CN110950829A - Spirobenzanthrone derivatives and electronic devices - Google Patents

Abstract

The present invention relates to spirobenzanthrone derivatives and electronic devices. The spirobenzanthrone derivative provided by the invention has excellent film forming property and thermal stability by introducing a spirobenzanthrone rigid structure, and can be used for preparing organic electroluminescent devices, organic field effect transistors and organic solar cells. In addition, the spirobenzanthrone derivative 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 and the like. In addition, the preparation method of the spirobenzanthrone derivative is simple, raw materials are easy to obtain, and the development requirement of industrialization can be met.

Description

Spirobenzanthrone derivatives and electronic devices

Technical Field

The invention belongs to the technical field of organic photoelectric materials, and relates to a spirobenzanthrone derivative and an electronic device containing the spirobenzanthrone derivative. More particularly, the present invention relates to spirobenzanthrone derivatives suitable for use in electronic devices, particularly organic electroluminescent devices, organic field effect transistors and organic solar cells, and electronic devices 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 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 spirobenzanthrone derivative. The spirobenzanthrone derivative has high thermal stability, good transmission performance, high triplet state and simple preparation method, and an organic light-emitting device prepared from the spirobenzanthrone derivative has the advantages of high light-emitting efficiency, long service life and low driving voltage, and is an organic electroluminescent material with excellent performance.

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

Means for solving the problems

The spirobenzanthrone compound has a special biphenyl structure, has high thermal stability, chemical stability and carrier transport property, and more importantly has proper singlet state, triplet state and molecular orbital energy level. Therefore, the organic electroluminescent material is introduced into molecules with electroluminescent characteristics, so that the stability and the luminous efficiency of a device are improved, and the driving voltage of the device is reduced.

Namely, the present invention is as follows.

[1] A spirobenzanthrone derivative represented by the following general formula (1):

wherein L is₁～L₃Each independently represents a single bond, a carbonyl group, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or an aromatic hydrocarbon group having 5 to 18 carbon atomsOne or more of a group heterocyclyl;

m, n and p are each independently an integer of 0 to 4, and m, n and p are not 0 at the same time;

A₁～A₃each independently represents Ar₁、Ar₂、Ar₃、

One or more of;

Ar₁～Ar₆each independently represents optionally substituted one or more R¹Substituted, aromatic hydrocarbon radical having 6 to 30 carbon atoms or optionally substituted by one or more R¹One or more substituted aromatic heterocyclic groups having 5 to 30 carbon atoms;

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;

x represents O, S or SO₂。

[2] The spirobenzanthrone derivative according to the above [1], which is represented by the following general formula (I) or (II):

L₁～L₃、Ar₁～Ar₆x and m, n and p have the formula [1] as defined above]The meaning as defined.

[3]According to the above [1]]The spirobenzanthrone derivative is shown in the specification, wherein Ar is₁～Ar₆Each independently selected from the following groups:

wherein the dotted line represents and L₁、L₂、L₃Or a bond of an N-bond,

R¹having the structure according to [1] above]The meaning as defined.

[4] The spirobenzanthrone derivative according to any one of the above [1] to [3], wherein,

m, n and p are each independently an integer of 0-2, and m, n and p are not 0 at the same time;

L₁～L₃each 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 spirobenzanthrone derivative according to any one of the above [1] to [4], wherein the spirobenzanthrone derivative represented by the general formula (1) is selected from the following compounds:

[6] an electronic device comprising the spirobenzanthrone derivative according to any one of the above [1] to [5].

[7] The electronic device according to the above [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 spirobenzanthrone derivative according to any one of the above [1] to [5].

[8] The electronic device according to the above [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.

ADVANTAGEOUS EFFECTS OF INVENTION

The spirobenzanthrone derivative disclosed by the invention has good film forming property and thermal stability by introducing a spirobenzanthrone rigid structure, can be used for preparing electronic devices such as organic electroluminescent devices, organic field effect transistors and organic solar cells, especially used as a constituent material of a hole injection layer, a hole transmission layer, a light emitting layer, an electron blocking layer, a hole blocking layer or an electron transmission layer in the organic electroluminescent devices, can show the advantages of high luminous efficiency, long service life and low driving voltage, and is obviously superior to the existing organic electroluminescent devices.

In addition, the preparation method of the spirobenzanthrone derivative is simple, raw materials are easy to obtain, and the development requirement of industrialization can be met.

The spirobenzanthrone derivative has good application effect in electronic devices such as organic electroluminescent devices, organic field effect transistors, organic solar cells and the like, and has wide industrialization prospect.

The spirobenzanthrone derivative has high electron injection and moving speed. Therefore, the organic electroluminescent device having the electron injection layer and/or the electron transport layer prepared using the spirobenzanthrone derivative of the present invention improves the electron transport efficiency from the electron transport layer to the light emitting layer, thereby improving the light emitting efficiency. And, the driving voltage is reduced, thereby enhancing durability of the resulting organic electroluminescent device.

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

The spirobenzanthrone derivative 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 shows a fluorescence spectrum (PL) of example 2 (compound 33) of the present invention in methylene chloride.

FIG. 2 is a thermogravimetric plot (TGA) of example 2 (Compound 33) of the present invention.

Fig. 3 is an electroluminescence spectrum of the organic electroluminescence device of example 9 (organic electroluminescence device 3) of the present invention and comparative example 1.

FIG. 4 is a view showing the configurations of organic electroluminescent devices of examples 7 to 13 and organic electroluminescent devices of comparative examples 1 and 2.

Description of the reference numerals

1 substrate

2 anode

3 hole injection layer

4 hole transport layer

5 Electron blocking layer

6 light-emitting layer

7 hole blocking layer

8 electron transport layer

9 electron injection layer

10 cathode

Detailed Description

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

The spirobenzanthrone derivative of the present invention is a novel compound having a fluorene ring structure, and is represented by the following general formula (1).

Specifically, the spirobenzanthrone derivative of the present invention has a structure of the following general formula (I) or (II):

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

L₁～L₃each 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;

m, n and p are each independently an integer of 0 to 4, and m, n and p are not 0 at the same time;

A₁～A₃each independently represents Ar₁、Ar₂、Ar₃、

One or more of;

Ar₁～Ar₆each independently represents optionally substituted one or more R¹Substituted, aromatic hydrocarbon radical having 6 to 30 carbon atoms or optionally substituted by one or more R¹One or more substituted aromatic heterocyclic groups having 5 to 30 carbon atoms;

R¹represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, NO₂、N(R²)₂、OR²、SR²、C(＝O)R²、P(＝O)R²、Si(R²)₃Substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 20 carbon atomsOne or more of an alkynyl group of (a), 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.

<L₁To L₃>

L₁～L₃Each 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 L₁～L₃The 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, anthryl, benzanthryl, phenanthryl, benzophenanthryl, pyrenyl, perylenyl, fluoranthenyl,Benzofluoranthenyl, tetracenyl, pentacenyl, benzopyrenyl, biphenylyl, idophenyl, terphenyl, quaterphenyl, pentabiphenyl, terphenyl, fluorenyl, spirobifluorenyl, dihydrophenanthrenyl, dihydropyrenyl, tetrahydropyrenyl, cis-or trans-indenofluorenyl, cis-or trans-monobenzindenofluorenyl, cis-or trans-dibenzoindenofluorenyl, triindenyl, isotridecyl, spiroisotridecyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, 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, quinoxaloimidazolyl, oxazolyl, benzoxazolyl, naphthooxazolyl, anthraoxazolyl, phenanthroixazolyl, isoxazolyl, 1, 2-thiazolyl, 1, 3-thiazolyl, benzothiazolyl, pyridazinyl, benzopyrazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1, 5-diazenanthrayl, 2, 7-diazapyryl, 2, 3-diazapyl, 1, 6-diazapyl, 1, 8-diazapyl, 4, 5-diazapyranyl, 4, 5-tetraazapyryl, 9, 10-tetraazapyrylperylene, pyrazinyl, phenazinyl, naphthoxazinyl, etc, Phenoxazinyl, phenothiazinyl, fluorerynyl, naphthyridinyl, azacarbazolyl, benzocarbazinyl, phenanthrolinyl, 1,2, 3-triazolyl, 1,2, 4-triazolyl, benzotriazolyl, 1,2, 3-oxadiazolyl, 1,2, 4-oxadiazolyl, 1,2, 5-oxadiazolyl, 1,3, 4-oxadiazolyl, 1,2, 3-thiadiazolyl, 1,2, 4-thiadiazolyl, 1,2, 5-thiadiazolyl, 1,3, 4-thiadiazolyl, 1,3, 5-triazinyl, 1,2, 4-triazinyl, 1,2, 3-triazinyl, tetrazolyl, 1,2,4, 5-tetrazinyl, 1,2,3, 4-tetrazinyl, 1,2,3, 5-tetrazinyl, purinyl, pteridinyl, Indolizinyl, benzothiadiazolyl, and the like.

In the present invention, preferably, L₁～L₃Each independently represents a single bond, a carbonyl group, an aromatic hydrocarbon group having 6 to 12 carbon atoms orOne or more aromatic heterocyclic groups having 5 to 12 carbon atoms. More preferably, L₁～L₃Each independently represents one or more of a single bond, a carbonyl group, a phenyl group, a triazinyl group or a biphenyl group.

From L₁～L₃The aromatic hydrocarbon group having 6 to 18 carbon atoms or the aromatic heterocyclic group having 5 to 18 carbon atoms represented may be unsubstituted, but may also have a substituent. The substituents may be exemplified by the following: a deuterium atom; a cyano group; a nitro group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; an alkyl group having 1 to 6 carbon atoms, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a n-pentyl group, an isopentyl group, a neopentyl group, or a n-hexyl group; alkoxy having 1 to 6 carbon atoms such as methoxy, ethoxy or propoxy; alkenyl, such as vinyl or allyl; aryloxy groups such as phenoxy or tolyloxy; arylalkoxy, such as benzyloxy or phenethyloxy; aromatic hydrocarbon radicals or condensed polycyclic aromatic radicals, e.g. phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, fluorenyl, indenyl, pyrenyl, perylenyl, fluoranthryl, benzo [9,10 ] benzo]Phenanthryl or spirobifluorenyl; an aromatic heterocyclic group such as pyridyl, thienyl, furyl, pyrrolyl, quinolyl, isoquinolyl, benzofuryl, benzothienyl, indolyl, carbazolyl, benzoxazolyl, benzothiazolyl, quinoxalyl, benzimidazolyl, pyrazolyl, dibenzofuryl, dibenzothienyl, azafluorenyl, diazafluorenyl, carbolinyl, azaspirobifluorenyl or diazaspiro-bifluorenyl; arylethenyl, such as styryl or naphthylethenyl; and acyl groups such as acetyl or benzoyl and the like.

The alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms may be linear or branched. Any of the above substituents may be further substituted with the above exemplary substituents. The above substituents may be present independently of each other, but may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom to form a ring.

< m, n and p >

m, n and p each represents-L linked to the spirobenzanthrone skeleton structure₁-A₁Structural unit, -L₂-A₂Structural unit and-L₃-A₃The number of the structural units, m, n and p are each independently an integer of 0 to 4, and m, n and p are not 0 at the same time. Preferably, m, n and p are each independently an integer of 0 to 2, more preferably 0,1 or 2, but not simultaneously 0.

<A₁To A₃>

A₁～A₃Each independently represents Ar₁、Ar₂、Ar₃、

One or more of the above.

(Ar₁To Ar₆)

Ar₁～Ar₆Each independently represents optionally substituted one or more R¹Substituted, aromatic hydrocarbon radical having 6 to 30 carbon atoms or optionally substituted by one or more R¹One or more substituted aromatic heterocyclic groups having 5 to 30 carbon atoms.

From Ar₁～Ar₆The 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, anthryl, benzofluoranthenyl, tetracenyl, pentacenyl, benzopyrenyl, biphenyl, idophenyl, terphenyl, quaterphenyl, pentabiphenyl, terphenyl, fluorenyl, spirobifluorenyl, dihydrophenanthryl, dihydropyrenyl, tetrahydropyrenyl, cis-or trans-indenofluorenyl, cis-or trans-monobenzindenofluorenyl, cis-or trans-dibenzoindenofluorenyl, trimeric indenyl, isotridecyl, spirotrimeric indenyl, spiroisotridecyl, furanyl, benzofuranyl, isobenzofuranyl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, benzothienyl, benzothiophenocarbazolyl, pyrrolyl, indolyl, isoindolyl, carbazolyl, indolocarbazolyl, and dibenzocarbazolylOxazolyl, 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, naphthoxazolyl, anthraoxazolyl, phenanthrooxazolyl, isoxazolyl, thiazolyl, isothiazolyl, benzothiazolyl, benzothiadiazolyl, pyridazinyl, benzopyrazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, quinazolinyl, azafluorenyl, diazahthranyl, diazapyrnyl, phenanthridinyl, phenanthridin, Tetraazaperylenyl, diazanaphthyl, pyrazinyl, phenazinyl, phenoxazinyl, phenothiazinyl, fluorescenzinyl, naphthyridinyl, azacarbazolyl, benzocarbazolyl, phenanthrolinyl, triazolyl, benzotriazolyl, oxadiazolyl, thiadiazolyl, triazinyl, tetrazolyl, tetrazinyl, purinyl, pteridinyl, indolizinyl, benzothiadiazolyl, pyridopyrrolyl, pyridotriazolyl, xanthenyl, benzofurocarbazolyl, benzofluorenocarbazolyl, N-phenylcarbazolyl, diphenyl-benzimidazolyl, diphenyl-oxadiazolyl, diphenyl boron, triphenylphosphoxy, diphenylphosphinoxy, triphenylsilyl, tetraphenylsilyl, and the like.

In the present invention, preferably, Ar₁～Ar₆Each independently selected from the following groups:

wherein the dotted line represents and L₁、L₂、L₃Or an N-bonded bond;

R¹have the meaning defined above.

From Ar₁～Ar₆The 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～Ar₆The 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 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 of the following R²And (4) substitution. In addition, one or more non-adjacent CH in the alkyl group₂The group can be represented by R²C＝CR²、C≡C、Si(R²)₃、C＝O、C＝NR²、P(＝O)R²、SO、SO₂、NR²O, S or CONR²And wherein one or more hydrogen atoms may be replaced with deuterium atom, fluorine atom, chlorine atom, bromine atom, iodine atom, cyano group, nitro group.

From R¹The alkenyl group having 2 to 20 carbon atoms represented may be exemplified by: vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, 2-ethylhexenyl, allyl, cyclohexenyl and the like. The alkenyl group having 2 to 20 carbon atoms may be linear, branched or cyclic.

From R¹The alkenyl group having 2 to 20 carbon atoms represented may be unsubstituted or may have a substituent. The substituents can be exemplified by the group consisting of R¹The alkyl group having 1 to 20 carbon atoms represented by (b) may have the same substituent as that represented by the substituent(s). The substituents may take the same pattern as that of the exemplary substituents.

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

From R¹The alkynyl group having 2 to 20 carbon atoms represented may be unsubstituted or may have a substituent. The substituents can be exemplified by the group consisting of R¹The alkyl group having 1 to 20 carbon atoms represented by (b) may have the same substituent as that represented by the substituent(s). The mold that the substituent may takeThe formula is the same as the pattern for the exemplary substituent.

From R¹The aromatic hydrocarbon group having 6 to 40 carbon atoms or the aromatic heterocyclic group having 5 to 40 carbon atoms represented by the formula are exemplified by the groups represented by the above formula Ar₁～Ar₆The aromatic hydrocarbon group having 6 to 30 carbon atoms or the aromatic heterocyclic group having 5 to 30 carbon atoms represented by the above formula represent the same groups.

From R¹The aromatic hydrocarbon group having 6 to 40 carbon atoms or the aromatic heterocyclic group having 5 to 40 carbon atoms represented may be unsubstituted or may have a substituent. The substituents can be exemplified by the group consisting of R¹The alkyl group having 1 to 20 carbon atoms represented by (b) may have the same substituent as that represented by the substituent(s). The substituents may take the same pattern as that of the exemplary substituents. In addition, two adjacent R¹Substituents or two adjacent R²The substituents optionally may form a mono-or polycyclic aliphatic, aromatic or heteroaromatic ring system, which may be substituted by one or more R²Substitution; where two or more substituents R¹May be connected to each other and may form a ring.

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

(R²)

R²Represents a hydrogen atom, a deuterium atom, a fluorine atom,One or more of 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.

(X)

X represents O, S or SO₂。

< production method >

The spirobenzanthrone derivative 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 spirobenzanthrone derivatives 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 spirobenzanthrone derivatives of the invention can be produced by using the spirobenzanthrone derivatives according to the invention for producing organic materials which can be configured in particular in the form of layers. In particular, the spirobenzanthrone derivatives of the present invention can be used in organic electroluminescent devices, organic solar cells, organic diodes, in particular organic field effect transistors. Particularly in the case of an organic electroluminescent device or a solar cell, the assembly may have a plug structure (the device has one or more p-doped hole transport layers and/or one or more n-doped electron transport layers) or an inverted structure (from the light emitting layer, the upper electrode and the hole transport layer are located on the same side while the substrate is on the opposite side), without being limited to these structures. The injection layer, transport layer, light-emitting layer, barrier layer, etc. can be produced, for example, by forming a layer containing or consisting of the spirobenzanthrone derivative according to the invention between the electrodes. However, the use of the spirobenzanthrone derivatives 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 electrode 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 the spirobenzanthrone derivative of the present invention.

Fig. 4 is a view showing the configuration of an organic electroluminescent device of the present invention. As shown in fig. 4, in the organic electroluminescent device of the present invention, for example, ananode 2, ahole injection layer 3, ahole transport layer 4, anelectron blocking layer 5, alight emitting layer 6, ahole blocking layer 7, anelectron transport layer 8, anelectron injection layer 9, and acathode 10 are sequentially disposed on asubstrate 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 thehole injection layer 3 between theanode 2 and thehole transport layer 4, thehole blocking layer 7 between the light emittinglayer 6 and theelectron transport layer 8, and theelectron injection layer 9 between theelectron transport layer 8 and thecathode 10 are omitted, and theanode 2, thehole transport layer 4, thelight emitting layer 6, theelectron transport layer 8, and thecathode 10 are sequentially provided on thesubstrate 1.

The organic electroluminescent device according to the present invention may be manufactured by materials and methods well known in the art, except that the above organic layer contains the compound represented by the above general formula (1). In addition, in the case where the organic electroluminescent device includes a plurality of organic layers, the organic layers may be formed of the same substance or different substances.

For example, the organic electroluminescent device according to the present invention may be manufactured by sequentially laminating a first electrode, an organic layer, and a second electrode on a substrate. At this time, the following can be made: an anode is formed by depositing metal, a metal oxide having conductivity, or an alloy thereof on a substrate by a PVD (physical vapor deposition) method such as a sputtering method or an electron beam evaporation method, an organic layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer is formed on the anode, and a substance which can be used as a cathode is deposited on the organic layer. However, the production method is not limited thereto.

In one example, the first electrode is an anode and the second electrode is a cathode, or the first electrode is a cathode and the second electrode is an anode.

The anode of the organic electroluminescent device of the present invention may be made of a known electrode material. For example, an electrode material having a large work function, such as a metal of vanadium, chromium, copper, zinc, gold, or an alloy thereof; metal oxides such as zinc oxide, Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), and the like; such as ZnO, Al or SNO₂A combination of a metal such as Sb and an oxide; poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxy) thiophene]And conductive polymers such as PEDOT, polypyrrole, and polyaniline. Among these, ITO is preferable.

As the hole injection layer of the organic electroluminescent device of the present invention, a known material having a hole injection property can be used. Examples thereof include: porphyrin compounds represented by copper phthalocyanine, naphthalenediamine derivatives, star-shaped triphenylamine derivatives, triphenylamine trimers such as arylamine compounds having a structure in which 3 or more triphenylamine structures are connected by a single bond or a divalent group containing no heteroatom in the molecule, tetramers, receptor-type heterocyclic compounds such as hexacyanoazatriphenylene, and coating-type polymer materials. These materials can be formed into a thin film by a known method such as a vapor deposition method, a spin coating method, and an ink jet method.

The spirobenzanthrone derivatives of the present invention are preferably used as the hole transport layer of the organic electroluminescent element 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.

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

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

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

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

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

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

Examples

The production of the compound represented by the above general formula (1) and the organic electroluminescent device comprising the same is specifically described in the following examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.

Example 1: synthesis ofCompound 3

(Synthesis of intermediate 1-1)

The synthetic route of intermediate 1-1 is shown below:

to a dry, clean, 250mL three-necked flask, 2.5g (8.9mmol) of 1-bromo-8-phenylnaphthalene and 150mL of anhydrous tetrahydrofuran were added under nitrogen, and dissolved with stirring at room temperature. The system was cooled to-78 ℃ and 3.9mL (2.5M, 9.8mmol) of n-butyllithium were added dropwise at this temperature and stirring continued at this temperature for 1.5 h. 2.2g (8.1mmol) of 3-bromoxanthone are then added in one portion, the cooling bath is removed after the addition, the reaction is allowed to warm to room temperature and stirring is continued overnight. And after the reaction is finished, washing with water, drying and spin-drying to obtain a white solid.

The white solid was transferred to a 250mL single-neck flask equipped with a reflux condenser, 100mL glacial acetic acid was added and heated to reflux, 3mL concentrated HCl was added dropwise, and the reaction was continued under reflux overnight. After the reaction, the heating was turned off, the reaction mixture was cooled to room temperature, poured into ice water, and filtered to obtain a white solid. The crude product was further purified by column chromatography (petroleum ether: dichloromethane ═ 5: 1(V/V)) to give 3.2g of white crystals in 86% yield. Ms (ei): m/z: 461.18[ M ]⁺]。Anal.calcd for C₂₉H₁₇BrO(％)：C75.50，H 3.71；found：C 75.47，H 3.75。

(Synthesis of Compound 3)

The synthetic route forcompound 3 is shown below:

under nitrogen protection, intermediate 1-1(1.9g, 4.2mmol), bis (4-biphenylyl) amine (1.6g, 5mmol), palladium acetate (18mg, 0.08mmol), tri-tert-butylphosphine tetrafluoroborate (73mg, 0.25mmol), sodium tert-butoxide (806mg, 8.4mmol) and 120mL of toluene were added in this order to a 250mL Schlenk flask, and the reaction was stirred under reflux for 12 hours. After the completion of the reaction, the solvent was distilled off, the residue was dissolved in 200mL of dichloromethane and 50mL of water, washed with water, the organic layer was separated, the aqueous layer was extracted twice with 15mL of dichloromethane, the organic layers were combined, the solvent was distilled off, and the residue was separated by column chromatography (petroleum ether: dichloromethane ═ 2: 1(V/V)), the solvent was distilled off, and after drying, 2.6g of a white solid was obtained in 88% yield. Ms (ei): m/z: 701.65[ M ]⁺]。Anal.calcd forC₅₃H₃₅NO(％)：C 90.70，H 5.03，N 2.00；found：C 90.66，H 5.06，N 1.98。

Example 2: synthesis ofCompound 33

(Synthesis of intermediate 1-2)

The synthetic route of intermediate 1-2 is shown below:

to a dry, clean, 250mL three-necked flask, 2.2g (8.9mmol) of 2-bromodiphenyl ether and 150mL of anhydrous tetrahydrofuran were added under nitrogen, and dissolved at room temperature with stirring. The system was cooled to-78 ℃ and 3.9mL (2.5M, 9.8mmol) of n-butyllithium were added dropwise at this temperature and stirring continued at this temperature for 1.5 h. 2.5g (8.1mmol) of 9-bromobenzanthrone are then added in one portion, the cold bath is removed after the addition is complete, the reaction is allowed to warm to room temperature and stirring is continued overnight. And after the reaction is finished, washing with water, drying and spin-drying to obtain a white solid.

The white solid was transferred to a 250mL single-neck flask equipped with a reflux condenser, 100mL glacial acetic acid was added and heated to reflux, 3mL concentrated HCl was added dropwise, and the reaction was continued under reflux overnight. After the reaction, the heating was turned off, the reaction mixture was cooled to room temperature, poured into ice water, and filtered to obtain a white solid. The crude product was further purified by column chromatography (petroleum ether: dichloromethane ═ 5: 1(V/V)) to give 3.4g of white crystals in 90% yield. Ms (ei): m/z: 461.20[ M ]⁺]。Anal.calcd for C₂₉H₁₇BrO(％)：C75.50，H 3.71；found：C 75.48，H 3.73。

(Synthesis of Compound 33)

The synthetic route forcompound 33 is shown below:

under nitrogen protection, intermediates 1-2(1.9g, 4.2mmol), bis (4-biphenylyl) amine (1.6g, 5mmol), palladium acetate (18mg, 0.08mmol), tri-tert-butylphosphine tetrafluoroborate (73mg, 0.25mmol), sodium tert-butoxide (806mg, 8.4mmol) and 120mL of toluene were added in this order to a 250mL Schlenk flask, and the reaction was stirred under reflux for 12 hours. After the completion of the reaction, the solvent was distilled off, the residue was dissolved in 200mL of dichloromethane and 50mL of water, washed with water, the organic layer was separated, the aqueous layer was extracted twice with 15mL of dichloromethane, the organic layers were combined, the solvent was distilled off, and the residue was separated by column chromatography (petroleum ether: dichloromethane ═ 2: 1(V/V)), the solvent was distilled off, and after drying, 2.3g of a white solid was obtained in a yield of 79%. MS (Mass Spectrometry)(EI)：m/z：701.58[M⁺]。Anal.calcd forC₅₃H₃₅NO(％)：C 90.70，H 5.03，N 2.00；found：C 90.68，H 5.05，N 1.96。

Example 3: synthesis of Compound 63

(Synthesis ofintermediates 1 to 3)

The synthetic route of intermediates 1-3 is shown below:

to a dry, clean, 250mL three-necked flask, 2.2g (8.9mmol) of 2-bromodiphenyl ether and 150mL of anhydrous tetrahydrofuran were added under nitrogen, and dissolved at room temperature with stirring. The system was cooled to-78 ℃ and 3.9mL (2.5M, 9.8mmol) of n-butyllithium were added dropwise at this temperature and stirring continued at this temperature for 1.5 h. 2.5g (8.1mmol) of 3-bromobenzanthrone are then added in one portion, the cold bath is removed after the addition is complete, the reaction is allowed to warm to room temperature and stirring is continued overnight. And after the reaction is finished, washing with water, drying and spin-drying to obtain a white solid.

The white solid was transferred to a 250mL single-neck flask equipped with a reflux condenser, 100mL glacial acetic acid was added and heated to reflux, 3mL concentrated HCl was added dropwise, and the reaction was continued under reflux overnight. After the reaction, the heating was turned off, the reaction mixture was cooled to room temperature, poured into ice water, and filtered to obtain a white solid. The crude product was further purified by column chromatography (petroleum ether: dichloromethane ═ 5: 1(V/V)) to give 3.0g of white crystals in 80% yield. Ms (ei): m/z: 461.26[ M ]⁺]。Anal.calcd forC₂₉H₁₇BrO(％)：C75.50，H 3.71；found：C 75.47，H 3.74。

(Synthesis of Compound 63)

The synthetic route for compound 63 is shown below:

under the protection of nitrogen, 1-3(1.9g, 4.2mmol) of intermediate, 1.6g, 5mmol of bis (4-biphenyl) amine and,Palladium acetate (18mg, 0.08mmol), tri-tert-butylphosphine tetrafluoroborate (73mg, 0.25mmol), sodium tert-butoxide (806mg, 8.4mmol) and 120mL of toluene were reacted under reflux with stirring for 12 hours. After the completion of the reaction, the solvent was distilled off, the residue was dissolved in 200mL of dichloromethane and 50mL of water, washed with water, the organic layer was separated, the aqueous layer was extracted twice with 15mL of dichloromethane, the organic layers were combined, the solvent was distilled off, and the residue was separated by column chromatography (petroleum ether: dichloromethane ═ 2: 1(V/V)), the solvent was distilled off, and after drying, 2.6g of a white solid was obtained in 88% yield. Ms (ei): m/z: 701.62[ M ]⁺]。Anal.calcd forC₅₃H₃₅NO(％)：C 90.70，H 5.03，N 2.00；found：C 90.66，H 5.06，N 1.99。

Example 4: synthesis of Compound 93

(Synthesis ofintermediates 1 to 4)

The synthetic routes for intermediates 1-4 are shown below:

to a dry, clean, 250mL three-necked flask, 2.5g (8.9mmol) of 1-bromo-8-phenylnaphthalene and 150mL of anhydrous tetrahydrofuran were added under nitrogen, and dissolved with stirring at room temperature. The system was cooled to-78 ℃ and 3.9mL (2.5M, 9.8mmol) of n-butyllithium were added dropwise at this temperature and stirring continued at this temperature for 1.5 h. 2.4g (8.1mmol) of 3-bromothioxanthone are then added in one portion, the cold bath is removed after the addition, the reaction is allowed to warm to room temperature and stirring is continued overnight. And after the reaction is finished, washing with water, drying and spin-drying to obtain a white solid.

The white solid was transferred to a 250mL single-neck flask equipped with a reflux condenser, 100mL glacial acetic acid was added and heated to reflux, 3mL concentrated HCl was added dropwise, and the reaction was continued under reflux overnight. After the reaction, the heating was turned off, the reaction mixture was cooled to room temperature, poured into ice water, and filtered to obtain a white solid. The crude product was further purified by column chromatography (petroleum ether: dichloromethane ═ 5: 1(V/V)) to give 3.2g of white crystals in 83% yield. Ms (ei): m/z: 477.38[ M ]⁺]。Anal.calcd for C₂₉H₁₇BrS(％)：C72.96，H 3.59；found：C 72.94，H 3.63。

(Synthesis of Compound 93)

The synthetic route for compound 93 is shown below:

under nitrogen protection,intermediates 1 to 4(2.0g, 4.2mmol), bis (4-biphenylyl) amine (1.6g, 5mmol), palladium acetate (18mg, 0.08mmol), tri-tert-butylphosphine tetrafluoroborate (73mg, 0.25mmol), sodium tert-butoxide (806mg, 8.4mmol) and 120mL of toluene were added in this order to a 250mL Schlenk flask, and the reaction was stirred under reflux for 12 hours. After the completion of the reaction, the solvent was distilled off, the residue was dissolved in 200mL of dichloromethane and 50mL of water, washed with water, the organic layer was separated, the aqueous layer was extracted twice with 15mL of dichloromethane, the organic layers were combined, the solvent was distilled off, and the residue was separated by column chromatography (petroleum ether: dichloromethane ═ 2: 1(V/V)), the solvent was distilled off, and after drying, 2.3g of a white solid was obtained in a yield of 76%. Ms (ei): m/z: 717.82[ M ]⁺]。Anal.calcd forC₅₃H₃₅NS(％)：C 88.67，H 4.91，N 1.95；found：C 88.66，H 4.95，N 1.93。

Example 5: synthesis of Compound 123

(Synthesis ofintermediates 1 to 5)

The synthetic routes for intermediates 1-5 are shown below:

to a dry, clean, 250mL three-necked flask, 2.4g (8.9mmol) of 2-bromobisphenyl sulfide and 150mL of anhydrous tetrahydrofuran were added under nitrogen, and dissolved with stirring at room temperature. The system was cooled to-78 ℃ and 3.9mL (2.5M, 9.8mmol) of n-butyllithium were added dropwise at this temperature and stirring continued at this temperature for 1.5 h. 2.5g (8.1mmol) of 9-bromobenzanthrone are then added in one portion, the cold bath is removed after the addition is complete, the reaction is allowed to warm to room temperature and stirring is continued overnight. And after the reaction is finished, washing with water, drying and spin-drying to obtain a white solid.

Transferring the white solid toThe mixture was transferred to a 250mL single-neck flask equipped with a reflux condenser, 100mL of glacial acetic acid was added and heated to reflux, 3mL of concentrated hydrochloric acid was added dropwise, and the reaction was continued under reflux overnight. After the reaction, the heating was turned off, the reaction mixture was cooled to room temperature, poured into ice water, and filtered to obtain a white solid. The crude product was further purified by column chromatography (petroleum ether: dichloromethane ═ 5: 1(V/V)) to give 2.9g of white crystals in 75% yield. Ms (ei): m/z: 477.36[ M ]⁺]。Anal.calcd for C₂₉H₁₇BrS(％)：C72.96，H 3.59；found：C 72.95，H 3.62。

(Synthesis of Compound 123)

The synthetic route for compound 123 is shown below:

under nitrogen protection,intermediates 1 to 5(2.0g, 4.2mmol), bis (4-biphenylyl) amine (1.6g, 5mmol), palladium acetate (18mg, 0.08mmol), tri-tert-butylphosphine tetrafluoroborate (73mg, 0.25mmol), sodium tert-butoxide (806mg, 8.4mmol) and 120mL of toluene were added in this order to a 250mL Schlenk flask, and the reaction was stirred under reflux for 12 hours. After the completion of the reaction, the solvent was distilled off, the residue was dissolved in 200mL of dichloromethane and 50mL of water, washed with water, the organic layer was separated, the aqueous layer was extracted twice with 15mL of dichloromethane, the organic layers were combined, the solvent was distilled off, and the residue was separated by column chromatography (petroleum ether: dichloromethane ═ 2: 1(V/V)), the solvent was distilled off, and after drying, 2.1g of a white solid was obtained in 71% yield. Ms (ei): m/z: 717.82[ M ]⁺]。Anal.calcd forC₅₃H₃₅NS(％)：C 88.67，H 4.91，N 1.95；found：C 88.66，H 4.63，N 1.91。

Example 6: synthesis of Compound 153

(Synthesis ofintermediates 1 to 6)

The synthetic routes for intermediates 1-6 are shown below:

to a dry, clean, 250mL three-necked flask, 2.4g (8.9mmol) of 2-bromobisphenyl sulfide and 150mL of anhydrous tetrahydrofuran were added under nitrogen, and dissolved with stirring at room temperature. The system was cooled to-78 ℃ and 3.9mL (2.5M, 9.8mmol) of n-butyllithium were added dropwise at this temperature and stirring continued at this temperature for 1.5 h. 2.5g (8.1mmol) of 3-bromobenzanthrone are then added in one portion, the cold bath is removed after the addition is complete, the reaction is allowed to warm to room temperature and stirring is continued overnight. And after the reaction is finished, washing with water, drying and spin-drying to obtain a white solid.

The white solid was transferred to a 250mL single-neck flask equipped with a reflux condenser, 100mL glacial acetic acid was added and heated to reflux, 3mL concentrated HCl was added dropwise, and the reaction was continued under reflux overnight. After the reaction, the heating was turned off, the reaction mixture was cooled to room temperature, poured into ice water, and filtered to obtain a white solid. The crude product was further purified by column chromatography (petroleum ether: dichloromethane ═ 5: 1(V/V)) to give 3.3g of white crystals in 85% yield. Ms (ei): m/z: 477.30[ M ]⁺]。Anal.calcd for C₂₉H₁₇BrS(％)：C72.96，H 3.59；found：C 72.92，H 3.62。

(Synthesis of Compound 153)

The synthetic route for compound 153 is shown below:

under nitrogen protection,intermediates 1 to 5(2.0g, 4.2mmol), bis (4-biphenylyl) amine (1.6g, 5mmol), palladium acetate (18mg, 0.08mmol), tri-tert-butylphosphine tetrafluoroborate (73mg, 0.25mmol), sodium tert-butoxide (806mg, 8.4mmol) and 120mL of toluene were added in this order to a 250mL Schlenk flask, and the reaction was stirred under reflux for 12 hours. After the completion of the reaction, the solvent was distilled off, the residue was dissolved in 200mL of dichloromethane and 50mL of water, washed with water, the organic layer was separated, the aqueous layer was extracted twice with 15mL of dichloromethane, the organic layers were combined, the solvent was distilled off, and the residue was separated by column chromatography (petroleum ether: dichloromethane ═ 2: 1(V/V)), the solvent was distilled off, and after drying, 2.1g of a white solid was obtained in 70% yield. Ms (ei): m/z: 717.76[ M ]⁺]。Anal.calcd forC₅₃H₃₅NS(％)：C 88.67，H 4.91，N 1.95；found：C 88.65，H 4.93，N 1.91。

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

Ahole injection layer 3, ahole transport layer 4, anelectron blocking layer 5, alight emitting layer 6, ahole blocking layer 7, anelectron transport layer 8, anelectron injection layer 9 and acathode 10 were sequentially formed on atransparent anode 2 previously formed on aglass substrate 1 to prepare an organic electroluminescent device as shown in fig. 4.

Specifically, a glass substrate on which an ITO film having a film thickness of 100nm was formed was subjected to ultrasonic treatment in a Decon 90 alkaline cleaning solution, rinsed in deionized water, washed three times in acetone and ethanol, respectively, baked in a clean environment to completely remove moisture, washed with ultraviolet light and ozone, and bombarded on the surface with a low-energy cation beam. Placing the glass substrate with ITO electrode into a vacuum chamber, and vacuumizing to 4 × 10^-4-2×10^-5Pa. Then, 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazatriphenylene (HAT-CN) was deposited on the ITO electrode-equipped glass substrate at a deposition rate of 0.2 nm/sec to form a layer having a film thickness of 10nm as a hole injection layer. N, N '-diphenyl-N, N' - (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. 3,3 '-bis (N-carbazolyl) -1,1' -biphenyl (mCBP) was deposited on the hole transport layer at a deposition rate of 0.2nm/s to form a layer having a thickness of 10nm as an Electron Blocking Layer (EBL). On the electron-blocking layer, double-source co-evaporation was performed at a deposition rate of 0.2nm/s for the compound of example 1 (compound 3) as a host material and 0.016nm/s for GD1 as a dopant material to form a layer with a thickness of 20nm as a light-emitting layer, and the proportion by weight of the dopant of GD1 was 8 wt%. On the light-emitting layer, aluminum (III) bis (2-methyl-8-quinolinolato) -4-phenylphenolate (BALq) was vapor-deposited 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). On the hole-blocking layer, BALq was deposited at a deposition rate of 0.2nm/s to form a layer having a thickness of 40nm as an electron-transporting layer (ETL). On the electron transport layer, 8-hydroxyquinoline-lithium (Liq) was vapor-deposited at a vapor deposition rate of 0.1nm/s to form a layer having a film thickness of 2nm as an electron injection layer. Finally, 0.Aluminum is deposited at a deposition rate of 5nm/s or more to form a cathode having a film thickness of 100 nm.

Examples 8 to 13: preparation oforganic EL devices 2 to 7

An organic EL device was produced under the same conditions as theorganic EL device 1 except that the compounds in table 1 below were used instead of the compounds in each layer of example 7, respectively.

Comparative examples 1 to 2: preparation of organic EL device comparative examples 1 to 2

Comparative examples of organic EL devices were prepared under the same conditions as theorganic EL device 1 except that the compounds in table 1 below were used instead of the compounds in each layer of example 7, respectively.

The examples and comparative examples relate to the following structures of compounds:

TABLE 1

The light emission characteristics of theorganic EL devices 1 to 7 produced in examples 7 to 13 and the organic EL devices produced in comparative examples 1 to 2 were measured at normal temperature under the application of a direct current voltage in the atmosphere. The measurement results are shown in table 2.

The current-luminance-voltage characteristics of the device were obtained from a Keithley source measuring system (Keithley 2400Sourcemeter, Keithley 2000Currentmeter) with calibrated silicon photodiodes, the electroluminescence spectra were measured by a Photo research PR655 spectrometer, and the external quantum efficiencies of the devices were calculated by the method of the documents adv.mater, 2003,15, 1043-.

The lifetime of the device was measured as: the emission luminance (initial luminance) at the start of light emission was set to 10000cd/m²Constant current driving is performed until the light emission luminance decays to 9000cd/m²(corresponding to 90%, where the initial brightness is taken as 100%: 90% decay). Device lifetime with GD1 as dopant is referred to as 10000cd/m²For initial luminance, attenuation is to 9000cd/m²(corresponding to 90%, where the initial brightness is taken as 100%: 90% decay). The lifetime of the device with 4CzIPN as dopant is 10000cd/m²For initial luminance, attenuation is to 9000cd/m²(corresponding to 90%, where the initial brightness is taken as 100%: 90% decay). All devices were encapsulated in a nitrogen atmosphere.

The fluorescence spectra of the compounds in the examples were measured using a Hitachi F4600 spectrofluorometer, with the concentration of the substance in the solution being 10^-5M; the thermal weight loss characteristic is detected by adopting a Merterler-Toliduo TGA1 model thermal weight loss analyzer under the nitrogen atmosphere, and the heating rate is 10K/min.

TABLE 2

As can be seen from table 2, the spirobenzanthrone derivatives of the present invention gave excellent performance data.

Organic EL device comparative example 2 andorganic EL device 2 used GD1 as a dopant, and the host material of theorganic EL device 2 wascompound 33 of the present invention. As can be seen from the comparison of the device performance data, theorganic EL device 2 has lower working voltage, the external quantum efficiency is greatly improved, the service life (90%) of the device is also obviously improved, and the service life is changed from 200h to 930 h.

In addition, in both of comparative example 1 andorganic EL device 3 of the organic EL device, 4CzIPN was used as a dopant, and the host material of theorganic EL device 3 was the compound 63 of the present invention, and it was found from a comparison of the device performance data that theorganic EL device 3 had a longer device life.

Compared with the materials commonly used in the prior art, the spirobenzanthrone derivative disclosed by the invention can effectively reduce the working voltage, improve the external quantum efficiency and prolong the service life of a device.

Industrial applicability

The spirobenzanthrone derivative has excellent luminous efficiency, life characteristics and low driving voltage. Therefore, an organic electroluminescent device having an excellent lifetime can be prepared from the compound.

Claims (8)

1. A spirobenzanthrone derivative represented by the following general formula (1):

wherein L is₁～L₃Each 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;

m, n and p are each independently an integer of 0 to 4, and m, n and p are not 0 at the same time;

A₁～A₃each independently represents Ar₁、Ar₂、Ar₃、

One or more of;

Ar₁～Ar₆each independently represents optionally substituted one or more R¹Substituted, aromatic hydrocarbon radical having 6 to 30 carbon atoms or optionally substituted by one or more R¹One or more substituted aromatic heterocyclic groups having 5 to 30 carbon atoms;

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 a hydrogen atom, a deuterium atom, a fluorine atom,One or more of 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;

x represents O, S or SO₂。

2. The spirobenzanthrone derivative according to claim 1, which is represented by the following general formula (I) or (II):

L₁～L₃、Ar₁～Ar₆x and m, n and p have the meanings defined in claim 1.

3. Spirobenzanthrone derivatives according to claim 1, wherein Ar is Ar₁～Ar₆Each independently selected from the following groups:

wherein the dotted line represents and L₁、L₂、L₃Or a bond of an N-bond,

R¹have the meaning as defined in claim 1.

4. A spirobenzanthrone derivative according to any one of claims 1 to 3, wherein,

m, n and p are each independently an integer of 0-2, and m, n and p are not 0 at the same time;

L₁～L₃each 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. A spirobenzanthrone derivative according to any one of claims 1 to 4, wherein the spirobenzanthrone derivative represented by the general formula (1) is selected from the following compounds:

6. an electronic device comprising the spirobenzanthrone derivative 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 spirobenzanthrone derivative as defined in any one of claims 1 to 5, 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.

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.

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