CN111635391A - Fluorene compound and electronic device - Google Patents

Fluorene compound and electronic device Download PDF

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Publication number
CN111635391A
CN111635391A CN202010641172.2A CN202010641172A CN111635391A CN 111635391 A CN111635391 A CN 111635391A CN 202010641172 A CN202010641172 A CN 202010641172A CN 111635391 A CN111635391 A CN 111635391A
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group
carbon atoms
fluorene
layer
substituted
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崔林松
朱向东
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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Priority to CN202010641172.2A priority Critical patent/CN111635391A/en
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Abstract

The invention provides a fluorene compound and an electronic device. The fluorene compound has excellent film forming property and thermal stability by introducing a fluorene rigid structure, and can be used for preparing organic electroluminescent devices, organic field effect transistors and organic solar cells. The fluorene compound 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. More importantly, the fluorene compound can effectively isolate donor groups from acceptor groups, so that the fluorene compound is an ideal framework for constructing a thermal activation delayed fluorescence material. The preparation method of the fluorene compound is simple, the raw materials are easy to obtain, and the industrial development requirement can be met.

Description

Fluorene compound and electronic device
Technical Field
The invention belongs to the technical field of organic photoelectric materials, and relates to a fluorene compound and an electronic device containing the fluorene compound. More particularly, the present invention relates to a 1, 8-disubstituted fluorene-based compound suitable for electronic devices, particularly organic electroluminescent devices, organic field effect transistors and organic solar cells, and an electronic device using the fluorene-based compound.
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. Third generation organic electroluminescent materials, generally having a small singlet-triplet energy level difference (Δ E)ST) The triplet excitons may be converted into singlet excitons through reverse intersystem crossing (RISC) to emit light, which may simultaneously utilize singlet excitons and triplet excitons formed under electrical excitation, and the internal quantum efficiency of the device may reach 100%, thus being considered as one of organic light emitting materials widely used in the future. However, the operational lifetime of devices, particularly blue devices, remains an open problem in this area. 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 compound. The fluorene compound has the advantages of high thermal stability, good transmission performance, high triplet state, simple preparation method, high fluorescence quantum yield and small singlet state-triplet state energy level difference, and an organic light-emitting device prepared from the fluorene compound 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 compound, 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.
That is, the present invention is as defined in the above-mentioned embodiments.
ADVANTAGEOUS EFFECTS OF INVENTION
The fluorene compound 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 and a thermal activation delayed fluorescence material 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 compound is simple, raw materials are easy to obtain, and the industrial development requirement can be met.
The fluorene compound 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 compound 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 compound 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 compound 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 a hole blocking layer prepared using the fluorene-based compound 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 compound can be used as a thermally activated delayed fluorescence guest material to be applied to a light emitting layer of an organic electroluminescent device, and the organic electroluminescent device with high light emitting efficiency, low driving voltage and long device service life can be obtained by using the compound to manufacture the organic electroluminescent device.
The fluorene compound of the present invention can be used as a constituent material of 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 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 is a thermogravimetric plot (TGA) of examples 2 and 3 (compounds 2-40 and 2-23) of the present invention.
FIG. 2 shows organic electroluminescence spectra of the organic electroluminescence devices 1 to 3 and 8 in examples 8 to 10 and 15 of the present invention.
FIG. 3 is a view showing the structures of organic electroluminescent devices of examples 8 to 16 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 compound of the present invention is a novel compound having a fluorene ring structure, and is represented by the following general formula (1).
Figure BDA0002571181100000041
Specifically, the fluorene compound of the present invention has the following general formula (I) or (II):
Figure BDA0002571181100000042
in the above general formulae (1), (I) 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、
Figure BDA0002571181100000051
One or more of;
Ar1～Ar4each independently represents a hydrogen atom, a cyano group or optionally substituted by 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 (E):
Figure BDA0002571181100000052
wherein the dotted line represents a bond;
x represents an alkyl group having 1 to 8 carbon atoms or a single bond;
y represents C (R)1)2、NR1、O、S、SO2、P(＝O)R1、Si(R1)2、Ge(R1)2Or a single bond;
w represents C (R)1)2、NR1、O、S、SO2、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, quinoxaloimidazolyl, oxazolyl, benzoxazolyl, naphthooxazolyl, anthraoxazolyl, phenanthroixazolyl, isoxazolyl, 1, 2-thiazolyl, 1, 3-thiazolyl, benzothiazolyl, pyridazinylOxazinyl, benzopyrazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1, 5-diazanthryl, 2, 7-diazpyrenyl, 2, 3-diazpyrenyl, 1, 6-diazpyrenyl, 1, 8-diazpyrenyl, 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, pyrazinyl, phenazinyl, phena, 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, benzeneAnd [9,10 ]]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、
Figure BDA0002571181100000081
One or more of the above.
(Ar1To Ar4)
Ar1～Ar4Each independently represents a hydrogen atom, a cyano group or optionally substituted by 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, anthryl, benzanthryl, phenanthryl, benzophenanthryl, pyrenyl, perylenyl, fluoranthenyl, benzofluoranthenyl, tetracenyl, pentacenyl, benzopyrenyl, biphenyl, idophenyl, terphenyl, quaterphenyl, pentabiphenyl, terphenyl, fluorenyl, spirocyclic groupBisfluorenyl, dihydrophenanthryl, dihydropyrenyl, tetrahydropyrenyl, cis-or trans-indenofluorenyl, cis-or trans-monobenzindenofluorenyl, cis-or trans-dibenzoindenofluorenyl, trimerization indenyl, isotridecyl, spirotrimerization indenyl, spiroisotridecyl, furyl, benzofuryl, isobenzofuryl, dibenzofuryl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, benzothienocarbazolyl, pyrrolyl, indolyl, isoindolyl, carbazolyl, indocarbazolyl, indenocarbazolyl, pyridyl, bipyridyl, terpyridyl, quinolyl, isoquinolyl, acridinyl, phenanthridinyl, benzo-5, 6-quinolyl, benzo-6, 7-quinolyl, benzo-7, 8-quinolyl, phenothiazinyl, phenoxazinyl, pyrazolyl, phenanthridinyl, and the like, Indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxalinimidazolyl, oxazolyl, benzoxazolyl, benzoxadiazolyl, naphthooxazolyl, anthraoxazolyl, phenanthrooxazolyl, isoxazolyl, thiazolyl, isothiazolyl, benzothiazolyl, benzothiadiazolyl, pyridazinyl, benzopyrazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, quinazolinyl, azafluorenyl, diazahnthracenyl, diazapyranyl, tetraazaperynyl, naphthyridinyl, pyrazinyl, phenazinyl, phenoxazinyl, phenothiazinyl, fluoresceinyl, naphthyridinyl, azacarbazolyl, benzocaineyl, phenanthrolinyl, triazolyl, benzotriazolyl, oxadiazolyl, thiadiazolyl, triazinyl, tetrazolyl, tetrazinyl, purinyl, pteridinyl, indolizinyl, Benzothiadiazolyl, pyridopyrrolyl, pyridotriazolyl, xanthyl, benzofurocarbazolyl, benzofluorenocarbazolyl, N-phenylcarbazolyl, diphenyl-benzimidazolyl, diphenyl-oxadiazolyl, diphenyl boron group, triphenylphosphoxy group, diphenylphosphinoxy group, triphenylsilyl group, tetraphenylsilyl group and the like.
In the present invention, preferably, Ar1、Ar2、Ar3And Ar4Each independently selected from a hydrogen atom, a cyano group or the following group:
Figure BDA0002571181100000101
Figure BDA0002571181100000111
Figure BDA0002571181100000121
Figure BDA0002571181100000131
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 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)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 R1Having 1 to 20 carbon atomsAlkyl groups 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 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、SO2、NR2O, S or CONR2And wherein one or more hydrogen atoms may be replaced by deuterium atoms, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, cyano groups, nitro groups.
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 R1A substituent optionally having an alkyl group having 1 to 20 carbon atoms represented byThe same substituents are shown. 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 R1The aromatic hydrocarbon group having 6 to 40 carbon atoms or the aromatic heterocyclic group having 5 to 40 carbon atoms represented by the above formula may be exemplified by the group consisting of 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, benzofurocarbazolylBenzofluorenocarbazolyl, benzanthracenyl, benzophenanthryl, fluorenyl, spirobifluorenyl, triazinyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, indenocarbazolyl, benzimidazolyl, diphenyl-oxadiazolyl, diphenyl boron, triphenylphosphoxy, diphenylphosphineoxy, triphenylsilyl, tetraphenylsilyl, 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 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 the formula1The 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, e.g. N, C-H, C-F, C-Cl, C-Br, C-I, C-CN, C-NO2Carbon-phenyl, carbon-biphenyl, and the like.
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 (E):
Figure BDA0002571181100000161
wherein the dotted line represents a bond;
x represents an alkyl group having 1 to 8 carbon atoms or a single bond; such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, 2-methylhexyl, n-octyl, and the like;
y represents C (R)1)2、NR1、O、S、SO2、P(＝O)R1、Si(R1)2、Ge(R1)2Or a single bond; such as an oxygen atom, a sulfur atom, a sulfone group, a phosphorus oxy group, a dimethyl group, etc.;
w represents C (R)1)2、NR1、O、S、SO2、P(＝O)R1、Si(R1)2、Ge(R1)2Or a single bond; such as an oxygen atom, a sulfur atom, a sulfone group, a phosphorus oxy group, a dimethyl group, etc.;
Z、R1and R2Have the meaning as defined above.
< production method >
The fluorene compound of the present invention can be produced, for example, by the following method:
Figure BDA0002571181100000162
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 compounds of the present invention are shown below, but the present invention is by no means limited to these compounds.
Figure BDA0002571181100000171
Figure BDA0002571181100000181
Figure BDA0002571181100000191
Figure BDA0002571181100000201
Figure BDA0002571181100000211
Figure BDA0002571181100000221
Figure BDA0002571181100000231
Figure BDA0002571181100000241
Figure BDA0002571181100000251
Figure BDA0002571181100000261
< electronic device >
Various electronic devices containing the fluorene-based compound of the present invention can be produced using the fluorene-based compound according to the present invention for producing an organic material that can be particularly configured in the form of a layer. In particular, the fluorene compound 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 (the upper electrode and the hole transport layer are located on the same side while the substrate is on the opposite side as viewed from the light emitting layer), without being limited to these structures. The injection layer, the transport layer, the light emitting layer, the barrier layer, and the like may be fabricated, for example, by forming a layer including or consisting of the fluorene-based compound according to the present invention between electrodes. However, the use of the fluorene-based compound 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-based compound of the present invention.
Fig. 3 is a view showing the configuration of an organic electroluminescent device of the present invention. As shown in fig. 3, 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 compounds, star-shaped triphenylamine compounds, 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 hetero atom 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.
The fluorene compound of the present invention is preferably contained as the hole transport layer of the organic electroluminescent device of the present invention. 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.
The fluorene compound of the present invention is preferably contained as the electron blocking layer of the organic electroluminescent device of the present invention. 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 light-emitting layer of the organic electroluminescent device of the present invention preferably contains the fluorene compound 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. The fluorene compound of the present invention is preferably contained as the host material. 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, the fluorene derivative of the present invention is preferably contained. In addition to these, aromatic amine derivatives, styryl amine compounds, boron complexes, fluoranthene compounds, metal complexes, and 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.
The fluorene compound of the present invention is preferably contained as a hole blocking layer of the organic electroluminescent device of the present invention. 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.
The fluorene compound of the present invention is preferably contained in the electron transport layer of the organic electroluminescent device of the present invention. 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; an anthracene derivative; a carbodiimide derivative; quinoxaline derivatives; pyridoindole derivatives; phenanthroline derivatives; silole derivatives and the like. They may be formed into films alone or mixed with other materialsThe film may be used in the form of a single layer, or may be formed in a stacked structure of layers formed by film formation alone, a stacked structure of layers formed by film mixing, or a stacked structure of layers formed by film formation alone and layers formed by film mixing. 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 Compounds 1-41
(Synthesis of intermediate M1)
The synthetic route for intermediate M1 is shown below:
Figure BDA0002571181100000311
to a clean 100mL single-neck flask were added 30mL of methylene chloride, 7.2g of (71.3mmol) of diisopropylamine and 10.0g (95.0mmol) of triethylamine, 10.0g (47.5mmol) of 2, 6-dichlorobenzoyl chloride are then slowly added dropwise to the single-neck flask in dichloromethane solution. 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. A white solid was formed, collected by suction filtration, compressed, dried and further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane 15: 1(V/V)) to give 10.8g of a white solid in 83% yield. Ms (ei): m/z: 273.26[ M ]+]。Anal.calcd for C13H17Cl2NO(％)：C 56.95，H 6.25；found：C56.83，H 6.20。
(Synthesis of intermediate M2)
The synthetic route for intermediate M2 is shown below:
Figure BDA0002571181100000321
to a clean 250mL three-necked flask, 7.4g (47.8mmol) of 3-chlorobenzeneboronic acid, 8.4g (79.6mmol) of anhydrous sodium carbonate, 10.9g (39.8mmol) of M1, 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 11.6g of a white solid in 83% yield. Ms (ei): m/z: 349.26[ M ]+]。Anal.calcd for C19H21Cl2NO(％)：C 65.15，H 6.04；found：C 65.10，H 6.01。
(Synthesis of intermediate M3)
The synthetic route for intermediate M3 is shown below:
Figure BDA0002571181100000322
to a dry, clean, 250mL three-necked flask, 3.1g (8.9mmol) of M1 and 150mL of anhydrous tetrahydrofuran were added under nitrogen, and dissolved at room temperature with stirring. 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 20 minutes after addition was complete. After the reaction was complete, the mixture was quenched with 5% HCl at-78 ℃. The product was washed with water, dried and spin-dried to give a white solid which was further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane: 15: 1(V/V)) to give 1.9g of a white solid in 90% yield. Ms (ei): m/z: 248.08[ M ]+]。Anal.calcd for C13H6Cl2O(％)：C 62.69，H 2.43；found：C 62.51，H 2.40。
(Synthesis of intermediate M4)
The synthetic route for intermediate M4 is shown below:
Figure BDA0002571181100000331
a dry, clean 250mL three-necked flask was charged with 5.7g (23mmol) of intermediate M3, 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 N-methylpyrrolidone was added, the temperature was gradually raised to 180 ℃ and the reaction was allowed to proceed 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 11.0g of a yellow solid in 95% yield. Ms (ei): m/z: 510.58[ M ]+]。Anal.calcd for C37H22N2O(％)：C 87.04，H 4.34，N 5.49；found：C 87.01，H4.36，N 5.47。
(Synthesis of intermediate M5)
The synthetic route for intermediate M5 is shown below:
Figure BDA0002571181100000332
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 M4 was added in one portion, and after further heating and refluxing for 4h, cooling to room temperature, pouring into water to precipitate a large amount of white solid, filtering, washing with water and drying to obtain 6.0g of white crystalline solid with a yield of 82%. Ms (ei): m/z: 496.48[ M ]+]。Anal.calcd for C37H24N2(％)：C 89.49，H 4.87，N 5.64；found：C 89.46，H4.89，N 5.63。
(Synthesis of Compounds 1-41)
The synthetic routes for compounds 1-41 are shown below:
Figure BDA0002571181100000341
6.9g (13.9mmol) of the M5 solid are transferred into a 250mL three-necked flask equipped with a dropping funnel, 100mL of tetrahydrofuran are added under nitrogen, dissolved with stirring and cooled in 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，H 5.38，N 5.34；found：C 89.25，H 5.43；N 5.31。
Example 2: synthesis of Compounds 2-40
(Synthesis of Compounds 2 to 40)
The synthetic routes for compounds 2-40 are shown below:
Figure BDA0002571181100000342
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 M4 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。
The thermogravimetric curves of the compounds 2 to 40 were measured using a model SDT-2960 thermogravimetric analyzer.
Example 3: synthesis of Compounds 2-23
(Synthesis of intermediate M6)
The synthetic route for intermediate M6 is shown below:
Figure BDA0002571181100000351
to a 250mL three-necked flask equipped with a reflux condenser, under nitrogen protection, were added 2.49g (10.0mmol) of M3, 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. Filtering after the reaction is finished, spin-drying the filtrate, and separating by column chromatography (350-mesh silica gel)The leacheate is petroleum ether: dichloromethane ═ 4: 1(V/V)) gave 2.4g of a yellow solid in 56% yield. Ms (ei): m/z: 432.12[ M ]+]。Anal.calcd for C25H30B2O5(％)：C 69.49，H 7.00；found：C 69.45，H 7.04。
(Synthesis of intermediate M7)
The synthetic route for intermediate M7 is shown below:
Figure BDA0002571181100000361
to a clean 250mL three-necked flask, 4.3g (10mmol) of M6, 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 a yellow solid in 85% yield. Ms (ei): m/z: 642.59[ M ]+]。Anal.calcd for C43H26N6O(％)：C80.36，H 4.08，N 13.08；found：C 80.34，H4.11，N 13.06。
(Synthesis of Compounds 2 to 23)
The synthetic routes for compounds 2-23 are shown below:
Figure BDA0002571181100000362
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 M7 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 5.3g of white crystals in 84% yield. MS (EI) M/z 778.20[ M ]+]。Anal.calcdfor C55H34N6(％)：C 84.81，H 4.40，N 10.79；found：C 84.77，H 4.39，N 10.75。
The thermogravimetric curves of the compounds 2 to 23 were measured using a model SDT-2960 thermogravimetric analyzer.
Example 4: synthesis of Compounds 3-23
(Synthesis of Compounds 3 to 23)
The synthetic route for compounds 3-23 is shown below:
Figure BDA0002571181100000371
to a dry, clean, 250mL three-necked flask, 2.9g (8.9mmol) of 2-bromotriphenylamine and 150mL of anhydrous tetrahydrofuran were 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 M7 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 green 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 is finished, the heating is closed, the reaction solution is cooled to room temperature, poured into ice water, and filtered to obtain a green solid. CoarseThe product was further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane: 5: 1(V/V)) to give 5.9g of green crystals in 84% yield. MS (EI) M/z 869.20[ M ]+]。Anal.calcdfor C61H39N7(％)：C 84.21，H 4.52，N 11.27；found：C 84.15，H 4.51，N 11.25。
Example 5: synthesis of Compounds 6-23
(Synthesis of Compounds 6 to 23)
The synthetic route for compounds 6-23 is shown below:
Figure BDA0002571181100000381
to a dry, clean, 250mL three-necked flask, 3.2g (8.9mmol) of 10- (2-bromobenzene) -9, 9-dimethyl-9, 10-dihydroacridine and 150mL of anhydrous tetrahydrofuran were added under nitrogen, and the mixture was 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 M7 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 green 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 a green solid. The crude product was further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane ═ 5: 1(V/V)) to give 6.2g of green crystals in 84% yield. MS (EI) M/z 909.20[ M ]+]。Anal.calcdfor C64H43N7(％)：C 84.46，H 4.76，N 10.77；found：C 84.40，H 4.72，N 10.75。
Example 6: synthesis of Compounds 3-21
(Synthesis of intermediate M8)
The synthetic route for intermediate M8 is shown below:
Figure BDA0002571181100000382
to a clean 250mL three-necked flask, 4.3g (10mmol) of M7, 4.2g (40mmol) of anhydrous sodium carbonate, 6.5g (25mmol) of 2-bromodibenzothiophene, 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 4.6g of a yellow solid in 85% yield. Ms (ei): m/z: 544.59[ M ]+]。Anal.calcd for C37H20OS2(％)：C 81.59，H 3.70；found：C 81.54，H 3.68。
(Synthesis of Compounds 3 to 21)
The synthetic route for compounds 3-21 is shown below:
Figure BDA0002571181100000391
to a dry, clean, 250mL three-necked flask, 2.9g (8.9mmol) of 2-bromotriphenylamine and 150mL of anhydrous tetrahydrofuran were 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. 4.4g (8.1mmol) of M8 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. CoarseThe product was further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane: 5: 1(V/V)) to give 5.2g of white crystals in 84% yield. MS (EI) M/z 771.20[ M ]+]。Anal.calcdfor C55H33NS2(％)：C 85.57，H 4.31，N 1.81；found：C 85.50，H 4.30，N 1.80。
Example 7: synthesis of Compounds 3 to 27
(Synthesis of intermediate M9)
The synthetic route for intermediate M9 is shown below:
Figure BDA0002571181100000401
to a clean 250mL three-necked flask, 4.3g (10mmol) of M6, 4.2g (40mmol) of anhydrous sodium carbonate, 9.7g (25mmol) of 2- (4-bromophenyl) -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 6.7g of a yellow solid in 85% yield. Ms (ei): m/z: 794.59[ M ]+]。Anal.calcd for C55H34N6O(％)：C 83.10，H 4.31，N 10.57；found：C83.01，H 4.30，N 10.51。
(Synthesis of Compounds 3 to 27)
The synthetic routes for compounds 3-27 are shown below:
Figure BDA0002571181100000402
to a dry, clean, 250mL three-necked flask, 2.9g (8.9mmol) of 2-bromotriphenylamine and 150mL of anhydrous tetrahydrofuran were 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. 6.4g (8.1mmol) of M9 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 green 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 is finished, the heating is closed, the reaction solution is cooled to room temperature, poured into ice water, and filtered to obtain a green solid. The crude product was further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane ═ 5: 1(V/V)) to give 6.9g of green crystals in 84% yield. MS (EI) M/z 1021.20[ M ]+]。Anal.calcd for C73H47N7(％)：C 85.77，H 4.63，N 9.59；found：C 85.65，H 4.61，N 9.55。
Example 8: 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. 3.
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, washed three times in acetone and ethanol, 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, the glass substrate with an ITO electrode was placed in a vacuum chamber, and evacuated 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 (compounds 3 to 21) of example 6 was vapor-deposited on the hole injection layer at a vapor deposition rate of 0.2nm/s to form a layer having a thickness of 30nm as a hole transport layer.The compound (compound 1-41) 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 1-41) as a host material and at a deposition rate of 0.2nm/s for GD1 as a dopant material to form a layer having a thickness of 20nm as a light-emitting layer, and the doping weight ratio of GD1 was 8 wt%. The compound (compound 2-23) of example 3 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 2-23) of example 3 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 0.02nm/s to form a layer having a film thickness of 2nm as an electron injection layer. Finally, aluminum is vapor-deposited at a vapor deposition rate of 0.5nm/s or more to form a cathode having a film thickness of 100 nm.
Examples 9 to 16: preparation of organic EL devices 2 to 9
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 8, 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 8, respectively.
The examples and comparative examples relate to the following structures of compounds:
Figure BDA0002571181100000421
TABLE 1
Figure BDA0002571181100000431
The light emission characteristics of the organic EL devices 1 to 9 produced in examples 8 to 16 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). The lifetime of the device with BD1 as the dopant was 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 BDA0002571181100000451
As can be seen from Table 2, the fluorene compounds 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 the organic EL device 3 were compounds 3 to 21, compounds 1 to 41, and compounds 2 to 23 of the present invention. The comparison of device performance data shows that the organic EL device 3 has lower working voltage, the external quantum efficiency is relatively improved by more than 3 times, the service life (90%) of the device is also obviously improved, and the service life is changed from 2h to 640 h.
In addition, the organic EL device of comparative example 2 and the organic EL device 7 each used GD1 as a dopant, and the hole transport material, the host material, and the electron transport material of the organic EL device 7 were compounds 2 to 40, compounds 1 to 41, and compounds 3 to 23 of the present invention, and as can be seen from a comparison of the device performance data, the organic EL device 7 had a longer device life.
Further, fig. 2 is an organic electroluminescence spectrum of the organic EL devices 1 to 3 and 8 of the present invention. As can be seen from fig. 2, 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.
In addition, the organic EL devices 8 and 9 respectively adopt the compounds 3 to 23 and 3 to 27 as dopants, which are very good in blue light efficiency and lifetime, and prove to have application prospects as guest luminescent materials.
Compared with the common materials in the prior art, the fluorene compound can effectively reduce the working voltage, improve the external quantum efficiency and prolong the service life of devices.
Industrial applicability
The fluorene compound of the present invention has excellent luminous 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 (10)

1. A fluorene compound represented by the following general formula (1):
Figure FDA0002571181090000011
wherein L is1And 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、
Figure FDA0002571181090000012
One or more of;
Ar1～Ar4each independently represents a hydrogen atom, a cyano group or optionally substituted by 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 (E):
Figure FDA0002571181090000013
wherein the dotted line represents a bond;
x represents an alkyl group having 1 to 8 carbon atoms or a single bond;
y represents C (R)1)2、NR1、O、S、SO2、P(＝O)R1、Si(R1)2、Ge(R1)2Or a single bond;
w represents C (R)1)2、NR1、O、S、SO2、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 hydrogenOne or more of an 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 compound according to claim 1, which is represented by the following general formula (I) or general formula (II):
Figure FDA0002571181090000021
L1、L2、Ar1～Ar4m, W and Z have the meaning defined in claim 1.
3. The fluorene-based compound according to claim 1, wherein Ar is Ar1、Ar2、Ar3And Ar4Each independently selected from a hydrogen atom, a cyano group or the following group:
Figure FDA0002571181090000031
Figure FDA0002571181090000041
Figure FDA0002571181090000051
Figure FDA0002571181090000061
wherein the dotted line represents and L1、L2Or a bond of an N-bond,
R1with the benefit ofThe meaning defined in claim 1.
4. The fluorene-based compound according to any one of claims 1 to 3,
L1and L2Each independently represents one or more of a single bond, a carbonyl group, a phenyl group, a triazinyl group or a biphenyl 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.
5. The fluorene-based compound according to any one of claims 1 to 4, wherein the fluorene-based compound represented by the general formula (1) is selected from the group consisting of:
Figure FDA0002571181090000071
Figure FDA0002571181090000081
Figure FDA0002571181090000091
Figure FDA0002571181090000101
Figure FDA0002571181090000111
Figure FDA0002571181090000121
Figure FDA0002571181090000131
Figure FDA0002571181090000141
Figure FDA0002571181090000151
Figure FDA0002571181090000161
6. an electronic device comprising the fluorene-based compound according to any one of claims 1 to 5.
7. The electronic device according to claim 6, 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-based compound according to any one of claims 1 to 5.
8. The electronic device of claim 7, 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.
9. Use of the fluorene compound according to any one of claims 1 to 5 as a light emitting material, an electron transporting material, an electron blocking material, a hole injecting material or a hole blocking material in an electronic device.
10. Use according to claim 9, characterized in that the electronic device is an organic electroluminescent device, an organic field effect transistor or an organic solar cell.
CN202010641172.2A 2020-07-06 2020-07-06 Fluorene compound and electronic device Pending CN111635391A (en)

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