphenyl phosphoxy, diphenyl phosphoxy, triphenyl silicon group, tetraphenyl silicon group, and the like. 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 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 hydrocarbon group having 5 to 30 carbon atomsA group of heterocyclic groups.
From R2The alkyl group having 1 to 20 carbon atoms represented by R can be enumerated by1The 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 the formula 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 (C):
Figure BDA0001955167850000241
wherein the dotted line represents a bond,
x represents C (R)1)2、N(R1)2、O、S、BR1、P(＝O)R2、Si(R1)3Or a single bond.
Z、R1And R2Have the meaning as defined above.
< production method >
The fluorene derivative of the present invention can be produced, for example, by the following method:
Figure BDA0001955167850000242
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 BDA0001955167850000251
Figure BDA0001955167850000261
Figure BDA0001955167850000271
< electronic device >
Various electronic devices containing the fluorene-based derivatives of the present invention can be produced using the fluorene-based derivatives according to the present invention for producing organic materials that can 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, a fluorene derivative containing 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' -triphenyl-9H, 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, a fluorene derivative containing 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.
As the light-emitting layer of the organic electroluminescent device of the present invention, a light-emitting layer comprising the organic electroluminescent device of the present invention is preferably usedThe fluorene derivative of (1). 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, a 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, a fluorene derivative containing 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, a fluorene derivative containing 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) ); such as 2- [4- (9, 10-dinaphthalen-2-anthracen-2-yl) phenyl]Benzimidazole derivatives such as-1-phenyl-1H-benzimidazole (ZADN); a thiadiazole derivative; an anthracene derivative; 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 10
(Synthesis of intermediate 1)
The synthetic route for intermediate 1 is shown below:
Figure BDA0001955167850000321
10.0g (36.21mmol) of 2-amino-5, 4' -dibromo-benzophenone and 80mL of water were put into a 250mL three-necked flask equipped with a thermometer, a dropping funnel and mechanical stirring, 5.0g (50mmol) of 98% concentrated sulfuric acid was slowly dropped under stirring, stirred for 30 minutes, cooled to 0 ℃ and a solution of 1.5g (21mmol) of sodium nitrite in 5mL of water was dropped, after dropping, the temperature was maintained for 30 minutes, slowly warmed to 60 ℃ until bubbles were completely released, cooled to room temperature, and filtered to obtain a pale yellow crystalline solid. The solid was isolated by column chromatography (350 mesh silica gel, eluent: petroleum ether: dichloromethane: 20:1(V/V)), the solvent was evaporated and dried to give 7.50g of pale yellow crystals in 80% yield. MS (EI) M/z 338.2[ (M +1)+]。Anal.calcd for C13H6Br2O(％)：C 46.42，H 1.56；found：C 46.20，H 1.79。
(Synthesis of intermediate 10A)
The synthetic route for intermediate 10A is shown below:
Figure BDA0001955167850000331
in a 250mL three-necked flask equipped with a reflux condenser tube and a dropping funnel, 2g (11.8mmol) of elemental iodine and 100mL of glacial acetic acid were added under nitrogen protection, stirred and dissolved, and then about 7.8g (59.2mmol) of hypophosphorous acid was added, and the mixture was heated to 120 ℃ for reflux. Then 10g (29.6mmol) of intermediate 1 was added in one portion, heating and refluxing were continued for 4h, then cooling to room temperature, pouring into water to precipitate a large amount of white solid, filtering, washing with water and drying to obtain a white crystalline solid.
The resulting white crystalline solid was transferred to a 250mL three-necked flask equipped with a dropping funnel, 100mL of tetrahydrofuran was added under nitrogen, the mixture was dissolved by stirring, 8.5g (88.8mmol) of sodium tert-butoxide was added in ice bath, the temperature was kept for 10min, 12.6g (88.8mmol) of methyl iodide was added, the temperature was raised to room temperature, and the reaction was stirred overnight. After the reaction, the reaction mixture was filtered, and the filtrate was spin-dried, separated by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane: 20:1(V/V)), evaporated to remove the solvent, and dried to obtain 7.0g of white crystals with a yield of 70%. MS (EI) M/z 352.07[ (M +1)+]。Anal.calcd for C15H12Br2(％)：C 51.17；H 3.44；Br 45.39；found：C 51.25，H 3.40；Br 45.35。
(Synthesis of Compound 10)
The synthetic route for compound 10 is shown below:
Figure BDA0001955167850000341
in a 250mL three-necked flask equipped with a reflux condenser, 10g (28.4mmol) of intermediate 10A, 14.25g (85.21mmol) of carbazole, 318mg (1.42mmol) of palladium acetate, 824mg (2.84mmol) of tri-tert-tetrafluoroborate were added under nitrogen protectionButylphosphine, 27.3g (284mmol) of sodium tert-butoxide and 100ml of anhydrous toluene were heated to reflux and reacted overnight. After the reaction, the reaction mixture was filtered, and the filtrate was spin-dried, separated by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane 4:1(V/V)), evaporated to remove the solvent, and dried to obtain 12.0g of white crystals, with a yield of 80%. MS (EI) M/z 354.23[ (M +1)+]。Anal.calcd for C39H28N2(％)：C 89.28；H 5.38；N 5.34；found：C 89.35；H 5.47；N 5.18。
Example 2: synthesis of Compound 5
The synthetic route for compound 5 is shown below:
Figure BDA0001955167850000342
in a 250mL three-necked flask equipped with a reflux condenser, 10g (28.4mmol) of intermediate 2A, 18.69g (85.21mmol) of 1-naphthylaminobenzene, 318mg (1.42mmol) of palladium acetate, 824mg (2.84mmol) of tri-tert-butylphosphine tetrafluoroborate, 27.3g (284mmol) of sodium tert-butoxide and 100mL of anhydrous toluene were added under nitrogen protection, and the mixture was heated to reflux and reacted overnight. After the reaction, the reaction mixture was filtered, and the filtrate was spin-dried, separated by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane 4:1(V/V)), evaporated to remove the solvent, and dried to obtain 15.0g of white crystals with a yield of 84%. MS (EI) M/z 628.82[ (M +1)+]。Anal.calcd for C47H36N2(％)：C 89.77；H 5.77；N 4.46；found：C 89.50；H 5.98；N 4.52。
Example 3: synthesis of Compound 17
The synthetic route for compound 17 is shown below:
Figure BDA0001955167850000351
in a 250mL three-necked flask equipped with a reflux condenser, 10g (28.4mmol) of intermediate 2A, 29.0g (59.65mmol) of N- (4- (9-phenylcarbazol-3-yl) phenyl) biphenyl-4-amine, 318mg (1.42mmol) of palladium acetate, 824mg (2.84 mm) of palladium acetate were added under nitrogen protectionol) Tri-tert-butylphosphine tetrafluoroborate, 5.46g (56.8mmol) of sodium tert-butoxide and 100ml of anhydrous toluene, the mixture was heated to reflux and reacted overnight. After completion of the reaction, the reaction mixture was filtered, and the filtrate was spin-dried, separated by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane ═ 4:1(V/V)), evaporated in vacuo and dried to give 29.0g of white crystals, yield 87%. MS (EI) M/z 1163.48[ (M +1)+]。Anal.calcd for C87H62N4(％)：C 89.81；H 5.37；N 4.82；found：C 89.60；H 5.48；N 4.92。
Example 4: synthesis of Compound 18
(Synthesis of intermediate 18A)
The synthetic route for intermediate 18A is shown below:
Figure BDA0001955167850000352
in a 250ml three-necked flask, 8.3g (35.5mmol) of 2-bromobiphenyl and 100ml of anhydrous tetrahydrofuran are added under the protection of nitrogen, stirred and dissolved, 14.2ml (2.5M) of n-butyllithium is slowly dropped at-78 ℃, and after the addition is finished, the temperature is kept and stirring is continued for 1.5 h. After 1.5h, 10g (29.6mmol) of intermediate 1 were added in one portion and the reaction temperature was raised to room temperature and stirred overnight. And after the reaction is finished, washing with water, drying and spin-drying to obtain a white solid.
The white solid obtained by spin-drying was transferred to a 250mL three-necked flask equipped with a reflux condenser, 100mL of glacial acetic acid was added and heated under reflux, and 3mL of concentrated hydrochloric acid was added dropwise and refluxed overnight. After the reaction, heating was turned off, cooling was performed to room temperature, the reaction solution was poured into ice water, and filtration was performed to obtain a white crystalline solid, which was separated by column chromatography (350 mesh silica gel, eluent was petroleum ether: dichloromethane: 50:1(V/V)), and the solvent was evaporated and dried to obtain 10.0g of a white crystal with a yield of 71%. MS (EI) M/z 474.2[ (M +1)+]。Anal.calcd for C25H14Br2(％)：C 63.32；H 2.98；Br 33.70；found：C 63.44；H 2.85；Br 33.71。
(Synthesis of Compound 18)
The synthetic route for compound 18 is shown below:
Figure BDA0001955167850000361
in a 250mL three-necked flask equipped with a reflux condenser, 10g (21.1mmol) of intermediate 18A and 16.8g (46.4mmol) of N- [1,1' -biphenyl were added under nitrogen protection]-2-yl-9, 9-dimethyl-9H-fluoren-2-amine, 236.7mg (1.05mmol) palladium acetate, 611.8mg (2.1mmol) tri-tert-butylphosphine tetrafluoroborate, 4.0g (42.2mmol) sodium tert-butoxide and 100ml anhydrous toluene were heated to reflux and reacted overnight. After the reaction, the reaction mixture was filtered, and the filtrate was spin-dried, separated by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane 4:1(V/V)), evaporated to remove the solvent, and dried to obtain 18.0g of white crystals with a yield of 83%. MS (EI) M/z 1035.35[ (M +1)+]。Anal.calcd for C79H58N2(％)：C 91.65；H 5.65；N 2.71。found：C 91.50；H 5.86；N 2.64。
Example 5: synthesis of Compound 36
(Synthesis of intermediate 36A)
The synthetic route for intermediate 36A is shown below:
Figure BDA0001955167850000362
15.4g (47.3mmol) of 2-bromotriphenylamine and 100ml of anhydrous tetrahydrofuran are added into a 250ml three-neck flask under the protection of nitrogen, stirred and dissolved, 18.9ml (2.5M) of n-butyllithium is slowly dropped at-78 ℃, and after the addition is finished, the temperature is kept for stirring for 1.5 h. After 1.5h, 10g (29.6mmol) of intermediate 1 were added in one portion and the reaction temperature was raised to room temperature and stirred overnight. And after the reaction is finished, washing with water, drying and spin-drying to obtain a white solid.
The white solid obtained by spin-drying was transferred to a 250mL three-necked flask equipped with a reflux condenser, 100mL of glacial acetic acid was added and heated under reflux, and 3mL of concentrated hydrochloric acid was added dropwise and refluxed overnight. Heating, cooling to room temperature, pouring the reaction solution into ice water, filtering to obtain white crystalline solid, and separating by column chromatography (350 mesh silica gel, eluent)Is petroleum ether: dichloromethane 50:1(V/V)), the solvent was evaporated and dried to obtain 11.0g of white crystals with a yield of 66%. MS (EI) M/z 565.31[ (M +1)+]。Anal.calcd for C31H19Br2N(％)：C 65.87；H 3.39；Br 28.27；N 2.48；found：C 65.60；H 3.45；Br 28.16；N 2.58。
(Synthesis of Compound 36)
The synthetic route for compound 36 is shown below:
Figure BDA0001955167850000371
in a 250mL three-necked flask equipped with a reflux condenser, 10g (17.7mmol) of intermediate 36A and 14.1g (38.9mmol) of N- [1,1' -biphenyl were added under nitrogen protection]-2-yl-9, 9-dimethyl-9H-fluoren-2-amine, 198.6mg (0.9mmol) palladium acetate, 513.2mg (1.8mmol) tri-tert-butylphosphine tetrafluoroborate, 3.4g (35.4mmol) sodium tert-butoxide and 100ml anhydrous toluene, warmed to reflux and reacted overnight. After completion of the reaction, the reaction mixture was filtered, and the filtrate was spin-dried, separated by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane ═ 4:1(V/V)), evaporated in vacuo and dried to give 16.5g of white crystals in 81% yield. MS (EI) M/z 1126.46[ (M +1)+]。Anal.calcd for C85H63N3(％)：C 90.63；H 5.64；N 3.73。found：C 90.77；H 5.41；N 2.82。
Example 6: synthesis of Compound 25
(Synthesis of intermediate 25A)
The synthetic route for intermediate 25A is shown below:
Figure BDA0001955167850000381
in a 200mL three-necked flask equipped with a reflux condenser, 3.49g (10.0mmol) of intermediate 10A, 7.6g (30.0mmol) of pinacol diboron, and 198.6mg (0.9mmol) of [1,1' -bis (diphenylphosphino) ferrocene]Palladium dichloride, 6.2g (30.0mmol) of potassium phosphate and 50ml of dioxane, the temperature is raised to reflux,the reaction was allowed to proceed overnight. After the reaction, the reaction mixture was filtered, and the filtrate was spin-dried, separated by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane 4:1(V/V)), evaporated to remove the solvent, and dried to obtain 3.5g of white crystals with a yield of 75%. MS (EI) M/z 1126.46[ (M +1)+]。Anal.calcd for C85H63N3(％)：C 72.68；H 8.13。found：C 72.64；H 5.41。
(Synthesis of Compound 25)
The synthetic route for compound 25 is shown below:
Figure BDA0001955167850000382
in a 200mL Schlenk flask, intermediate 25A4.5g (10.0mmol), 2-chloro-4, 6-diphenyl-1, 3, 5-triazine 5.87g (22.0mmol), tetrakis (triphenylphosphine) palladium 0.26g (0.23mmol), anhydrous potassium carbonate 3.0g (22.0mmol), tetrahydrofuran 50mL and water 8mL were added, and the reaction was stirred at 70 ℃ for 30h under argon gas protection, whereupon the reaction was completed. The solvent was distilled off, the residue was dissolved in 50mL of dichloromethane and 50mL of water, washed with water, the organic layer was separated, the aqueous layer was extracted twice with 15mL of dichloromethane, the organic layers were combined, washed twice with 50mL of water to neutrality, the solvent was distilled off, and then the residue was separated by column chromatography (silica gel 350 mesh, eluent: petroleum ether: trichloromethane 2.5:1(V/V)), the solvent was distilled off, and after drying, 5.6g of white crystals were obtained in 78% yield. MS (EI) M/z 785.93[ M ]+]。Anal.calcd for C59H35N3(％)：C 82.29，H 4.91，N 12.80；found：C 82.25，H 4.86，N 12.86。
Example 7: synthesis of Compound 26
(Synthesis of intermediate 26A)
The synthetic route for intermediate 26A is shown below:
Figure BDA0001955167850000391
in a 200mL three-necked flask equipped with a reflux condenser, 4.72g (10.0mmol) of intermediate 1 was added under nitrogen protection8A, 7.6g (30.0mmol) of pinacol diboron, 198.6mg (0.9mmol) of [1,1' -bis (diphenylphosphino) ferrocene]Palladium dichloride, 6.2g (30.0mmol) of potassium phosphate and 50ml of dioxane were heated to reflux and reacted overnight. After the reaction, the reaction mixture was filtered, and the filtrate was spin-dried, separated by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane 4:1(V/V)), evaporated to remove the solvent, and dried to obtain 4.8g of white crystals, with a yield of 85%. MS (EI) M/z 1126.46[ (M +1)+]。Anal.calcd for C85H63N3(％)：C 78.20；H 6.74。found：C 78.16；H 6.71。
(Synthesis of Compound 26)
The synthetic route for compound 26 is shown below:
Figure BDA0001955167850000392
in a 200mL Schlenk flask, 5.7g (10.0mmol) of intermediate 26A, 5.87g (22.0mmol) of 2-chloro-4, 6-diphenyl-1, 3, 5-triazine, 0.26g (0.23mmol) of tetrakis (triphenylphosphine) palladium, 3.0g (22.0mmol) of anhydrous potassium carbonate, 50mL of tetrahydrofuran and 8mL of water were added, and the reaction was stirred at 70 ℃ for 30 hours under argon atmosphere to complete the reaction. The solvent was distilled off, the residue was dissolved in 50mL of dichloromethane and 50mL of water, washed with water, the organic layer was separated, the aqueous layer was extracted twice with 15mL of dichloromethane, the organic layers were combined, washed twice with 50mL of water to neutrality, the solvent was distilled off, and then the residue was separated by column chromatography (silica gel 350 mesh, eluent: petroleum ether: trichloromethane 2.5:1(V/V)), the solvent was distilled off, and after drying, 6.2g of white crystals were obtained in a yield of 79%. MS (EI) M/z 785.93[ M ]+]。Anal.calcd for C59H35N3(％)：C 84.81，H 4.40，N 10.79；found：C 84.78，H 4.41，N 10.76。
Example 8: synthesis of Compound 40
(Synthesis of intermediate 40A)
The synthetic route for intermediate 40A is shown below:
Figure BDA0001955167850000401
in a 200mL three-necked flask equipped with a reflux condenser, 5.6g (10.0mmol) of intermediate 36A, 7.6g (30.0mmol) of pinacol diboron, and 198.6mg (0.9mmol) of [1,1' -bis (diphenylphosphino) ferrocene]Palladium dichloride, 6.2g (30.0mmol) of potassium phosphate and 50ml of dioxane were heated to reflux and reacted overnight. After the reaction, the reaction mixture was filtered, and the filtrate was spin-dried, separated by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane ═ 4:1(V/V)), evaporated to remove the solvent, and dried to obtain 5.8g of white crystals with a yield of 87%. MS (EI) M/z 1126.46[ (M +1)+]。Anal.calcd for C85H63N3(％)：C 78.32；H 6.57。found：C 78.30；H 6.55。
(Synthesis of Compound 40)
The synthetic route for compound 40 is shown below:
Figure BDA0001955167850000402
in a 200mL Schlenk flask, 6.6g (10.0mmol) of intermediate 40A6, 5.87g (22.0mmol) of 2-chloro-4, 6-diphenyl-1, 3, 5-triazine, 0.26g (0.23mmol) of tetrakis (triphenylphosphine) palladium, 3.0g (22.0mmol) of anhydrous potassium carbonate, 50mL of tetrahydrofuran and 8mL of water were added, and the reaction was stirred at 70 ℃ for 30 hours under the protection of argon gas, whereupon the reaction was completed. The solvent was distilled off, the residue was dissolved in 50mL of dichloromethane and 50mL of water, washed with water, the organic layer was separated, the aqueous layer was extracted twice with 15mL of dichloromethane, the organic layers were combined, washed twice with 50mL of water to neutrality, the solvent was distilled off, and then the residue was separated by column chromatography (silica gel 350 mesh, eluent: petroleum ether: trichloromethane 2.5:1(V/V)), the solvent was distilled off, and after drying, 7.8g of white crystals were obtained in a yield of 89%. MS (EI) M/z 785.93[ M ]+]。Anal.calcd for C59H35N3(％)：C 84.21，H 4.52，N 11.27；found：C 84.23，H 4.51，N 11.23。
Example 9: 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 a Decon 90 alkaline cleaning solution, rinsed in deionized water, washed three times in acetone and ethanol, respectively, baked in a clean environment to completely remove moisture, washed with ultraviolet light and ozone, and bombarded on 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 5) of example 2 was vapor-deposited on the hole injection layer at a vapor deposition rate of 2.0nm/s to form a layer having a film thickness of 30nm as a hole transport layer. The compound (compound 10) of example 1 was vapor-deposited on the hole-transporting layer at a vapor deposition rate of 2.0nm/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 2.0nm/s for the compound of example 1 (compound 10) as a host material and at a deposition rate of 0.16nm/s for GD1 as a dopant material to form a layer with a thickness of 20nm as a light-emitting layer, and the doping weight ratio of GD1 was 8 wt%. The compound (compound 26) of example 7 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 26) of example 7 was vapor-deposited on the hole-blocking layer at a vapor deposition rate of 2.0nm/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 10 to 19: preparation of organic EL devices 2 to 11
Organic EL devices were 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 9, 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 9.
The examples and comparative examples relate to the following structures of compounds:
Figure BDA0001955167850000431
TABLE 1
Figure BDA0001955167850000441
The light emission characteristics of the organic EL devices 1 to 11 produced in examples 9 to 19 and the organic EL devices produced in comparative examples 1 to 2 were measured when a dc voltage was applied in the atmosphere at normal temperature. 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). And device lifetime with BD1 as dopantMeans at 5000cd/m2For initial luminance, decay to 4500cd/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 BDA0001955167850000461
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 5, compound 10, and compound 26 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 nearly 4 times, and the service life (90%) of the device is also remarkably improved from 2h to 620 h.
In addition, in both of comparative example 2 and organic EL device 7, GD1 was used as a dopant, and the hole-transporting material, host material, and electron-transporting material of organic EL device 7 were compound 5, compound 40, and compound 26 of the present invention, and it was found from a comparison of the device performance data that organic EL device 7 had a longer device life.
Further, fig. 4 is 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 (5)

1. A fluorene derivative represented by the following general formula (III):
Figure FDA0002959885830000011
wherein the content of the first and second substances,
L1and L2Each independently represents a single bond;
Ar1and Ar2Each independently represents a group selected from:
Figure FDA0002959885830000012
wherein the dotted line represents and L1Or L2A bonded bond;
z represents CH;
m represents a group represented by the following structural formula (A):
Figure FDA0002959885830000013
wherein the dotted line represents a bond;
R1represents phenyl, biphenyl or terphenyl;
z in the formula (A) has the meaning as defined above.
2. The fluorene derivative according to claim 1, wherein the fluorene derivative represented by the general formula (III) is selected from the following compounds:
Figure FDA0002959885830000014
3. an electronic device characterized in that it comprises the fluorene-based derivative according to claim 1 or 2.
4. The electronic device according to claim 3, 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 claim 1 or 2.
5. The electronic device of claim 4, 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.
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