CN110627834A

CN110627834A - Phosphaphenanthridinone derivatives, synthesis method thereof, and electronic device containing the same

Info

Publication number: CN110627834A
Application number: CN201911013344.5A
Authority: CN
Inventors: 崔林松; 刘向阳; 张业欣; 陈华
Original assignee: Suzhou Jiuxian New Materials Co Ltd
Current assignee: Suzhou Jiuxian New Materials Co Ltd
Priority date: 2019-10-23
Filing date: 2019-10-23
Publication date: 2019-12-31

Abstract

The invention relates to the technical field of organic photoelectric materials, in particular to a phosphaphenanthrone derivative, a synthetic method thereof and an electronic device containing the phosphaphenanthrone derivative, which are represented by a general formula (1): wherein L is₁And L₂Each independently represents a single bond, a carbonyl group, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or an aromatic heterocyclic group having 5 to 18 carbon atoms. The phosphaphenanthrone derivative has excellent film forming property and thermal stability by introducing a ring-shaped rigid structure, and can be used for preparing organic electroluminescent devices, organic field effect transistors and organic solar cells; in addition, the phosphaphenanthrone derivatives of the present invention can be used as a hole injection layer, a hole transport layer, a light emitting layer, an electron blocking layer, a hole blocking layer, or an electron blocking layerThe constituent material of the sub-transmission layer has the advantages of reducing the driving voltage, improving the efficiency and brightness, prolonging the service life and the like.

Description

Phosphaphenanthridinone derivatives, synthesis method thereof, and electronic device containing the same

Technical Field

The invention relates to the technical field of organic photoelectric materials, in particular to a phosphaphenanthrone derivative, a synthetic method thereof and an electronic device containing the phosphaphenanthrone derivative.

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

The invention aims to provide a phosphaphenanthrone derivative and a synthesis method thereof, the phosphaphenanthrone derivative has the characteristics of high thermal stability, good transmission performance and high triplet state, the synthesis method is simple, and an organic light-emitting device prepared from the phosphaphenanthrone 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 containing the phosphaphenanthrone derivative, which has advantages of high efficiency, high durability and long life.

In order to achieve the above purpose, the invention provides the following technical scheme:

a phosphaphenanthrone derivative represented by the following general formula (1):

wherein L is₁And L₂Each independently represents a single bond, a carbonyl group, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or an aromatic heterocyclic group having 5 to 18 carbon atoms;

A₁and A₂Each independently represents Ar₁、Ar₂、

Ar is₁-Ar₄Each independently represents optionally substituted one or more R¹Substituted, aromatic hydrocarbon radical having 6 to 30 carbon atoms or optionally substituted by one or more R¹A substituted aromatic heterocyclic group having 5 to 30 carbon atoms;

the R is¹Represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, NO₂、N(R²)₂、OR²、SR²、C(＝O)R²、P(＝O)R²、Si(R²)₃A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 40 carbon atoms, orA substituted or unsubstituted aromatic heterocyclic group having 5 to 40 carbon atoms;

the R is²Represents 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.

Specifically, it is further represented by the following general formulae (I) and (II):

wherein X represents an alkyl group having 1 to 8 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or an aromatic heterocyclic group having 5 to 18 carbon atoms.

Specifically, Ar is₁、Ar₂、Ar₃And Ar₄Each independently selected from the following groups:

wherein the dotted line represents and L₁、L₂Or a bond to an N atom.

Specifically, the R is₁And R₂Each independently represents phenyl, biphenyl, terphenyl, quaterphenyl, pentabiphenyl, benzothienocarbazole, benzofurocarbazole, benzofluorenocarbazole, benzanthracene, triphenylene, fluorenyl, spirobifluorenyl, triazinyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, indenocarbazyl, benzimidazolyl, diphenyl-oxadiazolyl, dibenzazolylPhenylboronyl, triphenylphosphoxy, diphenylphosphido, triphenylsilyl or tetraphenylsilyl.

Specifically, the phosphaphenanthrone derivative further represented by the general formula (1) is selected from the following compounds:

the synthetic method of the phosphaphenanthrone derivative comprises the following synthetic route:

in particular to the application of the phosphaphenanthrone derivative in electronic devices.

Specifically, the electronic device is an organic electroluminescent device, an organic field effect transistor or an organic solar cell;

wherein the organic electroluminescent device 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, wherein the at least one organic layer includes a phosphaphenanthrone derivative.

Specifically, 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.

Furthermore, the phosphaphenanthrone derivative has a special cyclic 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.

The invention has the beneficial effects that:

(1) the phosphaphenanthrone derivative has good film forming property and thermal stability by introducing a ring-shaped rigid structure, can be used for preparing electronic devices such as organic electroluminescent devices, organic field effect transistors and organic solar cells, particularly used as a constituent material of a hole injection layer, a hole 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.

(2) The preparation method of the phosphaphenanthrone derivative is simple, the raw materials are easy to obtain, and the industrialized development requirement can be met.

(3) The phosphaphenanthrone 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.

(4) The phosphaphenanthrone derivatives of the present invention have high electron injection and movement rates. Therefore, with the organic electroluminescent device having an electron injection layer and/or an electron transport layer prepared using the phosphaphenanthrone derivatives of the present invention, the electron transport efficiency from the electron transport layer to the light emitting layer is improved, thereby improving the light emitting efficiency; and, the driving voltage is reduced, thereby enhancing durability of the resulting organic electroluminescent device.

(5) The phosphaphenanthrone derivative of the present invention has excellent hole blocking ability, excellent electron transport property, and is stable in a thin film state. Therefore, the organic electroluminescent device having a hole blocking layer prepared using the phosphaphenanthrone 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.

(6) The phosphaphenanthrone derivative of the present invention has excellent electron transport properties and a wide band gap. Accordingly, the phosphaphenanthrone derivative of the present invention is used as a host material on which a fluorescent emitting substance, a phosphorescent emitting substance, or a delayed fluorescent emitting substance called a dopant is carried so as to form an emission layer, which makes it possible to realize an organic electroluminescent device that is driven at a reduced voltage and has characteristics of improved luminous efficiency.

(7) The phosphaphenanthrone 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, and by using the organic electroluminescent device, excitons generated in the light-emitting layer can be limited, and the possibility of recombination of holes and electrons can be further increased, so that high luminous efficiency can be obtained; in addition, the driving voltage is so low that high durability can be achieved.

Drawings

FIG. 1 is a graph showing fluorescence spectra (PL) of a compound of example 1 of the present invention (Compound 71) in various solvents;

FIG. 2 shows fluorescence spectra (PL) of a compound of example 2 of the present invention (compound 72) in various solvents;

fig. 3 is a structural view of an organic electroluminescent device according to the present invention.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

In the following embodiments, unless otherwise specified, the technical means used are conventional means well known to those skilled in the art.

The phosphaphenanthrone derivative of the present invention is a novel heterocyclic compound having a polycyclic structure, and is represented by the following general formula (1):

further, the phosphaphenanthrone derivatives of the present invention have the following structures of the general formulae (I) and (II):

in the above general formulae (1), (I) and (II), L₁And L₂Each independently represents a single bond, a carbonyl group, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or an aromatic heterocyclic group having 5 to 18 carbon atoms;

A₁and A₂Each independently represents Ar₁、Ar₂、

Ar₁-Ar₄Each independently represents optionally substituted one or more R¹Substituted, aromatic hydrocarbon radical having 6 to 30 carbon atoms or optionally substituted by one or more R¹A substituted aromatic heterocyclic group having 5 to 30 carbon atoms;

R¹represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, NO₂、N(R²)₂、OR²、SR²、C(＝O)R²、P(＝O)R²、Si(R²)₃A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 40 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 40 carbon atoms;

R²represents a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms.

<L₁And L₂>

L₁And L₂Each independently represents a single bond, a carbonyl group, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or an aromatic heterocyclic group having 5 to 18 carbon atoms.

In the present invention, the hetero atom in the aromatic heterocyclic group having 5 to 18 carbon atoms is preferably selected from N, O and/or S. In the present invention, the number of hetero atoms may be 1 to 5. An aromatic hydrocarbon group or aromatic heterocyclic group in the sense of the present invention means a system which does not necessarily contain only aryl or heteroaryl groups, but in which a plurality of aryl or heteroaryl groups may also be interrupted by non-aromatic units (preferably less than 10% of non-hydrogen atoms), which may be, for example, carbon atoms, nitrogen atoms, oxygen atoms or carbonyl groups. For example, systems of 9, 9' -spirobifluorenes, 9, 9-diarylfluorenes, triarylamines, diaryl ethers, etc., as well as systems in which two or more aryl groups are interrupted, for example by linear or cyclic alkyl groups or by silyl groups, are also intended to be considered aromatic hydrocarbon groups in the sense of the present invention. Furthermore, systems in which two or more aryl or heteroaryl groups are bonded directly to one another, such as biphenyl, terphenyl or quaterphenyl, are likewise intended to be regarded as aromatic hydrocarbon groups or aromatic heterocyclic groups.

From L₁And L₂The aromatic hydrocarbon group having 6 to 18 carbon atoms or the aromatic heterocyclic group having 5 to 18 carbon atoms represented may be exemplified by: phenyl, naphthyl, anthracenyl, benzanthracenyl, phenanthrenyl, benzophenanthrenyl, pyrenyl, perylenyl, fluoranthenyl, benzofluoranthenyl, tetracenyl, pentacenyl, benzopyrenyl, biphenyl, idophenyl, terphenyl, quaterphenyl, pentabiphenyl, terphenyl, fluorenyl, spirobifluorenyl, dihydrophenanthrenyl, hydropyranyl, cis-or trans-indenofluorenyl, cis-or trans-monobenzindenofluorenyl, cis-or trans-dibenzoindenofluorenyl, trimeric indenyl, isotridecyl, spirotrimeric indenyl, spiroisotridecyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, indolyl, isoindolyl, carbazolyl, indolocarbazolyl, indenocarbazolyl, pyridyl, quinolyl, isoquinolyl, acridinyl, perylenyl, anthryl, benzopyrenyl, terphenylenyl, terphenylindenyl, etc, Phenanthridinyl, benzo-5, 6-quinolinyl, benzo-6, 7-quinolinyl, benzo-7, 8-quinolinyl, phenothiazinyl, phenoxazinyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxalinylimidazolyl, oxazolyl, benzoxazolyl, naphthooxazolyl, anthraoxazolyl, phenanthrooxazolyl, isoxazolyl, 1, 2-thiazolyl, 1, 3-thiazolyl, benzothiazolyl, pyridazinyl, benzopyrazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1, 5-diazenanthrayl, 2, 7-diazapyranyl, 2, 3-diazapyranyl, 1, 6-diazapyranyl, 1, 8-diazapyranyl, 4, 5-diazepanyl, 4,5,9, 10-tetraazaperylenyl, pyrazinyl, phenazinyl, phenoxazinylPhenothiazinyl, fluorrycyl, naphthyridinyl, azacarbazolyl, benzocarbazinyl, phenanthrolinyl, 1,2, 3-triazolyl, 1,2, 4-triazolyl, benzotriazolyl, 1,2, 3-oxadiazolyl, 1,2, 4-oxadiazolyl, 1,2, 5-oxadiazolyl, 1,3, 4-oxadiazolyl, 1,2, 3-thiadiazolyl, 1,2, 4-thiadiazolyl, 1,2, 5-thiadiazolyl, 1,3, 4-thiadiazolyl, 1,3, 5-triazinyl, 1,2, 4-triazinyl, 1,2, 3-triazinyl, tetrazolyl, 1,2,4, 5-tetrazinyl, 1,2,3, 4-tetrazinyl, 1,2,3, 5-tetrazinyl, purinyl, pteridinyl, indolizinyl, Benzothiadiazolyl, and the like.

In the present invention, preferably, L₁And L₂Each independently represents a single bond, a carbonyl group, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or an aromatic heterocyclic group having 5 to 12 carbon atoms. More preferably, L₁And L₂Each independently represents a single bond, a carbonyl group, a phenyl group, a triazinyl group or a biphenyl group.

From L₁And L₂The aromatic hydrocarbon group having 6 to 18 carbon atoms or the aromatic heterocyclic group having 5 to 18 carbon atoms represented may be unsubstituted, but may also have a substituent. The substituents may be exemplified by the following: a deuterium atom; a cyano group; a nitro group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; an alkyl group having 1 to 6 carbon atoms, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a n-pentyl group, an isopentyl group, a neopentyl group, or a n-hexyl group; alkoxy having 1 to 6 carbon atoms such as methoxy, ethoxy or propoxy; alkenyl, such as vinyl or allyl; aryloxy groups such as phenoxy or tolyloxy; arylalkoxy, such as benzyloxy or phenethyloxy; aromatic hydrocarbon radicals or condensed polycyclic aromatic radicals, e.g. phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, fluorenyl, indenyl, pyrenyl, perylenyl, fluoranthryl, benzo [9,10 ] benzo]Phenanthryl or spirobifluorenyl; aromatic heterocyclic radicals, e.g. pyridyl, thienyl, furyl, pyrrolyl, quinolyl, isoquinolyl, benzofuryl, benzothienyl, indolyl, carbazolyl, benzoxazolyl, benzothiazolyl, quinoxalyl, benzimidazolyl, pyrazolyl, dibenzofuryl, dibenzothienylAn azafluorenyl group, a diazafluorenyl group, a carbolinyl group, an azaspirobifluorenyl group or a diazafluorosbifluorenyl group; arylethenyl, such as styryl or naphthylethenyl; and acyl groups such as acetyl or benzoyl and the like.

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

<A₁And A₂>

A₁And A₂Each independently represents Ar₁、Ar₂、

<Ar₁To Ar₄>

Ar₁-Ar₄Each independently represents optionally substituted one or more R¹Substituted, aromatic hydrocarbon radical having 6 to 30 carbon atoms or optionally substituted by one or more R¹A substituted aromatic heterocyclic group having 5 to 30 carbon atoms.

From Ar₁-Ar₄The aromatic hydrocarbon group having 6 to 30 carbon atoms or the aromatic heterocyclic group having 5 to 30 carbon atoms represented may be exemplified by: phenyl, naphthyl, 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, trimeric indenyl, isotridecyl, spirotrimeric indenyl, spiroisotridecyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thienyl, benzothienyl, isobenzothienyl, dibenzothiathienylThienyl, benzothiophenocarbazolyl, pyrrolyl, indolyl, 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, pyrazinoiyl, quinoxaloiyl, oxazolyl, benzoxazolyl, benzoxadiazolyl, naphthooxazolyl, anthraoxazolyl, phenanthroixazolyl, isoxazolyl, thiazolyl, isothiazolyl, benzothiazolyl, benzothiadiazolyl, pyridazinyl, pyrimidyl, Benzopyrimidinyl, quinoxalinyl, quinazolinyl, azafluorenyl, diazananthracenyl, pyrenylyl, tetraazaperylenyl, naphthyridinyl, pyrazinyl, phenazinyl, phenothiazinyl, fluorescenzyl, naphthyridinyl, azacarbazolyl, benzocarbazinyl, phenanthrolinyl, triazolyl, benzotriazolyl, oxadiazolyl, thiadiazolyl, triazinyl, tetrazolyl, tetrazinyl, purinyl, pteridinyl, indolizinyl, benzothiadiazolyl, pyridopyrrolyl, pyridotriazolyl, xanthenyl, benzofurocarbazolyl, benzofluorenocarbazolyl, N-phenylcarbazolyl, diphenyl-benzimidazolyl, diphenyl-oxadiazolyl, diphenyl boranyl, triphenylphoxy, diphenylphosphinoxy, triphenylsilyl, tetraphenyls, and the like.

In the present invention, preferably, Ar₁、Ar₂、Ar₃And Ar₄Each independently selected from the following groups:

wherein the dotted line represents and L₁、L₂Or a bond to an N atom.

From Ar₁-Ar₄The aromatic hydrocarbon group having 6 to 30 carbon atoms or the aromatic heterocyclic group having 5 to 30 carbon atoms represented may be unsubstituted, but may also have a substituent. Preferably, from Ar₁-Ar₄The aromatic hydrocarbon group having 6 to 30 carbon atoms or the aromatic heterocyclic group having 5 to 30 carbon atoms represented by¹Substituted, aromatic hydrocarbon radicals having 5 to 30 carbon atoms or substituted by one or more R¹A substituted aromatic heterocyclic group having 5 to 30 carbon atoms.

<R¹>

R¹Represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, NO₂、N(R²)、OR²、SR²、C(＝O)R²、P(＝O)R²、Si(R²)₃A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 40 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 40 carbon atoms.

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

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 substituents may take the same pattern as that of the exemplary substituents.

From R¹The aromatic hydrocarbon group having 6 to 40 carbon atoms or the aromatic heterocyclic group having 5 to 40 carbon atoms represented by the above formula may be exemplified by the group consisting of Ar₁-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, from 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 atomDeuterium atom, fluorine atom, cyano group, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms.

From R²The alkyl group having 1 to 20 carbon atoms represented by R can be enumerated by¹The alkyl groups represented by the formulae having 1 to 20 carbon atoms represent the same groups.

From R²The aromatic hydrocarbon group having 6 to 30 carbon atoms or the substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms represented by the formula R¹The same groups as those shown for the aromatic hydrocarbon group having 6 to 30 carbon atoms or the substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms.

From R²The alkyl group having 1 to 20 carbon atoms, the aromatic hydrocarbon group having 6 to 30 carbon atoms, or the substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms represented may be unsubstituted, or may also have a substituent. The substituents may be exemplified by: a deuterium atom; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; cyano, and the like.

<X>

X represents an alkyl group having 1 to 8 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or an aromatic heterocyclic group having 5 to 18 carbon atoms.

< synthetic method >

The phosphaphenanthrone derivative is synthesized 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 phosphaphenanthrone derivatives according to the invention can be produced using the phosphaphenanthrone derivatives according to the invention for producing organic materials which can be configured in particular in the form of layers. In particular, the phosphaphenanthrone 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 comprising or consisting of the phosphaphenanthrone derivative according to the invention between the electrodes. However, the use of the phosphaphenanthrone derivatives according to 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, wherein each of the organic layers includes the phosphaphenanthrone derivative of the present invention.

Referring to fig. 3, in the organic electroluminescent device of the present invention, for example, an anode, a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode are sequentially disposed on a substrate.

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, there may be a configuration in which a hole injection layer between the anode and the hole transport layer, a hole blocking layer between the light emitting layer and the electron transport layer, and an electron injection layer between the electron transport layer and the cathode are omitted, and the anode, the hole transport layer, the light emitting layer, the electron transport layer, and the cathode are provided in this order on the substrate.

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 SNO₂: a 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 examples, ITO is preferable.

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

As the hole transport layer of the organic electroluminescent device of the present invention, a hole transport layer containing the phosphaphenanthrone derivative 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 device of the present invention, a material containing the phosphaphenanthrone 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.

As the light-emitting layer of the organic electroluminescent device of the present invention, a phosphorescent derivative containing the present invention is preferably used. In addition to this, Alq can also be used₃Various metal complexes such as metal complexes of a first hydroxyquinoline derivative, compounds having a pyrimidine ring structure, anthracene derivatives, bisstyrylbenzene derivatives, pyrene derivatives, oxazole derivatives, polyparaphenylene vinylene derivatives, and the like.

The light emitting layer may be composed of a host material and a dopant material. As the host material, a material containing the phosphaphenanthrone derivative of the present invention is preferably used. In addition to these, mCBP, mCP, thiazole derivatives, benzimidazole derivatives, polydialkylfluorene derivatives, heterocyclic compounds having a partial structure in which an indole ring is a condensed ring, and the like can be used.

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

As the hole blocking layer of the organic electroluminescent device of the present invention, a hole blocking layer containing the phosphaphenanthrone derivative of the present invention is preferably used. In addition, the hole-blocking layer may be formed using another compound having a hole-blocking property. For example, a phenanthroline derivative such as 2,4, 6-tris (3-phenyl) -1,3, 5-triazine (T2T), 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBi), Bathocuproine (BCP), a metal complex of a quinolyl derivative such as aluminum (III) bis (2-methyl-8-hydroxyquinoline) -4-phenylphenate (BAlq), and a compound having a hole-blocking effect such as various rare earth complexes, oxazole derivatives, triazole derivatives, and triazine derivatives can be used. These may be used as a single layer formed by separately forming a film or by mixing them with other materials to form a film, or may be used as a laminated structure of layers formed by separately forming a film, a laminated structure of layers formed by mixing films, or a laminated structure of layers formed by separately forming a film and layers formed by mixing films. These materials can be formed into a thin film by a known method such as a vapor deposition method, a spin coating method, and an ink jet method.

The above-described material having a hole-blocking property can also be used for formation of an electron transport layer described below. That is, by using the known material having a hole-blocking property, a layer which serves as both a hole-blocking layer and an electron-transporting layer can be formed.

As the electron transport layer of the organic electroluminescent device of the present invention, it is preferable to use a material containing the phosphaphenanthrone derivative of the present invention. In addition, the compound may be formed using other compounds having an electron-transporting property. For example, Alq can be used₃Metal complexes of quinolinol derivatives including BAlq; various metal complexes; a triazole derivative; a triazine derivative; an oxadiazole derivative; a pyridine derivative; bis (10-hydroxybenzo [ H ]]Quinoline) beryllium (Be (bq)₂) (ii) a Such as 2- [4- (9, 10-dinaphthalen-2-anthracen-2-yl) phenyl]Benzimidazole derivatives such as-1-phenyl-1H-benzimidazole (ZADN); thiadiazole derivatives(ii) a 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 phosphaphenanthrone derivatives, the synthesis methods thereof, and the electronic devices containing the phosphaphenanthrone derivatives are further specifically described in the following examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.

Example 1: synthesis of Compound 71

(Synthesis of intermediate 1)

The synthetic route for intermediate 1 is shown below:

methylamine (30mmol, 930mg) and 150mL anhydrous Tetrahydrofuran (THF) were added to a dry, clean 250mL three-necked flask in this order under a nitrogen atmosphere, the system was cooled to-78 deg.C, n-butyllithium (30mmol, 2.4M, 12.5mL) was added dropwise to the system, and after completion of the addition, stirring was continued at that temperature for 30mm, followed by addition of 10mL ethyl [1,1' -biphenyl]After the dropwise addition of a tetrahydrofuran solution of (E) -2-yl (phenyl) phosphonate (10mmol, 3.22g), the reaction is continued at-78 ℃ for 2h, then the cold bath is removed, the system is automatically raised to room temperature and the reaction is continued at room temperature overnight, after the reaction is finished, a small amount of water is added to quench the reaction, the reaction is extracted by dichloromethane, the solvent is evaporated under reduced pressure, and the crude product is purified by column chromatography (350 mesh silica gel, eluent is petroleum ether: ethyl acetate: 2: 1, V/V) to obtain 2.6g of a white solid with the yield of 86%. Ms (ei): m/z: 307.16[ M ]⁺]。Anal.calcd for C₁₉H₁₈NOP(％)：C 74.25，H 5.90，N 4.56；found：C 74.23，H 5.93，N 4.53。

(Synthesis of intermediate 2)

The synthetic route for intermediate 2 is shown below:

to a clean 250mL single-neck flask were added in sequence intermediate 1(10mmol, 3.07g), dibromohydantoin (20mmol, 5.72g) and 150mL toluene, the system was gradually warmed to 100 ℃ and allowed to react at that temperature overnight, after the reaction was complete, heating was stopped, the organic phase was washed three times with water, the aqueous phase was extracted with dichloromethane and the organic phases were combined. The organic phase was dried and concentrated to give a crude product, which was further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: ethyl acetate 1: 1, V/V) to give 3.0g of a white solid with a yield of 78%. Ms (ei): m/z: 384.18[ M ]⁺]。Anal.calcd for C₁₉H₁₅BrNOP(％)：C 59.40，H 3.94，N 3.65；found：C 59.38，H 3.98，N 3.62。

(Synthesis of Compound 71)

The synthetic route for compound 71 is shown below:

under nitrogen, adding the intermediate 2(10mmol, 3.84g), anhydrous potassium carbonate (20mmol, 2.76g), 4- (diphenylamino) phenylboronic acid (12mmol, 3.47g), tetrakis (triphenylphosphine palladium) (0.2mmol, 230mg) and 100mL of a mixed solvent (toluene: water: ethanol ═ 5: 1: 1, V/V) in sequence into a clean 250mL three-necked flask, heating the system to reflux, reacting overnight under reflux, stopping heating after the reaction is completed, and cooling the reaction system to room temperature. The reaction solution was poured into about 200mL of water, extracted with dichloromethane, and 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 2: 1, V/V) to obtain 2.3g of a white solid with a yield of 75%. Ms (ei): m/z: 548.55[ M ]⁺]。Anal.calcd for C₃₇H₂₉N₂OP (%): c81.00, H5.33, N5.11; found: c80.98, H5.36, N5.08. The fluorescence spectra (PL) of the compound of example 1 of the present invention (compound 71) in different solvents are shown in fig. 1.

Example 2: synthesis of Compound 72

(Synthesis of Compound 72)

The synthetic route for compound 72 is shown below:

under the nitrogen condition, adding an intermediate 2(10mmol, 3.84g), anhydrous potassium carbonate (20mmol, 2.76g), 4- (bis (4-tert-butylphenyl) amino) phenylboronic acid (12mmol, 4.81g), tetrakis (triphenylphosphine palladium) (0.2mmol, 230mg) and 100mL of a mixed solvent (toluene: water: ethanol ═ 5: 1: 1, V/V) in sequence into a clean 250mL three-necked bottle, heating the system to reflux, reacting the system in a reflux state overnight, stopping heating after the reaction is finished, automatically cooling the reaction system to room temperature, and cooling the reaction system to room temperatureThe solution was poured into about 200mL of water, extracted with dichloromethane, and 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 ═ 2: 1, V/V) to obtain 4.6g of a white solid with a yield of 70%. Ms (ei): m/z: 660.76[ M ]⁺]。Anal.calcd for C₄₅H₄₅N₂OP (%): c81.79, H6.86, N4.24; found: c81.74, H6.88, N4.21. The fluorescence spectra (PL) of the compound of example 2 of the present invention (compound 72) in different solvents are shown in fig. 2.

Example 3: synthesis of Compound 172

(Synthesis of intermediate 3)

The synthetic route for intermediate 3 is shown below:

adding the intermediate 1(10mmol, 3.07g), dibromohydantoin (30mmol, 8.58g) and 150mL toluene in sequence into a clean 250mL single-neck bottle, gradually heating the system to 100 ℃, reacting at the temperature overnight, stopping heating after the reaction is finished, washing an organic phase with dichloromethane for three times, extracting an aqueous phase with dichloromethane, combining the organic phases, drying and concentrating the organic phase to obtain a corresponding crude product, and further purifying the crude product by column chromatography (350-mesh silica gel, eluent is petroleum ether, ethyl acetate is 1: 1, V/V) to obtain 3.2g of a white solid with the yield of 68%. Ms (ei): m/z: 463.05[ M ]⁺]。Anal.calcd for C₁₉H₁₄Br₂NOP(％)：C 49.28，H 3.05，N 3.02；found：C 49.25，H 3.08，N 3.01。

(Synthesis of Compound 172)

The synthetic route for compound 172 is shown below:

to a clean 250mL three-necked flask, under nitrogen, were added intermediate 3(10mmol, 4.63g), anhydrous potassium carbonate (40mmol, 5.52g), and 4- (diphenylamino)Phenylboronic acid (24mmol, 6.94g), tetrakis (triphenylphosphine palladium) (0.4mmol, 460mg) and 150mL of mixed solvent (toluene: water: ethanol ═ 5: 1: 1, V/V), the system was heated to reflux and reacted under reflux overnight, after the reaction was completed, heating was stopped, the reaction system was cooled to room temperature by itself, the reaction solution was poured into about 200mL of water, 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 ═ 2: 1, V/V) to obtain 6.2g of white solid, yield 76%. Ms (ei): m/z: 791.18[ M ]⁺]。Anal.calcd for C₅₅H₄₂N₃OP(％)：C 83.42，H 5.35，N 5.31；found：C 83.39，H 5.38，N 5.26。

Example 4: synthesis of Compound 175

(Synthesis of Compound 175)

The synthetic route for compound 175 is shown below:

under nitrogen, intermediate 3(10mmol, 4.63g), anhydrous potassium carbonate (40mmol, 5.52g), 4- (bis (4-tert-butylphenyl) amino) phenylboronic acid (24mmol, 9.62g), tetrakis (triphenylphosphine palladium) (0.4mmol, 460mg) and 150mL of a mixed solvent (toluene: water: ethanol ═ 5: 1: 1, V/V) were added in this order to a clean 250mL three-necked flask, the system was heated to reflux and reacted under reflux overnight, after completion of the reaction, heating was stopped, the reaction system was cooled to room temperature by itself, the reaction solution was poured into about 200mL of water, 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 was petroleum ether: dichloromethane ═ 2: 1, V/V) to give 7.2g of a white solid with a yield of 71%. Ms (ei): m/z: 1016.17[ M ]⁺]。Anal.calcd for C₇₁H₇₄N₃OP(％)：C 83.90，H 7.34，N 4.13；found：C 83.88，H 7.38，N 4.09。

Example 5: synthesis of Compound 271

(Synthesis of intermediate 4)

The synthetic route for intermediate 4 is shown below:

aniline (30mmol, 2.8g) and 150mL of anhydrous Tetrahydrofuran (THF) were added sequentially to a dry, clean 250mL three-necked flask under a nitrogen atmosphere, and the system was cooled to-78 deg.C, n-butyllithium (30mmol, 2.4M, 12.5mL) was added dropwise to the system, and after completion of the addition, stirring was continued at that temperature for 30mm, followed by addition of 10mL of ethyl [1,1' -biphenyl]After the dropwise addition of a tetrahydrofuran solution of (E) -2-yl (phenyl) phosphonate (10mmol, 3.22g), the reaction is continued at-78 ℃ for 2h, then the cold bath is removed, the system is automatically raised to room temperature and the reaction is continued at room temperature overnight, after the reaction is finished, a small amount of water is added to quench the reaction, the reaction is extracted by dichloromethane, the solvent is evaporated under reduced pressure, and the crude product is purified by column chromatography (350 mesh silica gel, eluent is petroleum ether: ethyl acetate: 2: 1, V/V) to obtain 2.6g of a white solid with the yield of 70%. Ms (ei): m/z: 369.22[ M ]⁺]。Anal.calcd for C₂₄H₂₀NOP(％)：C 78.03，H 5.46，N 3.79；found：C 78.02，H 5.49，N 3.76。

(Synthesis of intermediate 5)

The synthetic route for intermediate 5 is shown below:

adding the intermediate 4(10mmol, 3.7g), dibromohydantoin (20mmol, 5.72g) and 150mL toluene in sequence into a clean 250mL single-neck bottle, gradually heating the system to 100 ℃, reacting overnight at the temperature, stopping heating after the reaction is finished, washing an organic phase with dichloromethane for three times, extracting an aqueous phase with dichloromethane, combining the organic phases, drying and concentrating the organic phase to obtain a corresponding crude product, and further purifying the crude product by column chromatography (350-mesh silica gel, eluent is petroleum ether, ethyl acetate is 1: 1, V/V) to obtain 3.2g of a white solid with the yield of 71 percent. Ms (ei): m/z: 446.09[ M ]⁺]。Anal.calcd for C₂₄H₁₇BrNOP(％)：C 64.59，H 3.84，N 3.14；found：C 64.58，H 3.88，N 3.10。

(Synthesis of Compound 271)

The synthetic route for compound 271 is shown below:

under nitrogen, intermediate 5(10mmol, 4.46g), anhydrous potassium carbonate (20mmol, 2.76g), 4- (diphenylamino) phenylboronic acid (12mmol, 3.47g), tetrakis (triphenylphosphine palladium) (0.2mmol, 230mg) and 100mL of a mixed solvent (toluene: water: ethanol ═ 5: 1: 1, V/V) were sequentially added to a clean 250mL three-necked flask, the system was heated to reflux and reacted under reflux overnight, after completion of the reaction, heating was stopped, the reaction system was cooled to room temperature by itself, the reaction solution was poured into about 200mL of water, 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 was petroleum ether: dichloromethane ═ 2: 1, V/V) to give 4.5g of a white solid with a yield of 73%. Ms (ei): m/z: 610.62[ M ]⁺]。Anal.calcd for C₄₂H₃₁N₂OP(％)：C 82.60，H 5.12，N 4.59；found：C 82.58，H 5.16，N 4.57。

Example 6: synthesis of Compound 272

(Synthesis of Compound 272)

The synthetic route for compound 272 is shown below:

under nitrogen, adding intermediate 5(10mmol, 4.46g), anhydrous potassium carbonate (20mmol, 2.76g), 4- (bis (4-tert-butylphenyl) amino) phenylboronic acid (12mmol, 4.81g), tetrakis (triphenylphosphine palladium) (0.2mmol, 230mg) and 100mL of a mixed solvent (toluene: water: ethanol ═ 5: 1: 1, V/V) in sequence into a clean 250mL three-necked flask, heating the system to reflux, reacting the system under reflux overnight, stopping heating after the reaction is finished, and reacting the system under refluxThe reaction mixture was cooled to room temperature by itself, poured into about 200mL of water, extracted with dichloromethane, and 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 ═ 2: 1, V/V) to obtain 4.9g of a white solid with a yield of 64%. Ms (ei): m/z: 755.84[ M ]⁺]。Anal.calcd for C₅₀H₄₇N₂OP(％)：C 83.07，H 6.55，N 3.88；found：C 83.05，H 6.58，N 3.85。

Example 7: preparation of organic electroluminescent device comprising electronic device of Phosphaphenanthridinone derivative according to example 1

Referring to fig. 3, a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode are sequentially formed on a transparent anode formed on a glass substrate in advance.

Specifically, a glass substrate on which an ITO film having a film thickness of 100nm is formed is subjected to ultrasonic treatment in a Decon 90 alkaline cleaning solution, rinsed in deionized water, rinsed three times in acetone and ethanol, baked in a clean environment to completely remove moisture, cleaned with ultraviolet light and ozone, and bombarded at the surface with a low-energy solar ion beam, the glass substrate with the ITO electrode is placed in a vacuum chamber, and the vacuum chamber is evacuated to 4 × 10^-4-2×10^-5Pa, then evaporating 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazatriphenylene (HAT-CN) on the glass substrate with the ITO electrode at the evaporation rate of 0.2nm/s to form a layer with the thickness of 10nm as a hole injection layer; depositing N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB) on the hole injection layer at a deposition rate of 0.2nm/s to form a layer having a thickness of 40nm as a hole transport layer; depositing 3,3 '-bis (N-carbazolyl) -1,1' -biphenyl (mCBP) 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 71) as a host material and at a deposition rate of 0.016nm/s for GD1 as a dopant material to form a layer with a thickness of 20nm as a light-emitting layer, and GD1 was doped at a weight ratio of 8wt%; depositing aluminum (III) bis (2-methyl-8-quinolinolato) -4-phenylphenolate (BALq) on the light-emitting layer at a deposition rate of 0.2nm/s to form a layer having a film thickness of 10nm as a Hole Blocking Layer (HBL); depositing BAlq on the hole blocking layer at a deposition rate of 0.2nm/s to form a layer having a thickness of 40nm as an Electron Transport Layer (ETL); evaporating 8-hydroxyquinoline-lithium (Liq) on the electron transport layer at an evaporation rate of 0.05nm/s to form a layer having a film thickness of 2nm as an electron injection layer; finally, aluminum is vapor-deposited at a vapor deposition rate of 0.5nm/s or more to form a cathode having a film thickness of 100 nm.

Examples 8 to 13: preparation of organic electroluminescent device containing Phosphaphenanthridinone derivative of example 2-6

The organic electroluminescent device was prepared under the same conditions 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 electroluminescent device comparative examples 1 to 2

Testing the performance of the device: the current-luminance-voltage characteristics of the device were obtained from a Keithley source measuring system (Keithley 2400 Sourcemeter, Keithley 2000 Currentmeter) with a calibrated silicon photodiode, the electroluminescence spectra were measured by a Photo research PR655 spectrometer, and the external quantum efficiency of the device was calculated by the method of the literature (adv. mater.,2003,15, 1043-. The device lifetime refers to the time for the luminance to decay to 9000 candelas per square meter (90%) starting at 10000 candelas per square meter. All devices were encapsulated in a nitrogen atmosphere.

The examples relate to compounds having the following structure:

table 1 shows the structures and film thicknesses of the respective layers of the organic electroluminescent devices prepared in examples 7 to 13 and comparative examples 1 to 2 described above as follows:

table 2 shows the results of comparing examples 7 to 13 of the present invention with comparative examples 1 to 2 when a DC voltage is applied to the composition at normal temperature in the atmosphere as follows:

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

Comparative example 2 and example 12 used GD1 as a dopant, and the host material constituting material of example 12 was compound 271 of the present invention. As can be seen from the comparison of the device performance data, example 12 has a lower working voltage, the external quantum efficiency is relatively improved by 15%, and the device lifetime (90%) is also remarkably improved, from 570h to 640 h.

In addition, both comparative example 1 and example 9 used 4CzIPN as the dopant, and the host material of example 9 was the compound 172 of the present invention, and it can be seen from the comparison of the device performance data that example 9 has a longer device lifetime.

Compared with the materials commonly used in the prior art, the phosphaphenanthrone derivative can effectively reduce the working voltage, improve the external quantum efficiency and prolong the service life of devices.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, but rather as the intention of all modifications, equivalents, improvements, and equivalents falling within the spirit and scope of the invention.

Claims

1. A phosphaphenanthrone derivative characterized by being represented by the following general formula (1):

A₁and A₂Each independently represents Ar₁、Ar₂、

the R is¹Represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, NO₂、N(R²)₂、OR²、SR²、C(＝O)R²、P(＝O)R²、Si(R²)₃A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 40 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 40 carbon atoms;

2. The phosphaphenanthrone derivative according to claim 1, further represented by the following general formulae (I) and (II):

3. The phosphaphenanthrone derivative of any one of claims 1-2, wherein Ar is Ar₁、Ar₂、Ar₃And Ar₄Each independently selected from the following groups:

wherein the dotted line represents and L₁、L₂Or a bond to an N atom.

4. The phosphaphenanthrone derivative of any one of claims 1-3, wherein R is₁And R₂Each independently represents phenyl, biphenyl, terphenyl, quaterphenyl, pentabiphenyl, benzothienocarbazole, benzofurocarbazole, benzofluorenocarbazole, benzanthracene, triphenylene, fluorenyl, spirobifluorenyl, triazinyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, indenocarbazolyl, benzimidazolyl, diphenyl-oxadiazolyl, diphenyl boronyl, triphenyl phosphoroxy, diphenyl phosphoroxy, triphenyl silyl, or tetraphenyl silyl.

5. The phosphaphenanthrone derivative according to any one of claims 1 to 4, wherein the phosphaphenanthrone derivative further represented by the general formula (1) is selected from the group consisting of:

6. the synthetic method of the phosphaphenanthrone derivative comprises the following synthetic route:

7. use of the phosphaphenanthrone derivative according to any one of claims 1 to 5 in an electronic device.

8. The electronic device according to claim 7, wherein the electronic device is an organic electroluminescent device, an organic field effect transistor, or an organic solar cell;

9. The electronic device of 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.