阅读说明：本技术 芴类化合物和电子器件 (Fluorene compound and electronic device ) 是由 崔林松 朱向东 刘向阳 张业欣 陈华 于 2020-07-06 设计创作，主要内容包括：本发明提供一种芴类化合物和电子器件。本发明的芴类化合物通过引入芴类刚性结构,其的成膜性和热稳定性优异,可用于制备有机电致发光器件、有机场效应晶体管和有机太阳能电池。另外,本发明的芴类化合物可以作为空穴注入层、空穴传输层、发光层、电子阻挡层、空穴阻挡层或电子传输层的构成材料,能够降低驱动电压,提高效率、亮度和寿命等。更为重要的是,本发明的芴类化合物能有效地隔离给体和受体基团,从而是构建热激活延迟荧光材料的理想骨架。本发明的芴类化合物的制备方法简单,原料易得,能够满足工业化的发展需求。(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.)

1. A fluorene compound represented by the following general formula (1):

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、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):

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):

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:

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:

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.

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).

Specifically, the fluorene compound of the present invention has the following general formula (I) or (II):

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、

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):

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、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:

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):

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:

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.

< 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.