CN111647009A

CN111647009A - Boron-containing compound and electronic device thereof

Info

Publication number: CN111647009A
Application number: CN202010489285.5A
Authority: CN
Inventors: 崔林松; 朱向东; 张业欣; 陈华
Original assignee: Suzhou Jiuxian New Material Co ltd
Current assignee: Weisipu New Material Suzhou Co ltd
Priority date: 2020-06-02
Filing date: 2020-06-02
Publication date: 2020-09-11
Anticipated expiration: 2040-06-02
Also published as: CN111647009B

Abstract

The invention belongs to the technical field of organic photoelectric materials, and relates to a boron-containing compound and an electronic device thereof. According to the invention, the boron-containing compound is obtained by introducing the boron-containing rigid structure, and can effectively inhibit vibration relaxation caused by molecular vibration and rotation, so that the boron-containing compound has a narrower luminous peak, excellent film-forming property and thermal stability and higher fluorescence quantum yield, and can be used for preparing organic electroluminescent devices, organic field effect transistors and organic solar cells. In addition, the boron-containing 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, and can reduce a driving voltage, improve efficiency, luminance, lifetime, color purity, and the like. In addition, the preparation method of the boron-containing compound is simple, the raw materials are easy to obtain, and the industrialized development requirement can be met.

Description

Boron-containing compound and electronic device thereof

Technical Field

The invention belongs to the technical field of organic photoelectric materials, and relates to a boron-containing compound and an electronic device containing the same. More particularly, the present invention relates to a boron-containing compound suitable for electronic devices, particularly organic electroluminescent devices, organic field effect transistors and organic solar cells, and an electronic device using the same.

Background

The organic electroluminescent device has a series of advantages of self-luminescence, low-voltage driving, full curing, wide viewing angle, simple composition and process and the like, and compared with a liquid crystal display, the organic electroluminescent device does not need a backlight source. Therefore, the organic electroluminescent device has wide application prospect.

Organic electroluminescent devices generally comprise an anode, a metal cathode and an organic layer sandwiched therebetween. The organic layer mainly comprises a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer. In addition, a host-guest structure is often used for the light-emitting layer. That is, the light emitting material is doped in the host material at a certain concentration to avoid concentration quenching and triplet-triplet annihilation, improving the light emitting efficiency. Therefore, the host material is generally required to have a higher triplet energy level and, at the same time, a higher stability.

At present, research on organic electroluminescent materials has been widely conducted in academia and industry, and a large number of organic electroluminescent materials with excellent performance have been developed. In view of the above, the future direction of organic electroluminescent devices is to develop high efficiency, long lifetime, low cost white light devices and full color display devices, but the design of thermally activated delayed fluorescent materials with high color purity 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 boron-containing compound. The boron-containing compound has the advantages of narrow luminous peak, high thermal stability, good transmission performance, high fluorescence quantum yield and simple preparation method, and an organic light-emitting device prepared from the boron-containing compound has the advantages of high luminous efficiency, long service life, short luminous wavelength, low driving voltage and high color purity, and is an organic electroluminescent material with excellent performance.

It is another object of the present invention to provide an electronic device using the boron-containing compound, which has advantages of high efficiency, high durability and long life.

Means for solving the problems

[1] A boron-containing compound represented by the following general formula (1):

wherein the content of the first and second substances,

B₁represents 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 ring atoms;

if present, each A₁Each independently represents Ar₁Or

m is 1Any integer of to 5;

if present, each Ar₁And Ar₂Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, a cyano group, optionally substituted by one or more R¹Substituted aromatic hydrocarbon radical having 6 to 30 carbon atoms or optionally substituted by one or more R¹A substituted aromatic heterocyclic group having 5 to 30 ring atoms;

each M independently represents a single bond, C (R)¹)₂、NR¹、O、S、S(＝O)₂、P(＝O)R¹、Si(R¹)₂Or Ge (R)¹)₂；

C₁Represents a group represented by any one of the following structural formulae C-1 to C-54:

C₂and C₃Each independently represents a group represented by any one of the following structural formulae C-55 to C-70:

in the structural formulae C-1 to C-70,

the dotted line represents a bond;

each Z independently represents CR¹Or N;

each W, if present, independently represents a single bond, C (R)¹)₂、NR¹、O、S、S(＝O)₂、P(＝O)R¹、Si(R¹)₂Or Ge (R)¹)₂；

If present, each R¹Each independently represents a hydrogen atom, a deuterium atom, or a fluorine atomAtom(s), chlorine atom, bromine atom, iodine atom, cyano group, NO₂、N(R²)₂、OR²、SR²、C(＝O)R²、P(＝O)R²、Si(R²)₃A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 40 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 40 ring atoms;

if present, each R²Each independently represents 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 ring atoms.

[2] The boron-containing compound according to [1], which is represented by the following general formula (I) or (II):

wherein, B₁、Ar₁To Ar₂M, M and C₁To C₃As defined in claim 1.

[3]According to [1]The boron-containing compound, wherein, if present, each Ar₁And Ar₂Each independently selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, a cyano group, or any one of the following groups:

wherein the dotted line represents a bond, R¹As defined in claim 1; preferred are phenyl, fluorenyl, dianilino, dianilinoindolyl, benzofurodianilino, benzothienodianilino, dibenzofuranyl, dibenzothienyl, carbazolyl, indenocarbazolyl, benzofurocarbazolyl, benzothienocarbazolyl, indonocarbazolyl, acridinyl, phenoxazinyl and phenothiazinyl.

[4] The boron-containing compound according to any one of [1] to [3], wherein,

B₁represents a single bond, carbonyl, phenyl, naphthyl, fluorenyl, phenanthryl, anthracyl or triazinyl, preferably phenyl, naphthyl, fluorenyl or anthracyl;

m is any integer from 1 to 4, preferably any integer from 1 to 3, more preferably 1 or 2;

if present, each Ar₁And Ar₂Each independently represents a phenyl group, a fluorenyl group, a dianilino group, a dianilinoindolyl group, a benzofurodianilino group, a benzothienodianilino group, a dibenzofuranyl group, a dibenzothiophenyl group, a carbazolyl group, an indenocarbazolyl group, a benzofurocarbazolyl group, a benzothienocarbazolyl group, an indonocarbazolyl group, an acridinyl group, a phenoxazinyl group and a phenothiazinyl group, preferably a carbazolyl group, an acridinyl group, a phenoxazinyl group, a phenothiazinyl group and a diphenylamine group;

each M independently represents a single bond, C (R)¹)₂、NR¹O and S, preferably NR¹And O;

C₁、C₂and C₃Each independently represents a fragment derived from any one of the following structures: optionally substituted by one or more C1-C6 alkyl groupsBenzene, carbazole, phenoxazine, phenothiazine, diphenylamine, dibenzofuran and dibenzothiophene optionally substituted with one or more alkyl or aryl groups, preferably benzene, tert-butyl benzene, N-methylcarbazole, N-phenylcarbazole, phenoxazine, phenothiazine, dibenzofuran and diphenylthiophene;

if present, each R¹And R²Each independently represents a phenyl group, a naphthyl group, a dimethylfluorenyl group, a dibenzothienyl group, a dibenzofuranyl group, a triazinyl group, a pyrimidinyl group, a pyridyl group, a biphenyl group, a terphenyl group, a quaterphenyl group, a pentabiphenyl group, a dianilino group, a trianilino group, a benzothienocarbazolyl group, a benzofurocarbazolyl group, a benzofluorenocarbazolyl group, a benzanthracenyl group, a benzophenanthrenyl group, a spirobifluorenyl group, a carbazolyl group, an N-phenylcarbazolyl group, an indenocarbazolyl group, a benzimidazolyl group, a diphenyl-oxadiazolyl group, a diphenyl boron group, a triphenylphosphoxy group, a diphenylphosphinoxy group, a triphenylsilyl group, a tetraphenylsilyl group, an acridinyl group, a phenoxaz.

[5] The boron-containing compound according to any one of [1] to [4], which is selected from the following compounds:

[6] an electronic device comprising the boron-containing compound according to any one of [1] to [5 ].

[7] The electronic device according to [6], wherein the electronic device is an organic electroluminescent device, an organic field effect transistor, or an organic solar cell.

[8] An organic electroluminescent device, comprising: 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, the at least one organic layer containing the boron-containing compound according to any one of [1] to [5 ].

[9] The organic electroluminescent device according to [8], wherein the at least one organic layer is a hole injection layer, a hole transport layer, a light emitting layer, an electron blocking layer, a hole blocking layer, or an electron transport layer.

[10] Use of the boron-containing compound according to any one of [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; preferably, the electronic device is an organic electroluminescent device, an organic field effect transistor or an organic solar cell.

ADVANTAGEOUS EFFECTS OF INVENTION

By introducing the rigid structure, the boron-containing compound has good film forming property and thermal stability and higher fluorescence quantum yield, can be used for preparing electronic devices such as organic electroluminescent devices, organic field effect transistors and organic solar cells, particularly used as a constituent material of a hole injection layer, a hole transport layer, a luminescent layer, an electron blocking layer, a hole blocking layer or an electron transport layer in the organic electroluminescent devices, can show the advantages of high luminous efficiency, long service life, short luminous wavelength and low driving voltage, and is obviously superior to the existing organic electroluminescent devices.

The boron-containing derivative compound adopted by the invention has a special rigid structure, and can effectively inhibit vibration relaxation caused by vibration and rotation of molecules, so that the boron-containing derivative compound has a narrower luminous peak, higher thermal stability, chemical stability and carrier transport property.

The boron-containing compound has higher electron injection and movement rate. Therefore, with the organic electroluminescent device having the electron injection layer and/or the electron transport layer prepared from the boron-containing 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 the durability of the resulting organic electroluminescent device.

The boron-containing compound has excellent hole blocking capacity and excellent electron transport performance, and is stable in a thin film state. Therefore, the organic electroluminescent device having the hole blocking layer prepared from the boron-containing compound of the present invention has high luminous efficiency, such that the driving voltage is reduced, the current resistance is improved, and the maximum luminous brightness of the organic electroluminescent device is increased.

The boron-containing compound can be 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 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 preparation method of the boron-containing compound is simple, the raw materials are easy to obtain, and the industrialized development requirement can be met.

The boron-containing 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.

Drawings

FIG. 1 is a fluorescence spectrum (PL) of the compounds of examples 2 and 4 of the present invention (compounds 1-1 and 1-8) in a toluene solution.

Fig. 2 shows the organic electroluminescence spectra of the organic electroluminescence devices (OLED2 and OLED4) of examples 8 and 10 of the present invention.

FIG. 3 shows the delayed fluorescence spectrum of the compound of example 2 (compound 1-1) of the present invention in a doped thin film.

FIG. 4 is a thermogravimetric analysis (TGA) of the compounds of examples 2 and 4 of the present invention (compounds 1-1 and 1-8) under a nitrogen atmosphere.

Fig. 5 is a view showing the configuration of organic electroluminescent devices of examples 7 to 12 of the present invention.

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.

< boron-containing Compound >

The boron-containing compound of the present invention is a novel compound having a ring-closed triphenylborane structure, and is represented by the following general formula (1).

Specifically, the boron-containing compound of the present invention has a structure represented by the following general formula (I) or (II):

in the above general formulae (1), (I) and/or (II),

if present, each A₁Each independently represents Ar₁Or

m is any integer of 1 to 5;

in the above structural formulae C-1 to C-70,

the dotted line represents a bond;

each Z independently represents CR¹Or N;

If present, each R¹Each independently represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, or NO₂、N(R²)₂、OR²、SR²、C(＝O)R²、P(＝O)R²、Si(R²)₃A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 40 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 40 ring atoms;

[ radical definitions ]

<B₁>

In the present invention, B in the above general formulae (1), (I) and/or (II)₁At the same time with C₁And one or more of A₁Structural fragment of a linkage, in particular a single bond (i.e. A)₁And C₁Directly linked), a carbonyl group, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or an aromatic heterocyclic group having 5 to 18 ring atoms.

In the present invention, the hetero atom in the aromatic heterocyclic group having 5 to 18 ring atoms is selected from N, O, S, P, As and/or Si, preferably N, O and/or S; the number of heteroatoms may be from 1 to 10, preferably from 1 to 5.

In the present invention, an aromatic hydrocarbon group or aromatic heterocyclic group refers to a system which does not necessarily contain only an aryl or heteroaryl group, 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, as well as systems in which two or more aryl groups are interrupted, for example by linear or cyclic alkyl groups or silyl groups, 9, 9' -spirobifluorenes, 9, 9-diarylfluorenes, triarylamines, diaryl ethers, etc. systems 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 B₁The aromatic hydrocarbon group having 6 to 18 carbon atoms or the aromatic heterocyclic group having 5 to 18 ring 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, dihydropyrenyl, tetrahydropyrenyl, cis-or trans-indenofluorenyl, cis-or trans-monobenzindenofluorenyl, cis-or trans-indofluorenylOr trans-dibenzoindenofluorenyl, trimeric indenyl, isotridecyl, spirotrimeric indenyl, spiroisotridecyl, furyl, benzofuryl, isobenzofuryl, dibenzofuryl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, indolyl, isoindolyl, carbazolyl, indolocarbazolyl, indenocarbazolyl, pyridyl, quinolyl, isoquinolyl, acridinyl, phenanthridinyl, benzo-5, 6-quinolyl, benzo-6, 7-quinolyl, benzo-7, 8-quinolyl, phenothiazinyl, phenoxazinyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxalinyl, oxazolyl, benzoxazolyl, naphthoxazolyl, phenothiazinyl, Anthraoxazolyl, phenanthrooxazolyl, isoxazolyl, 1, 2-thiazolyl, 1, 3-thiazolyl, benzothiazolyl, pyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1, 5-diazahthranyl, 2, 7-diazpyrenyl, 2, 3-diazpyrenyl, 1, 6-diazpyrenyl, 1, 8-diazpyrenyl, 4,5,9, 10-tetraazaperylenyl, pyrazinyl, phenazinyl, fluorerynyl, naphthyridinyl, azacarbazolyl, benzocarbazinyl, phenanthrolinyl, 1,2, 3-triazolyl, 1,2, 4-triazolyl, benzotriazolyl, 1,2, 3-oxadiazolyl, 1,2, 4-oxadiazolyl, 1,2, 5-oxadiazolyl, 1,3, 4-oxadiazolyl, 1,2, 3-thiadiazolyl, 1,2, 4-thiadiazolyl, 1,2, 5-thiadiazolyl, 1,3, 4-thiadiazolyl, 1,3, 5-triazinyl, 1,2, 4-triazinyl, 1,2, 3-triazinyl, tetrazolyl, 1,2,4, 5-tetrazinyl, 1,2,3, 4-tetrazinyl, 1,2,3, 5-tetrazinyl, purinyl, pteridinyl, indolizinyl, benzothiadiazolyl, and the like.

Preferably, in the present invention, B in the above general formula (1), (I) and/or (II)₁Represents 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 ring atoms, preferably a single bond, a carbonyl group, a phenyl group, a naphthyl group, a fluorenyl group, a phenanthryl group, an anthracyl group, or a triazinyl group, more preferably a phenyl group, a naphthyl group, a fluorenyl group, or an anthracyl group.

From B₁Having 6 to 18 carbon atoms or having 5 to 18 ring atomsThe aromatic heterocyclic group may be unsubstituted, but may have a substituent. The substituents may be exemplified by: 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; a straight-chain or branched alkyl group having 1 to 6 carbon atoms, such as 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; a linear or branched alkoxy group having 1 to 6 carbon atoms, such as a methoxy group, an ethoxy group, or a propoxy group; straight or branched alkenyl groups having 2 to 6 carbon atoms, such as vinyl or allyl; aryloxy groups such as phenoxy or tolyloxy; arylalkoxy, such as benzyloxy or phenethyloxy; monocyclic, fused-ring, or spiro aromatic hydrocarbon groups, e.g. phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, fluorenyl, indenyl, pyrenyl, perylenyl, fluoranthryl, benzo [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.

Any of the above exemplary substituents may be further substituted with the above exemplary substituents. The above exemplary substituents may be present independently of each other, but may also 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.

<A₁>

In the present invention, A in the above general formulae (1), (I) and/or (II)₁Is a reaction of with B₁The structural fragment of the linkage, in particular Ar₁Or

Specifically, A in the general formula (I)₁Represents Ar₁And A in the general formula (II)₁Then represent

In the present invention, A in the above general formulae (1), (I) and/or (II)₁The specific number of (b) is represented by m, and m may be any integer of 1 to 5, for example, 1,2,3,4 or 5, preferably 1,2,3 or 4, more preferably 1,2 or 3, and further preferably 1 or 2. When m is greater than 1, a plurality of A will be contained in the above formula₁. Specifically, in this case, the general formula (I) will contain a plurality of Ar₁And in the general formula (II) a plurality of Ar will be contained₁And Ar₂。

In the present invention, if a plurality of or Ar are simultaneously present in the structure₁Or a plurality of Ar₁And Ar₂Then each Ar is₁And Ar₂Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, a cyano group, optionally substituted by one or more R¹Substituted aromatic hydrocarbon radical having 6 to 30 carbon atoms or optionally substituted by one or more R¹Substituted aromatic heterocyclic groups having 5 to 30 ring atoms.

From Ar₁And/or Ar₂The aromatic hydrocarbon group having 6 to 30 carbon atoms or the aromatic heterocyclic group having 5 to 30 ring atoms represented may be exemplified by: phenyl, naphthyl, anthryl, benzanthryl, phenanthryl, benzophenanthryl, pyrenyl, perylenyl, anthryl, benzofluoranthenyl, tetracenyl, pentacenyl, benzopyrenyl, biphenyl, biphenylyl, terphenyl, quaterphenyl, pentabiphenyl, terphenyl, fluorenyl, spirobifluorenyl, dihydrophenanthryl, dihydropyrenyl, tetrahydropyrenyl, cis-or trans-indenofluorenyl, cis-or trans-monobenzindenofluorenyl, cis-or trans-dibenzoindenofluorenyl, dianilinyl, trianiliyl, trimeric indenyl, isotridecyl, spirotrimeric indenyl, spiroisotridecyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, benzothienocarbazolyl, pyrrolyl, indolyl, etc,Isoindolyl, carbazolyl, indolocarbazolyl, indenocarbazolyl, pyridyl, bipyridyl, terpyridyl, quinolyl, isoquinolyl, acridinyl, phenanthridinyl, benzo-5, 6-quinolyl, benzo-6, 7-quinolyl, benzo-7, 8-quinolyl, phenothiazinyl, phenoxazinyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxalinyl, oxazolyl, benzoxazolyl, benzooxadiazolyl, naphthooxazolyl, anthraoxazolyl, phenanthrooxazolyl, isoxazolyl, thiazolyl, isothiazolyl, benzothiazolyl, benzothiadiazolyl, pyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, quinazolinyl, azafluorenylyl, Diazanthryl, diazepanyl, tetraazaperylenyl, diazanaphthyl, pyrazinyl, phenazinyl, fluorerynyl, naphthyridinyl, azacarbazolyl, benzocarbazolyl, phenanthrolinyl, triazolyl, benzotriazolyl, oxadiazolyl, thiadiazolyl, triazinyl, tetrazolyl, tetrazinyl, purinyl, pteridinyl, indolizinyl, benzothiadiazolyl, pyridopyrrolyl, pyridotriazolyl, xanthenyl, benzofurocarbazolyl, benzofluorenocarbazyl, N-phenylcarbazolyl, diphenyl-benzimidazolyl, diphenyl-oxadiazolyl, diphenyl-boryl, triphenylphosphinyl, tetraphenylsilyl and the like, with preference given to phenyl, fluorenyl, dianilinyl, dianilinoindolyl, benzofurodianilinyl, benzothienodianilinyl, dibenzofuranyl, tetrazinyl, pteridinyl, etc, Dibenzothienyl, carbazolyl, indenocarbazolyl, benzofurocarbazolyl, benzothienocarbazolyl, indolocarbazolyl, acridinyl, phenoxazinyl and phenothiazinyl, more preferably carbazolyl, acridinyl, phenoxazinyl, phenothiazinyl and dianilinyl.

From Ar₁And/or Ar₂The aromatic hydrocarbon group having 6 to 30 carbon atoms or the aromatic heterocyclic group having 5 to 30 ring atoms represented may be unsubstituted, but may also have a substituent. Preferably, from Ar₁And/or Ar₂An aromatic hydrocarbon group having 6 to 30 carbon atoms or having 5 to 30Aromatic heterocyclic radicals of 30 ring atoms being substituted by one or more R¹Substituted aromatic hydrocarbon radical having 6 to 30 carbon atoms or substituted by one or more R¹Substituted aromatic heterocyclic groups having 5 to 30 ring atoms.

Preferably, in the present invention, each Ar is₁And Ar₂Each independently selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, a cyano group, or any one of the following groups:

wherein the dotted line represents the group with B₁Or an N-bonded bond.

<M>

In the present invention, M in the above general formulae (1), (I) and/or (II) is simultaneously C₁And C₂Or C₃Structural fragment of the linkage, specifically a single bond, C (R)¹)₂、NR¹、O、S、S(＝O)₂、P(＝O)R¹、Si(R¹)₂Or Ge (R)¹)₂E.g. NH, CH₂、CF₂、CCl₂、CBr₂、CI₂、C(CN)₂、C(NO₂)₂、C(Ph)₂、C(biPh)₂Etc., and two M's may beThe same, but may also be different.

Preferably, in the present invention, each M in the above general formulae (1), (I) and/or (II) independently represents a single bond, C (R)¹)₂、NR¹O and S, preferably NR¹And O.

<C₁To C₃>

In the present invention, C in the above general formula (1), (I) and/or (II)₁Is simultaneously with boron atom, B₁And two M-linked structural fragments, specifically representing a group represented by any one of the following structural formulae C-1 to C-54:

in the above structural formulae C-1 to C-70,

the dotted line represents a bond;

each Z independently represents CR¹Or N, e.g. N, CH, CF, CCl, CBr, CI, C (CN), C (NO)₂) C (Ph), C (biph), etc.;

each W, if present, independently represents a single bond, C (R)¹)₂、NR¹、O、S、S(＝O)₂、P(＝O)R¹、Si(R¹)₂Or Ge (R)¹)₂。

Preferably, in the present invention, C in the above general formula (1), (I) and/or (II)₁、C₂And C₃Each independently represents a fragment derived from any one of the following structures: benzene optionally substituted with one or more C1-C6 alkyl groups, carbazole, phenoxazine, phenothiazine, diphenylamine, dibenzofuran and dibenzothiophene optionally substituted with one or more alkyl or aryl groups, preferably benzene, toluene, xylene, or mixtures thereof,Tert-butylbenzene, N-methylcarbazole, N-phenylcarbazole, phenoxazines, phenothiazines, dibenzofurans, and diphenylthiophenes.

<R¹To R²>

As optionally substituted substituents, A₁M and/or C₁To C₃May contain one or more R in each of the iso-structural fragments¹，R¹Specifically, it represents a hydrogen atom, deuterium atom, fluorine atom, chlorine atom, bromine atom, iodine atom, cyano group, NO₂、N(R²)、OR²、SR²、C(＝O)R²、P(＝O)R²、Si(R²)₃A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 40 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 40 ring atoms.

From R¹The alkyl group having 1 to 20 carbon atoms represented may be exemplified by: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, 2-methylhexyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, 3-methylheptyl, n-nonyl, n-decyl, hexadecyl, octadecyl, eicosyl, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2, 3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2, 3-dimethylcyclohexyl, 3,4, 5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl and the like. The alkyl group having 1 to 20 carbon atoms may be linear, branched or cyclic.

From R¹The alkyl group having 1 to 20 carbon atoms represented may be unsubstituted, but may also have a substituent. Preferably, from R¹Alkyl having 1 to 20 carbon atoms represented by one or more 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)₂、C＝O、C＝NR²、P(＝O)R²、S＝O、S(＝O)₂、NR²O, S or C (═ O) NR²And wherein one or more hydrogen atoms may be replaced by deuterium atoms, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, cyano groups or 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, but may also have a substituent. The substituents can be exemplified by the group consisting of R¹The alkyl group having 1 to 20 carbon atoms represented by (b) may have the same substituent as that represented by the substituent(s). The substituents may take the same pattern as that of the exemplary substituents.

From R¹The alkynyl group having 2 to 20 carbon atoms represented may be exemplified by: ethynyl, isopropynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl and the like. The alkynyl group having 2 to 20 carbon atoms may be linear, branched or cyclic.

From R¹The alkynyl group having 2 to 20 carbon atoms represented may be unsubstituted, but may also 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 ring atoms represented by the above formula can be exemplified by the group consisting of Ar₁And/or Ar₂With an aromatic radical having 6 to 30 carbon atomsThe same group as that shown in the group consisting of an aromatic hydrocarbon group and an aromatic heterocyclic group having 5 to 30 ring atoms.

From R¹The aromatic hydrocarbon group having 6 to 40 carbon atoms or the aromatic heterocyclic group having 5 to 40 ring atoms represented may be unsubstituted, but may also 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 R¹Optionally forming a mono-or polycyclic aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more R²Substitution; here, two or more substituents R¹May be connected to each other and may form a ring.

Preferably, from R¹The aromatic hydrocarbon group having 6 to 40 carbon atoms or the aromatic heterocyclic group having 5 to 40 ring atoms represented may be exemplified by: phenyl, biphenyl, terphenyl, quaterphenyl, pentabiphenyl, benzothienocarbazolyl, benzofurocarbazolyl, benzofluorenocarbazolyl, benzanthracenyl, benzophenanthryl, fluorenyl, spirobifluorenyl, triazinyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, indenocarbazolyl, benzimidazolyl, diphenyl-oxadiazolyl, diphenyl boron, triphenyl phosphoxy, diphenyl phosphoxy, triphenyl silicon group, tetraphenyl silicon group, and the like. The aromatic hydrocarbon group having 6 to 40 carbon atoms or the aromatic heterocyclic group having 5 to 40 ring atoms is optionally substituted with one or more R²And (4) substitution.

As an optionally substituted substituent, each R¹May each contain one or more R²，R²Specifically, it represents 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 ring atoms.

From R²Having 1 to 20 carbonsThe alkyl group of the atom may be exemplified by the group 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 aromatic heterocyclic group having 5 to 30 ring atoms represented by R¹The aromatic hydrocarbon group having 6 to 30 carbon atoms or the aromatic heterocyclic group having 5 to 30 ring atoms represented by the above formula are the same groups as those shown.

From R²The alkyl group having 1 to 20 carbon atoms, the aromatic hydrocarbon group having 6 to 30 carbon atoms, or the aromatic heterocyclic group having 5 to 30 ring atoms represented may be unsubstituted, but 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.

In some embodiments of the invention, the boron-containing compounds of the invention have a structure represented by any one of the following compounds:

< production method >

The boron-containing 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.

< electronic device >

Various electronic devices containing the boron-containing compounds of the present invention can be produced, for example, by using the boron-containing compounds of the present invention to produce organic materials (particularly configured in the form of layers). In particular, the boron-containing compound can be used for organic electroluminescent devices, organic solar cells, organic diodes, 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), but is not limited to these structures. The injection layer, the transport layer, the light-emitting layer, the barrier layer, and the like can be formed by, for example, forming a layer containing or composed of the boron-containing compound of the present invention between electrodes. However, the range of use of the boron-containing compound of the present invention is not limited to the above-described exemplary embodiments.

< organic electroluminescent device >

The organic electroluminescent device of the present invention comprises: the organic light-emitting 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, the at least one organic layer including the boron-containing compound of the present invention.

Fig. 5 is a view showing the configuration of an organic electroluminescent device of the present invention. As shown in fig. 5, in the organic electroluminescent device of the present invention, for example, an anode 2, a hole injection layer 3, a hole transport layer 4, an electron blocking layer 5, a light emitting layer 6, a hole blocking layer 7, an electron transport layer 8, an electron injection layer 9, and a cathode 10 are sequentially disposed on a substrate 1.

The organic electroluminescent device of the present invention is not limited to such a structure, and for example, some organic layers may be omitted in the multi-layer structure. For example, it may be a configuration in which the hole injection layer 3 between the anode 2 and the hole transport layer 4, the hole blocking layer 7 between the light emitting layer 6 and the electron transport layer 8, and the electron injection layer 9 between the electron transport layer 8 and the cathode 10 are omitted, and the anode 2, the hole transport layer 4, the electron blocking layer 5, 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 of the present invention can 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 of the present invention can 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 a metal 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, naphthalene diamine compounds, star-shaped triphenylamine compounds, triphenylamine trimers such as arylamine compounds having a structure in which more than 3 triphenylamine structures are connected by single bonds or divalent groups containing no heteroatom in the molecule, tetramers, receptor-type heterocyclic compounds such as hexacyanoazatriphenylene, and coating-type high polymer materials. These materials can be formed into a thin film by a known method such as a vapor deposition method, a spin coating method, and an ink jet method.

As the hole transport layer of the organic electroluminescent device of the present invention, a compound containing boron of the present invention is preferably used. In addition, other known materials having a hole-transporting property can be used. Examples thereof include: a compound containing a m-carbazolylphenyl group; benzidine derivatives such as N, N ' -diphenyl-N, N ' -di (m-tolyl) benzidine (TPD), N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine (NPB), N ' -tetrakisbiphenylylbenzidine, and the like; 1, 1-bis [ (di-4-tolylamino) phenyl ] cyclohexane (TAPC); various triphenylamine trimers and tetramers; 9,9 ', 9 "-triphenyl-9H, 9' H, 9" H-3,3 ': 6', 3 "-tricarbazole (Tris-PCz), and the like. These may be used as a single layer formed by separately forming a film or by mixing them with other materials to form a film, or may be used as a laminated structure of layers formed by separately forming a film, a laminated structure of layers formed by mixing films, or a laminated structure of layers formed by separately forming a film and layers formed by mixing films. These materials can be formed into a thin film by a known method such as a vapor deposition method, a spin coating method, and an ink jet method.

In addition, in the hole injection layer or the hole transport layer, a material obtained by further P-doping tribromoaniline antimony hexachloride, an axial olefin derivative, or the like to a material generally used in the layer, a polymer compound having a structure of a benzidine derivative such as TPD in a partial structure thereof, or the like may be used.

As the electron blocking layer of the organic electroluminescent element of the present invention, a compound containing boron of the present invention is preferably used. In addition, other known compounds having an electron blocking effect may be used. For example, there may be mentioned: carbazole derivatives such as 4,4', 4 ″ -tris (N-carbazolyl) triphenylamine (TCTA), 9-bis [4- (carbazol-9-yl) phenyl ] fluorene, 1, 3-bis (carbazol-9-yl) benzene (mCP), and 2, 2-bis (4-carbazol-9-ylphenyl) adamantane (Ad-Cz); a compound having a triphenylsilyl and triarylamine structure represented by 9- [4- (carbazol-9-yl) phenyl ] -9- [4- (triphenylsilyl) phenyl ] -9H-fluorene; and compounds having an electron-blocking effect, such as monoamine compounds having a high electron-blocking property and various triphenylamine dimers. These may be used as a single layer formed by film formation alone or by mixing with other materials to form a film, or may be used as a laminated structure of layers formed by film formation alone, a laminated structure of layers formed by mixing into a film, or a laminated structure of layers formed by film formation alone and layers formed by mixing into a film. These materials can be formed into a thin film by a known method such as a vapor deposition method, a spin coating method, and an ink jet method.

The boron-containing compound of the present invention is preferably used as the light-emitting layer of the organic electroluminescent element 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 boron-containing compound of the present invention is preferably used 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, an aromatic amine derivative, a styryl amine compound, a boron complex, a fluoranthene compound, a metal complex, or the like can be used. Examples thereof include pyrene derivatives, anthracene derivatives, quinacridones, coumarins, rubrenes, perylenes and their derivatives, benzopyran derivatives, rhodamine derivatives, aminostyryl derivatives, spirobifluorene derivatives, and the like. These may be used as a single layer formed by film formation alone or by mixing with other materials to form a film, or may be used as a laminated structure of layers formed by film formation alone, a laminated structure of layers formed by mixing into a film, or a laminated structure of layers formed by film formation alone and layers formed by mixing into a film. These materials can be formed into a thin film by a known method such as a vapor deposition method, a spin coating method, and an ink jet method.

The boron-containing compound of the present invention is preferably used as a hole-blocking layer of the organic electroluminescent element 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.

As the electron transport layer of the organic electroluminescent element of the present invention, the boron-containing compound of the present invention is preferably used. In addition, the compound may be formed using other compounds having an electron-transporting property. For example, Alq can be used₃Metal complexes of quinolinol derivatives including BAlq; various metal complexes; a triazole derivative; a triazine derivative; an oxadiazole derivative; a pyridine derivative; bis (10-hydroxybenzo [ H ]]Quinoline) beryllium (Be (bq)₂) (ii) a Such as 2- [4- (9, 10-dinaphthalen-2-anthracen-2-yl) phenyl]Benzimidazole derivatives such as-1-phenyl-1H-benzimidazole (ZADN); a thiadiazole derivative; an anthracene derivative; a carbodiimide derivative; quinoxaline derivatives; pyridoindole derivatives; phenanthroline derivatives; silole derivatives and the like. These may be used as a single layer formed by separately forming a film or by mixing them with other materials to form a film, or may be used as a laminated structure of layers formed by separately forming a film, a laminated structure of layers formed by mixing films, or a laminated structure of layers formed by separately forming a film and layers formed by mixing films. These materials can be formed into a thin film by a known method such as a vapor deposition method, a spin coating method, and an ink jet method.

As the electron injection layer of the organic electroluminescent device of the present invention, a material known per se can be used. For example, alkali metal salts such as lithium fluoride and cesium fluoride; alkaline earth metal salts such as magnesium fluoride; metal complexes of quinolinol derivatives such as lithium quinolinol; and metal oxides such as alumina.

In the electron injection layer or the electron transport layer, a material obtained by further N-doping a metal such as cesium, a triarylphosphine oxide derivative, or the like can be used as a material generally used for the layer.

As the cathode of the organic electroluminescent device of the present invention, an electrode material having a low work function such as aluminum, magnesium, or an alloy having a low work function such as magnesium-silver alloy, magnesium-indium alloy, aluminum-magnesium alloy is preferably used as the electrode material.

As the substrate of the present invention, a substrate in a conventional organic light emitting device, such as glass or plastic, can be used. In the present invention, a glass substrate is selected.

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 1-3

[ Synthesis of Compound M1 ]

The synthetic route for compound M1 is shown below:

to a three-necked flask equipped with a reflux condenser tube, 4-bromo-2, 6-difluoroiodobenzene (13.25g, 41.67mmol), phenol (8.62g, 91.67mmol), potassium carbonate (23g, 166.68mmol), and N-methylpyrrolidone (NMP) (200mL) were sequentially added under nitrogen atmosphere, and heated under reflux for 6 h. After the reaction was completed, the system was cooled to room temperature. Adding a large amount of water to generate white precipitate, and performing suction filtration and collection. The precipitate was washed successively with water and 50% methanol (V/V). Finally, the filter cake obtained is dissolved in a proper amount of dichloromethane and further purified by column chromatography (mobile phase: petroleum ether: dichloromethane)3:1(V/V)) to give 15.74g of a white solid in 81% yield. MS (EI) M/z 466.32[ M ]⁺](ii) a Elemental analysis by Combustion method C₁₈H₁₂BrIO₂(%) calculated C46.29, H2.59; found C46.20, H2.57.

[ Synthesis of Compound M2 ]

The synthetic route for compound M2 is shown below:

to a dry clean three-necked flask, compound M1(4.7g, 10.1mmol) and M-xylene (M-xylene) (100mL) were added in this order under a nitrogen atmosphere, and the system was cooled to-40 ℃. N-butyllithium (5mL, 12.1mmol, 2.4M) was added dropwise to the system, and after completion of the addition, stirring was continued for 30 mm at that temperature, followed by further stirring at room temperature for 12 hours. The reaction was cooled to-40 ℃ again and boron tribromide (3.8g, 15.1mmol) was added dropwise. After the addition was complete, the reaction was continued at 50 ℃ for 4 h. The system was then cooled to 0 deg.C, N-ethyldiisopropylamine (2.58g, 20.2mmol) was added, after which the temperature was gradually raised to 125 deg.C and the reaction continued at this temperature for 12 h. After the reaction was completed, the solvent was distilled off under reduced pressure, and the crude product was purified by column chromatography (mobile phase: petroleum ether: dichloromethane: 9:1(V/V)) to obtain 1.8g of a yellow solid in 52% yield. MS (EI) M/z348.28[ M ]⁺](ii) a Elemental analysis by Combustion method C₁₈H₁₀BBrO₂(%) calculated C61.95, H2.89; found C61.88, H2.27.

[ Synthesis of Compound M3 ]

The synthetic route for compound M3 is shown below:

to a clean 250mL three-necked flask, under a nitrogen atmosphere, 3,4, 5-trifluorophenylboronic acid (8.4g, 47.8mmol), anhydrous sodium carbonate (8.4g, 79.6mmol), compound M2(13.8g, 39.8mmol), tetrakis (triphenylphosphine palladium) (470.8mg, 4.8mmol), and a ternary mixed solvent (100mL, toluene: water: ethanol ═ were sequentially added5:1:1 (V/V)). 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 water (about 200mL) 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 ═ 3:2(V/V)) to give 13.4g of a yellow solid in 84% yield. MS (EI) M/z 400.23[ M ]⁺](ii) a Elemental analysis by Combustion method C₂₄H₁₂BF₃O₂Calculated value of (%) -C72.04, H3.02; found C71.95, H3.00.

[ Synthesis of Compounds 1 to 3]

The synthetic routes for compounds 1-3 are shown below:

carbazole (23.2g, 139.3mmol), anhydrous potassium carbonate (8.4g, 79.6mmol), compound M3(14.7g, 39.8mmol), and DMSO (100mL) were added sequentially to a clean 250mL three-necked flask under a nitrogen atmosphere. 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 water (about 200mL) 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 ═ 3:2(V/V)) to give 21.4g of a green solid in 64% yield. MS (EI) M/z 841.83[ M ]⁺](ii) a Elemental analysis by Combustion method C₆₀H₃₆BN₃O₂Calculated values of percent are C85.61, H4.31, N4.99; found C85.41, H4.29N 4.90.

Example 2: synthesis of Compound 1-1

[ Synthesis of Compound M4 ]

The synthetic route for compound M4 is shown below:

into a clean 250mL three-necked flask, pentafluorophenylboronic acid (10.1g, 47.8mmol), anhydrous sodium carbonate (8.4g, 79.6mmol), compound M2(13.8g, 39.8mmol), tetrakis (triphenylphosphine palladium) (470.8mg, 4.8mmol), and a ternary mixed solvent (100mL, toluene: water: ethanol ═ 5:1:1(V/V)) were sequentially added under a nitrogen atmosphere. 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 water (about 200mL) 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 ═ 3:2(V/V)) to obtain 14.6g of a yellow solid in 84% yield. MS (EI) M/z 436.23[ M ]⁺](ii) a Elemental analysis by Combustion method C₂₄H₁₀BF₅O₂(%) Calculations C66.09, H2.31; found C65.97, H2.29.

[ Synthesis of Compound 1-1 ]

The synthetic route for compound 1-1 is shown below:

to a clean 250mL three-necked flask, 39.7g (237.6mmol) of carbazole, anhydrous potassium carbonate (12.6g, 119.4mmol), compound M4(17.4g, 39.8mmol), and DMSO (100mL) were added sequentially under a nitrogen atmosphere. 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 water (about 200mL) 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 ═ 3:2(V/V)) to give 15.8g of a green solid in 34% yield. MS (EI) M/z 1171.83[ M ]⁺](ii) a Elemental analysis by Combustion method C₈₄H₅₀BN₅O₂(%) calculated C86.07, H4.30, N5.97; found C85.90, H4.29, N5.90.

Example 3: synthesis of Compounds 1-10

[ Synthesis of Compound M5 ]

The synthetic route for compound M5 is shown below:

to a three-necked flask equipped with a reflux condenser tube, 4-bromo-2, 6-difluoroiodobenzene (13.25g, 41.67mmol), p-tert-butylphenol (13.7g, 91.67mmol), potassium carbonate (23g, 166.68mmol), and N-methylpyrrolidone (NMP) (200mL) were added in this order under a nitrogen atmosphere, and heated under reflux for 6 h. After the reaction was completed, the system was cooled to room temperature. Adding a large amount of water to generate white precipitate, and performing suction filtration and collection. The precipitate was washed successively with water and 50% methanol (V/V). The resulting filter cake was finally dissolved in an appropriate amount of dichloromethane and further purified by column chromatography (mobile phase: petroleum ether: dichloromethane ═ 3:1(V/V)) to give 19.5g of a white solid in 81% yield. MS (EI) M/z 578.32[ M ]⁺](ii) a Elemental analysis by Combustion method C₂₆H₂₈BrIO₂Calculated in% (%) C53.91, H4.87; found C53.80H 4.80.

[ Synthesis of Compound M6 ]

The synthetic route for compound M6 is shown below:

to a dry clean three-necked flask, compound M5(5.8g, 10.1mmol) and M-xylene (M-xylene) (100mL) were added in this order under a nitrogen atmosphere, and the system was cooled to-40 ℃. N-butyllithium (5mL, 12.1mmol, 2.4M) was added dropwise to the system, and after completion of the addition, stirring was continued for 30 mm at that temperature, followed by further stirring at room temperature for 12 hours. The reaction was cooled to-40 ℃ again and boron tribromide (3.8g, 15.1mmol) was added dropwise. After the addition was complete, the reaction was continued at 50 ℃ for 4 h. The system was then cooled to 0 deg.C, N-ethyldiisopropylamine (2.58g, 20.2mmol) was added, after which the temperature was gradually raised to 125 deg.C and the reaction continued at this temperature for 12 h. After the reaction is finished, the solvent is evaporated under reduced pressure, and the crude product is purified by column chromatography (mobile phase: petroleum ether: dichloromethane)9:1(V/V)) to give 2.4g of a yellow solid in 52% yield. MS (EI) M/z460.28[ M ]⁺](ii) a Elemental analysis by Combustion method C₁₈H₁₀BBrO₂(%) calculated C67.71, H5.68; found C67.65, H5.60.

[ Synthesis of Compound M7 ]

The synthetic route for compound M7 is shown below:

to a clean 250mL three-necked flask, 3,4, 5-trifluorophenylboronic acid (8.4g, 47.8mmol), anhydrous sodium carbonate (8.4g, 79.6mmol), compound M6(18.4g, 39.8mmol), tetrakis (triphenylphosphine palladium) (470.8mg, 4.8mmol), and a ternary mixed solvent (100mL, toluene: water: ethanol ═ 5:1:1(V/V)) were added in this order under a nitrogen atmosphere. 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 water (about 200mL) 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 ═ 3:2(V/V)) to give 17.1g of a yellow solid in 84% yield. MS (EI) M/z 512.23[ M ]⁺](ii) a Elemental analysis by Combustion method C₃₂H₂₈BF₃O₂Calculated in percent C75.01, H5.51; found C74.95, H5.45.

[ Synthesis of Compounds 1 to 10]

The synthetic routes for compounds 1-10 are shown below:

carbazole (23.2g, 139.3mmol), anhydrous potassium carbonate (8.4g, 79.6mmol), compound M7(20.4g, 39.8mmol), and DMSO (100mL) were added sequentially to a clean 250mL three-necked flask under a nitrogen atmosphere. 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 outThe mixture was taken up in water (about 200mL) 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 ═ 3:2(V/V)) to give 21.4g of a green solid in 64% yield. MS (EI) M/z 841.83[ M ]⁺](ii) a Elemental analysis by Combustion method C₆₈H₅₂BN₃O₂Calculated values of percent C85.61, H5.49, N4.40; found C85.51, H5.44, N4.35.

Example 4: synthesis of Compounds 1-8

[ Synthesis of Compound M8 ]

The synthetic route for compound M8 is shown below:

into a clean 250mL three-necked flask, pentafluorophenylboronic acid (10.1g, 47.8mmol), anhydrous sodium carbonate (8.4g, 79.6mmol), compound M6(18.4g, 39.8mmol), tetrakis (triphenylphosphine palladium) (470.8mg, 4.8mmol), and a ternary mixed solvent (100mL, toluene: water: ethanol ═ 5:1:1(V/V)) were sequentially added under a nitrogen atmosphere. 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 water (about 200mL) 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 ═ 3:2(V/V)) to give 18.4g of a yellow solid in 84% yield. MS (EI) M/z 548.23[ M ]⁺](ii) a Elemental analysis by Combustion method C₃₂H₂₆BF₅O₂Calculated in percent C70.09, H4.78; found C70.01, H4.72.

[ Synthesis of Compounds 1 to 8]

The synthetic routes for compounds 1-8 are shown below:

into a clean 250mL three-neck bottle under the nitrogen atmosphereCarbazole (39.7g, 237.6mmol), anhydrous potassium carbonate (12.6g, 119.4mmol), compound M8(21.9g, 39.8mmol), and DMSO (100mL) were added sequentially. 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 water (about 200mL) 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 ═ 3:2(V/V)) to give 17.4g of a green solid in 34% yield. MS (EI) M/z1283.63[ M ]⁺](ii) a Elemental analysis by Combustion method C₈₄H₅₀BN₅O₂Calculated values of (%), C86.03, H5.18, N5.45; found C85.95, H5.15, N5.40.

Example 5: synthesis of Compounds 13-29

[ Synthesis of Compound M9 ]

The synthetic route for compound M9 is shown below:

2, 5-dibromo-1, 3-diiodobenzene (20.3g, 41.7mmol), diphenylamine (15.5g, 91.7mmol), sodium tert-butoxide (4.5g, 43.5mmol), tri-tert-butylphosphine tetrafluoroborate (0.1g, 0.3mmol), and tris (dibenzylideneacetone) dipalladium (0.27g, 0.3mmol) were sequentially added to a three-necked flask equipped with a reflux condenser under a nitrogen atmosphere, and after the reaction system was degassed, toluene (150mL) was added under nitrogen protection, and the mixture was stirred and heated to reflux to react for 12 hours. After completion of the reaction, the system was cooled to room temperature, suction filtered under reduced pressure, and the residue was washed with a large amount of dichloromethane, and the filtrate was concentrated to give a crude product, which was isolated and purified on a silica gel column with an eluent of petroleum ether with dichloromethane of 6:1(V/V) to give 19.3g of a white solid in a yield of 81%. MS (EI) M/z 570.32[ M ]⁺](ii) a Elemental analysis by Combustion method C₃₀H₂₂Br₂N₂(%) Calculations C63.18, H3.89, N4.91; found C63.10, H3.87N 4.85.

[ Synthesis of Compound M10 ]

The synthetic route for compound M10 is shown below:

to a dry clean three-necked flask, compound M9(5.7g, 10.1mmol) and M-xylene (M-xylene) (100mL) were added in this order under a nitrogen atmosphere, and the system was cooled to-40 ℃. N-butyllithium (5mL, 12.1mmol, 2.4M) was added dropwise to the system, and after completion of the addition, stirring was continued for 30 mm at that temperature, followed by further stirring at room temperature for 12 hours. The reaction was cooled to-40 ℃ again and boron tribromide (3.8g, 15.1mmol) was added dropwise. After the addition was complete, the reaction was continued at 50 ℃ for 4 h. The system was then cooled to 0 deg.C, N-ethyldiisopropylamine (2.58g, 20.2mmol) was added, after which the temperature was gradually raised to 125 deg.C and the reaction continued at this temperature for 12 h. After the reaction was completed, the solvent was distilled off under reduced pressure, and the crude product was purified by column chromatography (mobile phase: petroleum ether: dichloromethane: 4:1(V/V)) to obtain 2.7g of a yellow solid in 55% yield. MS (EI) M/z498.28[ M ]⁺](ii) a Elemental analysis by Combustion method C₃₀H₂₀BBrN₂(%) Calculations C72.18, H4.04, N5.61; found C71.98, H4.00, N5.51.

[ Synthesis of Compound M11 ]

The synthetic route for compound M11 is shown below:

into a clean 250mL three-necked flask, pentafluorophenylboronic acid (10.1g, 47.8mmol), anhydrous sodium carbonate (8.4g, 79.6mmol), compound M10(19.8g, 39.8mmol), tetrakis (triphenylphosphine palladium) (470.8mg, 4.8mmol), and a ternary mixed solvent (100mL, toluene: water: ethanol ═ 5:1:1(V/V)) were sequentially added under a nitrogen atmosphere. 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 water (about 200mL) 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)Gum, eluent petroleum ether dichloromethane ═ 3:2(V/V)), gave 19.7g of yellow solid in 84% yield. MS (EI) M/z 586.23[ M ]⁺](ii) a Elemental analysis by Combustion method C₃₆H₂₀BF₅N₂(%) Calculations C73.74, H3.44, N4.78; found C73.61, H3.40, N4.75.

[ Synthesis of Compounds 13 to 29 ]

The synthetic route for compounds 13-29 is shown below:

carbazole (39.7g, 237.6mmol), anhydrous potassium carbonate (12.6g, 119.4mmol), compound M11(23.5g, 39.8mmol), and DMSO (100mL) were added sequentially to a clean 250mL three-necked flask under a nitrogen atmosphere. 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 water (about 200mL) 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 ═ 3:2(V/V)) to give 18.0g of a green solid in 34% yield. MS (EI) M/z 1322.63[ M ]⁺](ii) a Elemental analysis by Combustion method C₉₆H₆₀BN₇(%) Calcd for C87.19, H4.57, N7.41; found C86.95, H4.55, N7.40.

Example 6: synthesis of Compounds 13-31

[ Synthesis of Compound M12 ]

The synthetic route for compound M12 is shown below:

to a clean 250mL three-necked flask, 3,4, 5-trifluorophenylboronic acid (8.4g, 47.8mmol), anhydrous sodium carbonate (8.4g, 79.6mmol), compound M10(19.8g, 39.8mmol), tetrakis (triphenylphosphine palladium) (470.8mg, 4.8mmol), and a ternary mixed solvent (100mL, toluene: water: ethanol ═ 5:1:1(V/V)) were added in this order under a nitrogen atmosphere.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 water (about 200mL) 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 ═ 3:2(V/V)) to give 17.5g of a yellow solid in 80% yield. MS (EI) M/z 550.23[ M ]⁺](ii) a Elemental analysis by Combustion method C₃₆H₂₂BF₃N₂Calculated value of (%) -C78.56, H4.03, N5.09; found C78.45, H4.00, N5.07.

[ Synthesis of Compounds 13 to 31 ]

The synthetic routes for compounds 13-31 are shown below:

carbazole (23.2g, 139.3mmol), anhydrous potassium carbonate (8.4g, 79.6mmol), compound M12(20.9g, 39.8mmol), and DMSO (100mL) were added sequentially to a clean 250mL three-necked flask under a nitrogen atmosphere. 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 water (about 200mL) 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 ═ 3:2(V/V)) to give 33.5g of a green solid in 85% yield. MS (EI) M/z 991.83[ M ]⁺](ii) a Elemental analysis by Combustion method C₇₂H₄₆BN₅(%) calculated C87.18, H4.67, N7.06; found to be C87.10, H4.60, N7.00.

Example 7: preparation of organic electroluminescent device 1(OLED1)

A hole injection layer 3, a hole transport layer 4, an electron blocking layer 5, a light emitting layer 6, a hole blocking layer 7, an electron transport layer 8, an electron injection layer 9 and a cathode 10 were sequentially formed on a transparent anode 2 previously formed on a glass substrate 1 to prepare an organic electroluminescent device as shown in fig. 5.

Concretely, the glass substrate with the ITO transparent conducting layer with the film thickness of 100nm is treated by ultrasonic treatment in Decon 90 alkaline cleaning solution, washed in deionized water, washed three times in acetone and ethanol respectively, baked in a clean environment to completely remove moisture, washed by ultraviolet light and ozone, and bombarded on the surface by low-energy cation beams, the glass substrate with the ITO electrode is placed in a vacuum chamber and vacuumized 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 thickness of 10nm as a Hole Injection Layer (HIL). N, N '-diphenyl-N, N' -di (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB) was vapor-deposited on the hole injection layer at a vapor deposition rate of 0.2nm/s to form a layer having a film thickness of 40nm as a Hole Transport Layer (HTL). 3,3 '-bis (N-carbazolyl) -1,1' -biphenyl (mCBP) was vapor-deposited on the hole transport layer at a vapor deposition rate of 0.2nm/s to form a layer having a thickness of 15nm as an Electron Blocking Layer (EBL). On the electron blocking layer, 9- (2-naphthyl) -10- [4- (1-naphthyl) phenyl group as main material]Anthracene (NNPA) was co-evaporated at a deposition rate of 0.2nm/s and a deposition rate of 0.2nm/s for the compounds 1 to 3 as a dopant to form a layer having a thickness of 20nm, and the dopant was doped at a doping weight ratio of 6 wt% for a light-emitting layer. 2,4, 6-tris (3-biphenylyl) -1,3, 5-triazine (T2T) was vapor-deposited on the light-emitting layer at a vapor deposition rate of 0.2nm/s to form a layer having a film thickness of 10nm as a Hole Blocking Layer (HBL). 2- [4- (9, 10-bis (2-naphthyl) anthracen-2-yl) phenyl ] evaporated on the hole-blocking layer at an evaporation rate of 0.2nm/s]-1-phenyl-1H-benzimidazole (ZADN) to form a layer with a thickness of 40nm as Electron Transport Layer (ETL). 8-hydroxyquinoline-lithium (Liq) was vapor-deposited on the electron transport layer at a vapor deposition rate of 0.02nm/s to form a layer having a thickness of 2nm as an Electron Injection Layer (EIL). Finally, aluminum is deposited on the electron injection layer at a deposition rate of 0.5nm/s or more to form a cathode having a film thickness of 100 nm.

Examples 8 to 12: preparation of OLED 2-6

OLEDs 2-6 were prepared under the same production conditions as OLED1, except that compounds 1-1, 1-10, 1-8, 13-29, and 13-31 in Table 1 were used in place of compounds 1-3 in example 7, respectively.

Comparative examples 1 to 2: comparative preparation of OLED 1-2

Comparative OLEDs 1-2 were prepared under the same production conditions as OLED1, except that compounds DPAVBi and BD1 in Table 1 were used instead of compounds 1-3 in example 7, respectively.

The electroluminescence spectra were collected using a photon multichannel analyzer PMA-12(Hamamatsu C10027-01), which can be detected in the spectral region of 200 and 950 nm. The forward light intensity was measured using an integrating sphere (Hamamatsu a10094) to obtain the external quantum efficiency of the device. All measurements were performed at room temperature in an atmospheric environment.

The method for forming each structural layer in the organic electroluminescent device of the present invention is not particularly limited, and conventional vacuum evaporation methods, spin coating methods, and the like may be used.

The structures and film thicknesses of the respective layers of the OLEDs prepared in inventive examples 7-12 and comparative examples 1-2 are shown in Table 1.

TABLE 1 OLED COMPARATIVE EXAMPLES 7-12 AND COMPARATIVE EXAMPLES 1-2

Examples 7 to 12 and comparative examples 1 to 2 relate to compounds having the following structures:

the light emission characteristics of the OLEDs 1-6 produced in examples 7-12 and the comparative OLEDs 1-2 produced in comparative examples 1-2 were measured at room temperature in the atmosphere when a dc voltage was applied, and the measurement results are shown in table 2.

TABLE 2 device Performance data

As can be seen from table 2, the boron-containing compound of the present invention has excellent luminescence characteristics, stable structure and higher color purity by modifying and introducing other different chemical groups, and compared with commercial materials DPAVBi and BD1, the boron-containing compound of the present invention has higher efficiency, smaller CIEy value and significantly improved device life; and the preparation cost is low.

As can be seen from fig. 1 and 2, the half-widths of the photoluminescence spectrum and the electroluminescence spectrum of the boron-containing compound of the present invention are very narrow and the spectra reach deep blue spectrum, which indicates that their color purity is higher, so the CIE y value in the device is correspondingly lower and the color gamut is wider. As can be seen from FIG. 3, the delayed fluorescence phenomenon of the boron-containing compound of the present invention is very obvious, demonstrating that it is a thermally activated delayed fluorescence material, which can utilize 100% of excitons for light emission. As can be seen from fig. 4, the boron-containing compound of the present invention has a boron-containing rigid structure, so that the compound has excellent stability at high temperature, and the stability of the device can be improved.

Industrial applicability

The organic electroluminescent compounds (boron-containing compounds) of the present invention have excellent luminous efficiency and excellent color purity of materials. Therefore, the compound can be used for preparing a deep blue/blue organic electroluminescent device with excellent performance.

Claims

1. A boron-containing compound represented by the following general formula (1):

wherein the content of the first and second substances,

if present, each A₁Each independently represents Ar₁Or

m is any integer of 1 to 5;

in the structural formulae C-1 to C-70,

the dotted line represents a bond;

each Z independently represents CR¹Or N;

2. The boron-containing compound according to claim 1, which is represented by the following general formula (I) or (II):

wherein, B₁、Ar₁To Ar₂M, M and C₁To C₃As defined in claim 1.

3. The boron-containing compound according to claim 1, wherein each Ar, if present, is₁And Ar₂Each independently selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, a cyano group, or any one of the following groups:

4. The boron-containing compound according to any one of claims 1 to 3,

if present, each Ar₁And Ar₂Each independently represents a phenyl group, a fluorenyl group, a dianilino group, a benzofurodianilino group, a benzothienodianilino group, a dibenzofuranyl group, a dibenzothiophenyl group, a carbazolyl group, an indenocarbazolyl group, a benzofurocarbazolyl group, a benzothienocarbazolyl group, an indolocarbazolyl group, an acridinyl group, a benzofuranyl group, a benzothienocarbazolyl group, a benzofuranyl,Phenoxazinyl and phenothiazinyl, preferably carbazolyl, acridinyl, phenoxazinyl, phenothiazinyl and dianilinyl;

C₁、C₂and C₃Each independently represents a fragment derived from any one of the following structures: benzene optionally substituted with one or more C1-C6 alkyl groups, carbazole, phenoxazine, phenothiazine, diphenylamine, dibenzofuran and dibenzothiophene optionally substituted with one or more alkyl or aryl groups, preferably benzene, tert-butyl benzene, N-methylcarbazole, N-phenylcarbazole, phenoxazine, phenothiazine, dibenzofuran and diphenylthiophene;

5. The boron-containing compound according to any one of claims 1 to 4, which is selected from the following compounds:

6. an electronic device comprising the boron-containing 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.

8. An organic electroluminescent device, comprising: 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, the at least one organic layer containing the boron-containing compound according to any one of claims 1 to 5.

9. The organic electroluminescent device according to claim 8, wherein the at least one organic layer is a hole injection layer, a hole transport layer, a light emitting layer, an electron blocking layer, a hole blocking layer, or an electron transport layer.

10. Use of the boron-containing 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; preferably, the electronic device is an organic electroluminescent device, an organic field effect transistor or an organic solar cell.