阅读说明：本技术 一种芳香胺衍生物及其有机电致发光器件 (Aromatic amine derivative and organic electroluminescent device thereof ) 是由 赵璐 董秀芹 刘辉 赵倩 于 2021-02-09 设计创作，主要内容包括：本发明提供了一种芳香胺衍生物和包含该芳香胺衍生物的有机电致发光器件,涉及有机光电材料技术领域。本发明所述的芳香胺衍生物具有较高的玻璃化转变温度,使材料具有良好的热稳定性与成膜性,将其应用在有机电致发光器件中可延长器件的使用寿命,同时,该类芳香胺衍生物具有优异的空穴传输性能,同时具备合适的HOMO能级,能防止激子向空穴传输层扩散,提高激子在发光层的复合几率,从而降低有机电致发光器件的驱动电压,提高器件的发光效率。(The invention provides an aromatic amine derivative and an organic electroluminescent device containing the same, and relates to the technical field of organic photoelectric materials. The aromatic amine derivative has higher glass transition temperature, so that the material has good thermal stability and film-forming property, the service life of the device can be prolonged when the aromatic amine derivative is applied to an organic electroluminescent device, and meanwhile, the aromatic amine derivative has excellent hole transport performance and proper HOMO energy level, can prevent excitons from diffusing to a hole transport layer, and improves the recombination probability of the excitons in a light-emitting layer, thereby reducing the driving voltage of the organic electroluminescent device and improving the light-emitting efficiency of the device.)

1. An aromatic amine derivative having a structure represented by the following formula i:

in the formula I, Ar is₁～Ar₄At least one of them is selected from substituted or unsubstituted naphthylene, the others are independently selected from substituted or unsubstituted C6-C18 arylene;

a is described₁～A₇At least two of the groups are selected from the groups represented by A-1 or A-2, and the rest is independently selected from any one of hydrogen, deuterium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl and substituted or unsubstituted C6-C30 aryl;

wherein, R is₁、R₂Independently selected from any one of hydrogen, deuterium and alkyl of C1-C6; m is₁An integer selected from 0 to 4, m₂An integer selected from 0 to 4; "" is a connection site;

n is₁、n₂Is selected from 0 or 1.

2. A fragrance as claimed in claim 1Amine derivative characterized in that A is₁～A₇At least two of the groups are selected from any one of the groups represented by A-3-A-6, and the rest is independently selected from any one of hydrogen, deuterium, alkyl of C1-C6, cycloalkyl of C3-C12 and aryl of C6-C18;

3. the aromatic amine derivative according to claim 1, wherein a-1 is selected from any one of the following groups:

4. the aromatic amine derivative according to claim 1, wherein a-2 is selected from any one of the following groups:

5. the aromatic amine derivative according to claim 1, wherein Ar is Ar₁～Ar₄At least one of them is selected from substituted or unsubstituted naphthylene, the others are independently selected from any one of phenylene, biphenylene, terphenylene and naphthylene,

the phenylene group, the biphenylene group, the terphenylene group, and the naphthylene group may be substituted or unsubstituted with one or more substituents selected from the group consisting of deuterium, cyano, methyl, ethyl, isopropyl, tert-butyl, adamantyl, norbornanyl, and phenyl groups, and when the substituents are substituted with a plurality of substituents, the substituents may be the same or different from each other.

6. The aromatic amine derivative according to claim 1, wherein Ar is Ar₁～Ar₄At least one of them is selected from substituted or unsubstituted naphthylene, and the others are independently selected from any one of the following groups:

；

q is an integer of 0 to 6.

7. The aromatic amine derivative according to claim 1, wherein the structure represented by formula i is selected from any one of the following compounds:

8. an organic electroluminescent device comprising an anode, an organic layer and a cathode, wherein the organic layer comprises at least one aromatic amine derivative according to any one of claims 1 to 7.

9. An organic electroluminescent device according to claim 8, wherein the organic layer comprises a hole transport layer containing at least one of the aromatic amine derivatives according to any one of claims 1 to 7.

10. The organic electroluminescent device according to claim 8, wherein the organic layer comprises an electron blocking layer comprising at least one of the aromatic amine derivatives according to any one of claims 1 to 7.

Technical Field

The invention relates to the technical field of organic photoelectric materials, in particular to an aromatic amine derivative and an organic electroluminescent device thereof.

Background

An OLED is called an organic light-emitting diode (OLED), and refers to an organic semiconductor formed by using an extremely thin organic material coating and a substrate and emitting light when current passes through the organic semiconductor. The OLED is an indispensable element in a new generation of display screen, and is the basis of development of terminal fields in various industries such as consumer electronics, automotive electronics, wearable equipment and the like in the electronic industry.

As a new generation display technology, the OLED attracts attention at home and abroad, and compared with other displays, the OLED has the advantages of no alternatives, such as self-luminescence, thin panel, flexible shape design, low driving voltage, wide light-emitting viewing angle, low power consumption, high response speed, and the like, and is known as a star flat display in the twenty first century, and is also called as a "fantasy display" by the industry.

The light emission of the OLED belongs to electroluminescence, and because of the importance in application, the electroluminescence phenomenon is always a science of great interest, and it has been known as a light emitting mode capable of generating cold light. The electroluminescent device is first subjected to an inorganic electroluminescent device and then an organic electroluminescent device appears, and due to some special properties of organic materials, the performance of the device is greatly improved.

The light emitting principle of the OLED is as follows: under the drive of forward voltage, holes are injected from the anode, electrons are injected from the cathode, the holes are in hopping transmission on the highest occupied molecular orbit, the electrons are in hopping transmission on the lowest unoccupied molecular orbit, the holes and the electrons are combined in the luminescent layer to form electron-hole pairs, namely excitons, which are in the constraint energy level, the excitons are in radiation transition to emit photons, and energy is released.

An organic light emitting device based on the above light emitting principle generally includes an anode, a cathode, and an organic layer interposed therebetween, and the organic layer includes a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and the like, which are made of corresponding materials, respectively, a hole injection material, a hole transport material, a light emitting material, an electron transport material, and the like. The currently commonly used hole transport material is NPB, and although NPB has excellent hole transport performance, NPB has a low glass transition temperature, so that NPB is easily crystallized under a high temperature condition, and the performance of an organic electroluminescent device is reduced, so that the organic electroluminescent device has problems of high driving voltage, low luminous efficiency and the like, and therefore, the development of a hole transport material with excellent performance is urgently needed.

Disclosure of Invention

In order to solve the above problems, an object of the present invention is to provide an aromatic amine derivative having excellent properties, which is useful as a hole transport layer, an electron blocking layer, or the like of an organic electroluminescent device. It is another object of the present invention to provide an organic electroluminescent device comprising the aromatic amine derivative, which has a low driving voltage, high luminous efficiency, and a good lifespan.

The invention is realized by the following technical scheme:

an aromatic amine derivative having a structure represented by the following formula i:

in the formula I, Ar is₁～Ar₄At least one of them is selected from substituted or unsubstituted naphthylene, the others are independently selected from substituted or unsubstituted C6-C18 arylene;

a is described₁～A₇At least two of them are selected from the group represented by A-1 or A-2The rest is any one of hydrogen, deuterium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl and substituted or unsubstituted C6-C30 aryl;

wherein, R is₁、R₂Independently selected from any one of hydrogen, deuterium and alkyl of C1-C6; m is₁An integer selected from 0 to 4, m₂An integer selected from 0 to 4; "" is a connection site;

n is₁、n₂Is selected from 0 or 1.

An organic electroluminescent device comprising an anode, an organic layer and a cathode, the organic layer comprising at least one of the aromatic amine derivatives.

The invention has the beneficial effects that:

the aromatic amine derivative provided by the invention has higher glass transition temperature, so that the material has good thermal stability and film-forming property, thereby effectively inhibiting the crystallization of the material, further reducing the aging rate of a device and prolonging the service life of the device; the aromatic amine derivative provided by the invention has excellent hole transport performance, and can effectively improve the carrier mobility, so that the driving voltage of a device is reduced, and the luminous efficiency of the device is improved; meanwhile, the aromatic amine derivative has a proper HOMO energy level, so that excitons can be prevented from diffusing to a hole transport interface or one side of a hole transport layer, the recombination probability of the excitons in a light emitting layer is improved, and the light emitting efficiency of the device is further improved.

In conclusion, the aromatic amine derivatives provided by the invention are organic electroluminescent materials with excellent performance, and when the aromatic amine derivatives are used as a hole transport layer or an electron blocking layer in an organic electroluminescent device, the aromatic amine derivatives can reduce the driving voltage of the device, improve the luminous efficiency of the device and prolong the service life of the device.

Drawings

FIG. 1 is a drawing showing the preparation of Compound 1-1 of the present invention¹H NMR chart; drawing (A)2 is a compound of the invention 1-9¹H NMR chart;

FIG. 3 is a drawing of compounds 1-29 of the present invention¹H NMR chart; FIG. 4 is a drawing of compounds 1-186 of the present invention¹H NMR chart;

FIG. 5 is a drawing of compounds 1-209 of the present invention¹H NMR chart; FIG. 6 is a film profile of a sample prepared from the compound of the present invention;

fig. 7 is a current-voltage curve diagram of a single-carrier device prepared according to an embodiment of the invention.

Detailed Description

The following will clearly and completely describe the technical solutions of the specific embodiments of the present invention, 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 scope of protection of the present invention.

In the present specification, "+" means a moiety linked to another substituent.

The "substitution" as referred to herein means that a hydrogen atom in some functional groups is replaced with another atom or functional group (i.e., substituent), and the substituted position is not limited as long as the position is a position at which a hydrogen atom is substituted, and when two or more are substituted, two or more substituents may be the same as or different from each other.

The "substituted or unsubstituted" as referred to herein means not substituted or substituted with one or more substituents selected from the group consisting of: deuterium, a halogen atom, an amino group, a cyano group, a nitro group, an alkyl group having from C1 to C30, a cycloalkyl group having from C3 to C20, an alkoxy group having from C1 to C30, an aryl group having from C6 to C60, an aryloxy group having from C6 to C60, and a heteroaryl group having from C2 to C60, preferably deuterium, a halogen atom, a cyano group, a nitro group, an alkyl group having from C1 to C12, a cycloalkyl group having from C3 to C12, an aryl group having from C6 to C30, and a heteroaryl group having from C2 to C30, wherein when substituted with a plurality of substituents, the plurality of substituents are the same or different from each other; preferably, it means unsubstituted or substituted with one or more substituents selected from the group consisting of: deuterium, cyano, methyl, ethyl, isopropyl, tert-butyl, adamantyl, norbornyl, phenyl, and when substituted with a plurality of substituents, the plurality of substituents may be the same or different from each other.

The alkyl group in the present invention refers to a hydrocarbon group obtained by removing one hydrogen atom from an alkane molecule, and may be a straight chain or branched chain, and the number of carbon atoms thereof is not particularly limited, but is preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, and most preferably 1 to 6 carbon atoms. Specific examples may include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, pentyl, n-pentyl, isopentyl, neopentyl, 1-methylpentyl, 1-methylhexyl, and the like, but are not limited thereto.

The cycloalkyl group in the present invention means a hydrocarbon group obtained by removing one hydrogen atom from a cycloalkane molecule, and preferably has 3 to 12 carbon atoms, more preferably 3 to 8 carbon atoms, and particularly preferably 3 to 6 carbon atoms, and examples thereof may include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, and the like.

Alkoxy in the context of the present invention means-O-alkyl, wherein alkyl is as previously defined.

The aryl group in the present invention refers to a monovalent group formed by removing one hydrogen atom from an aromatic nucleus carbon of an aromatic hydrocarbon molecule, and may be a monocyclic aryl group, a polycyclic aryl group or a condensed ring aryl group, and the number of carbon atoms is not particularly limited, and preferably has 6 to 60 carbon atoms, more preferably 6 to 30 carbon atoms, particularly preferably 6 to 20 carbon atoms, and most preferably 6 to 14 carbon atoms. Specific examples may include phenyl, biphenyl, terphenyl, naphthyl, anthracyl, phenanthryl, triphenylene, pyrenyl, fluorenyl, perylenyl, fluoranthenyl, and the like, but are not limited thereto.

The aryloxy group in the present invention means an-O-aryl group, wherein the aryl group is as previously defined.

The heteroaryl group of the present invention may contain one or more of N, O, P, S, Si and Se as heteroatoms, and if two heteroatoms are contained in the heteroaryl group, the two heteroatoms may be the same or different. It may be a monocyclic heteroaryl group, a polycyclic heteroaryl group or a fused ring heteroaryl group, and the number of carbon atoms is not particularly limited, and preferably has 2 to 60 carbon atoms, more preferably 2 to 30 carbon atoms, particularly preferably 2 to 20 carbon atoms, and most preferably 2 to 12 carbon atoms. Specific examples may include thienyl, pyrrolyl, furyl, imidazolyl, thiazolyl, oxazolyl, oxadiazolyl, thiadiazolyl, pyridyl, bipyridyl, pyrazinyl, pyridazinyl, pyrimidinyl, triazinyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, phenothiazinyl, phenoxazinyl, indolyl, carbazolyl, N-arylcarbazolyl, N-heteroarylcarbazolyl, benzoxazolyl, benzothiazolyl, benzimidazolyl, benzothienyl, benzofuranyl, dibenzofuranyl, dibenzothienyl, and the like, but are not limited thereto.

The arylene group in the present invention refers to a divalent group formed by removing two hydrogen atoms from an aromatic core carbon of an aromatic hydrocarbon molecule, and may be a monocyclic arylene group, a polycyclic arylene group or a condensed ring arylene group, and the number of carbon atoms is not particularly limited, and preferably has 6 to 60 carbon atoms, more preferably 6 to 30 carbon atoms, particularly preferably 6 to 20 carbon atoms, and most preferably 6 to 14 carbon atoms, and specific examples may include phenylene, biphenylene, terphenylene, naphthylene, anthrylene, phenanthrylene, triphenylene, pyrenylene, fluorenylene, peryleneene, fluoranthenylene, and the like, but are not limited thereto.

The term "integer selected from 0 to M" as used herein means any one of the integers having a value selected from 0 to M, including 0,1, 2 … M-2, M-1, M. For example, "m₁The integer selected from 0 to 4 "means m₁Selected from 0,1, 2,3, 4; "m₂The integer selected from 0 to 4 "means m₂Selected from 0,1, 2,3, 4; "q is an integer selected from 0 to 6" means that q is selected from 0,1, 2,3, 4,5, 6; and so on.

As used herein, "at least one" means one, two, three, four, and if allowed more.

The term "at least two" as used herein means two, three, four, five, six, seven, and if permitted more.

The invention provides an aromatic amine derivative, which has a structure shown in the following chemical formula I:

in the formula I, Ar is₁～Ar₄At least one of them is selected from substituted or unsubstituted naphthylene, the others are independently selected from substituted or unsubstituted C6-C18 arylene;

a is described₁～A₇At least two of the groups are selected from the groups represented by A-1 or A-2, and the rest is independently selected from any one of hydrogen, deuterium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl and substituted or unsubstituted C6-C30 aryl;

wherein, R is₁、R₂Independently selected from any one of hydrogen, deuterium and alkyl of C1-C6; m is₁An integer selected from 0 to 4, m₂An integer selected from 0 to 4;

n is₁、n₂Is selected from 0 or 1.

Preferably, when A is₅、A₆、A₇When neither A-1 nor A-2 is present, n₁And n₂Cannot be 1 and A simultaneously₁～A₄Cannot be A-2.

Preferably, Ar is₁、Ar₂、Ar₃And/or Ar₄Selected from substituted or unsubstituted naphthylene.

Preferably, A is₁、A₂、A₃、A₄、A₅、A₆And/or A₇Selected from the group represented by A-1 or A-2.

Preferably, the A-1 is selected from A-3 or A-4, and the A-2 is selected from A-5 or A-6.

Preferably, A is₁～A₇Therein is at least provided withTwo groups are selected from any one of the groups represented by A-3-A-6, and the rest is independently selected from any one of hydrogen, deuterium, alkyl of C1-C6, cycloalkyl of C3-C12 and aryl of C6-C18;

preferably, A is₁、A₂Selected from the group represented by A-1 or A-2, wherein A is₃～A₇Independently selected from any one of hydrogen, deuterium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl and substituted or unsubstituted C6-C30 aryl.

Preferably, A is₁、A₃Selected from the group represented by A-1 or A-2, wherein A is₂、A₄～A₇Independently selected from any one of hydrogen, deuterium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl and substituted or unsubstituted C6-C30 aryl.

Preferably, A is₁～A₄Independently selected from any one of hydrogen, deuterium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl and substituted or unsubstituted C6-C30 aryl; a is described₅～A₇At least two of the groups are selected from the groups represented by A-1 or A-2, and the rest is independently selected from any one of hydrogen, deuterium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl and substituted or unsubstituted C6-C30 aryl.

Preferably, A is₅～A₇At least one of them is selected from the group represented by A-1 or A-2, wherein A is₁～A₄At least one of them is selected from the group represented by A-1 or A-2, and the others are independently selected from any one of hydrogen, deuterium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, and substituted or unsubstituted C6-C30 aryl.

Preferably, the A-1 is selected from any one of the following groups:

preferably, the A-2 is selected from any one of the following groups:

preferably, Ar is₁～Ar₄At least one of them is selected from substituted or unsubstituted naphthylene, the others are independently selected from any one of phenylene, biphenylene, terphenylene and naphthylene,

the phenylene group, the biphenylene group, the terphenylene group, and the naphthylene group may be substituted or unsubstituted with one or more substituents selected from the group consisting of deuterium, cyano, methyl, ethyl, isopropyl, tert-butyl, adamantyl, norbornanyl, and phenyl groups, and when the substituents are substituted with a plurality of substituents, the substituents may be the same or different from each other.

More preferably, Ar is₁～Ar₄At least one of them is selected from substituted or unsubstituted naphthylene, and the others are independently selected from any one of the following groups:

q is an integer of 0 to 6.

Most preferably, the structure represented by formula i is selected from any one of the compounds shown below:

some specific structural forms of the aromatic amine derivatives of the present invention are listed above, but the present invention is not limited to the above listed chemical structures, and all the substituents are defined as above and should be included based on the structure shown in formula I.

The invention also provides an organic electroluminescent device which comprises an anode, an organic layer and a cathode, wherein the organic layer comprises at least one of the aromatic amine derivatives.

Preferably, the organic layer includes a hole transport layer including at least one of the aromatic amine derivatives.

Preferably, the organic layer includes an electron blocking layer including at least one of the aromatic amine derivatives.

The organic layer of the organic electroluminescent device of the present invention may include a light-emitting layer, a hole injection layer, a hole transport layer, a hole blocking layer, an electron transport layer, an electron injection layer, an electron blocking layer, and the like, and the organic layer may be formed of a single layer structure or a multilayer structure in which the above organic layers are stacked; also, each of the organic layers may further include one or more layers, for example, the hole transport layer includes a first hole transport layer and a second hole transport layer.

However, the structure of the organic electroluminescent device is not limited thereto, and corresponding functional layers may be added or reduced as needed, for example, the outer side of the cathode of the organic electroluminescent device may further include a cover layer.

Preferably, the device structure of the organic electroluminescent device according to the present invention preferably includes several conditions:

(1) anode/hole transport layer/light emitting layer/electron transport layer/cathode

(2) Anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode

(3) Anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode/capping layer

(4) Anode/hole injection layer/hole transport layer/electron blocking layer/light-emitting layer/electron transport layer/electron injection layer/cathode-

(5) Anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/electron transport layer/electron injection layer/cathode/capping layer

(6) Anode/hole injection layer/hole transport layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode

(7) Anode/hole injection layer/hole transport layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode/capping layer

(8) Anode/hole injection layer/hole transport layer/electron transport layer/light-emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode

(9) Anode/hole injection layer/hole transport layer/electron transport layer/light-emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode/capping layer.

However, the structure of the organic electroluminescent device of the present invention is not limited to the above structure, and multiple organic layers may be omitted or simultaneously provided as necessary.

The materials for the functional layers of the organic electroluminescent device according to the invention can be any materials used in the prior art for said layers.

The anode material has higher work function, and can smoothly inject holes into an organic layer. Specific examples of the anode material include, but are not limited to, the following: metals such as aluminum, silver, copper, gold, vanadium, platinum, palladium, and the like, or alloys thereof; metal oxides such as Indium Tin Oxide (ITO), tin oxide (NESA), Indium Zinc Oxide (IZO), indium oxide (InO), zinc oxide (ZnO), Aluminum Zinc Oxide (AZO), and the like; combinations of oxides and metals, e.g. zinc oxide: aluminium (ZnO: Al), tin oxide: antimony (SnO)₂Sb), etc.; conducting polymers, e.g. poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxy) thiophene](PEDOT), polyaniline, and the like.

The cathode material has a smaller work function, and can smoothly inject electrons into an organic layer. Specific examples of the cathode material include, but are not limited to, the following: metals such as magnesium, silver, aluminum, lead, tin, calcium, lithium, and the like, or alloys thereof; laminate materials such as magnesium/aluminum (Mg/Al), magnesium/silver (Mg/Ag), aluminum/silver (Al/Ag), aluminum/gold (Al/Au), ytterbium/gold (Yb/Au), calcium/magnesium (Ca/Mg), calcium/silver (Ca/Ag), barium/silver (Ba/Ag), and the like.

The hole injection material has better hole injection capability, can reduce the surface roughness of the anode and reduce the hole injection barrier between the anode and the organic layer. Specific examples of the hole injection material include, but are not limited to, the following: metal oxides, e.g. molybdenum trioxide (MoO)₃) Silver oxide (AgO), vanadium pentoxide (V)₂O₅) Etc.; phthalocyanine derivatives such as copper phthalocyanine (CuPc), cobalt phthalocyanine (CoPc), zinc phthalocyanine (ZnPc), iron phthalocyanine (FePc), and the like;aromatic amine derivatives, e.g. triarylamine, tolyldiphenylamine, 4' -tris [ 2-naphthylphenylamino group]Triphenylamine (2T-NATA), 4' -tris (N-3-methylphenyl-N-phenylamino) triphenylamine (m-MTDATA), and the like; cyano-containing organic derivatives such as 1,4,5,8,9, 11-hexaazabenzonitrile (HAT-CN), and the like; conductive polymers such as polyaniline, polythiophene, and the like.

The hole transport material has better hole transport capability and can effectively inject holes into the light-emitting layer. Specific examples of the hole transport material include, but are not limited to, the following: aromatic amine derivatives such as N, N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine (NPB), N ' -diphenyl-N, N ' -bis (3-methylphenyl) -1,1' -biphenyl-4, 4' -diamine (TPD), 4',4 ″ -tris (carbazol-9-yl) triphenylamine (TCTA), and the like; conductive polymers such as polyvinylcarbazole, polysilane, and the like. Preferred are aromatic amine derivatives represented by formula I of the present invention.

The electron blocking material has better electron blocking capability and can block electrons in the luminescent layer. Specific examples of the electron blocking material include, but are not limited to, the following: examples of the organic compound having an electron donating property such as an aromatic amine derivative include 4,4',4 ″ -tris (carbazol-9-yl) triphenylamine (TCTA), N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine (NPB), N ' -diphenyl-N, N ' -bis (3-methylphenyl) -1,1' -biphenyl-4, 4' -diamine (TPD), and the like. Preferred are aromatic amine derivatives represented by formula I of the present invention.

The light-emitting layer of the present invention is capable of receiving holes and electrons and combining them to emit visible light. The light emitting material includes a blue light emitting material, a green light emitting material, and a red light emitting material. Specific examples of the light emitting material include, but are not limited to, materials described below: metal complexes, for example bis (4, 6-difluorophenylpyridine-C2, N) picolinoylium (FIrpic), tris (2-phenylpyridine) iridium (Ir (ppy)₃) (8-Hydroxyquinoline) aluminum (III) (Alq)₃) Bis (1-phenylisoquinoline) (acetylacetonato) iridium (III) (Ir (piq))₂(acac)) and the like; perylene derivatives, styrylamine derivatives, anthracene derivatives, fluorene derivatives, coumarin dyes, quinacridone derivatives, polycyclicSmall organic molecule materials such as aromatic hydrocarbons, diamine anthracene derivatives, carbazole derivatives, and DCM derivatives, for example, 2,5,8, 11-tetra-tert-butylperylene (TBPe), 4' -bis [4- (diphenylamino) styryl]Biphenyl (BDAVBi), 9- (9-phenylcarbazol-3-yl) -10-naphthalen-1-yl) anthracene (PCAN), 9- [4- (2- (7- (N, N-diphenylamino) -9, 9-diethylfluoren-2-yl) vinyl) phenyl]-9-phenyl-fluorene (DPAFVF), coumarin 545T, Quinacridone (QA), 5, 12-Diphenylnaphthonaphthalene (DPT), N10, N10, N10', N10' -tetraphenyl-9, 9' -dianthracene-10, 10' -diamine (BA-TAD), 9',9 "- (5- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) benzene-1, 2, 3-triyl) tris (3, 6-dimethyl-9H-carbazole) (TmCzTrz), 4- (dicyanomethylene) -2-methyl-6- (4-dimethylaminostyryl) -4H-pyran (DCM), and the like.

The light-emitting layer of the present invention may contain only the light-emitting material described above, or may be doped as a guest material into a host material. Specific examples of the host material include, but are not limited to, the following: metal complexes, e.g. tris (8-hydroxyquinoline) aluminium (III) (Alq)₃) 8-hydroxyquinoline zinc (Znq)₂) Etc.; fluorene derivatives, e.g. 2, 7-bis [9, 9-bis (4-methylphenyl) -fluoren-2-yl]9, 9-bis (4-methylphenyl) fluorene (TDAF), etc.; anthracene derivatives such as 9, 10-di (2-naphthyl) Anthracene (AND) AND the like; carbazole derivatives such as 4,4 '-bis (9-Carbazole) Biphenyl (CBP), 4',4 ″ -tris (carbazol-9-yl) triphenylamine (TCTA), and the like.

The hole blocking material has better hole blocking capability and can block holes in the light emitting layer. Specific examples of the hole blocking material include, but are not limited to, the following: conjugated aromatic compounds having electron-withdrawing properties such as imidazole derivatives and phenanthroline derivatives, for example, 1,3, 5-tris (N-phenyl-2-benzimidazole) benzene (TPBi), 4, 7-diphenyl-1, 10-phenanthroline (Bphen), and the like.

The electron transport material has better electron transport capability and can effectively inject electrons into the luminescent layer. Specific examples of the electron transport material include, but are not limited to, the following: metal complexes, e.g. tris (8-hydroxyquinoline) aluminium (III) (Alq)₃) Tris (4-methyl-8-quinolinolato) aluminum (Almq)₃) Etc.; triazole derivatives,Conjugated aromatic compounds having electron-withdrawing properties such as phenanthroline derivatives, pyridine derivatives, imidazole derivatives and the like, for example, triazole derivatives including 3- (biphenyl-4-yl) -4-phenyl-5- (4-tert-butylphenyl) -1,2, 4-Triazole (TAZ), 4, 7-diphenyl-1, 10-phenanthroline (Bphen), 3'- [5' - [3- (3-pyridyl) phenyl ] and the like](TmPyPB), 1,3, 5-tris (N-phenyl-2-benzimidazole) benzene (TPBi), and the like.

The electron injection material has better electron injection capability, and can reduce the electron injection barrier between the cathode and the organic layer. Specific examples of the electron injecting material include, but are not limited to, the following materials: alkali metal compounds, alkaline earth metal compounds, etc., such as lithium fluoride (LiF), sodium chloride (NaCl), cesium fluoride (CsF), lithium oxide (Li)₂O), barium oxide (BaO), and the like.

The organic electroluminescent device according to the present invention can be manufactured by sequentially laminating the above-described structures. The production method may employ a known method such as a dry film formation method or a wet film formation method. Specific examples of the dry film formation method include a vacuum deposition method, a sputtering method, a plasma method, an ion plating method, and the like. Specific examples of the wet film formation method include various coating methods such as a spin coating method, a dipping method, a casting method, and an ink jet method, but are not limited thereto. The organic light-emitting device can be widely applied to the fields of panel display, lighting sources, flexible OLEDs, electronic paper, organic solar cells, organic photoreceptors or organic thin film transistors, signs, signal lamps and the like.

The present invention also provides a method for preparing a compound represented by formula i, which can be prepared by reaction formula 1, substituents can be bonded by a method known in the art, and the kind and position of the substituents or the number of the substituents can be changed according to a technique known in the art.

[ reaction formula 1]

Ar₁～Ar₄、A₁～A₇、n₁、n₂The definition is the same as the above-mentioned definition, X_a、X_b、X₁、X₂Independently selected from any one of I, Br and Cl; the reaction type of the aromatic amine derivative is Buchwald-Hartwig reaction.

Preparation and characterization of the Compounds

Description of raw materials, reagents and characterization equipment:

the present invention is not particularly limited to the starting materials and sources of reagents used in the following examples, and they may be commercially available products or prepared by methods known to those skilled in the art.

The mass spectrum uses British Watts G2-Si quadrupole rod series time-of-flight high resolution mass spectrometer, chloroform is used as solvent;

the element analysis uses a Vario EL cube type organic element analyzer of Germany Elementar company, and the mass of a sample is 5-10 mg;

nuclear magnetic resonance (¹HNMR Spectroscopy) A nuclear magnetic resonance spectrometer model Bruker-510 (Bruker, Germany), 600MHz, CDCl was used₃As solvent, TMS as internal standard.

Synthesis example 1: preparation of intermediate L-6

Synthesis of intermediate C:

2,2 '-diiodo-4, 4' -dibromobiphenyl (56.38g, 100mmol) was dissolved in tetrahydrofuran (300mL) under nitrogen protection, and after dropwise addition of a hexane solvent and n-butyllithium (36mL, 90mmol) at-78 ℃, the mixture was stirred for 1 hour. Trimethyl borate (26mL, 112.8mmol) was then slowly added dropwise, and the reaction was stirred for 2 hours. 2M hydrochloric acid was added dropwise to neutralize and the product was extracted with ethyl acetate and water. Recrystallization from dichloromethane and hexane gave intermediate C (26.38g, 66%) with a solid purity ≧ 99.5% by HPLC.

Synthesis of intermediate L-6:

500mL of toluene solvent was added to a 1L reaction flask under nitrogen protection, then intermediate C (25.98g, 65mmol) was added,starting material L-a (34.08g, 130mmol), K₂CO₃(20.73g, 150mmol) and then the catalyst Pd (PPh) was added₃)₄(0.70g, 0.6mmol), 100mL of distilled water, the temperature was raised to reflux and the reaction was stirred for 10 hours. After the reaction was completed, 100mL of distilled water was added to terminate the reaction. Filtration under reduced pressure gave crude intermediate L-5, which was washed three times with distilled water and then recrystallized from toluene, ethanol (10:1) to give intermediate L-6(27.16g, 72% yield). The purity of the solid is not less than 99.7 percent by HPLC detection. Mass spectrum m/z: 578.1126 (theoretical value: 578.1184).

Synthesis example 2: preparation of intermediate L-7

The same procedure was repeated except for replacing the starting material L-a 'in Synthesis example 1 with an equimolar amount of the starting material L-a', to give intermediate L-7(21.14g, 65%). The purity of the solid is not less than 99.2 percent by HPLC detection. Mass spectrum m/z: 498.0591 (theoretical value: 498.0558).

Synthetic example 3: preparation of intermediate L-5

The same procedure was repeated except for replacing the starting material 1 in Synthesis example 1 with an equimolar amount of the starting material 2 to give intermediate L-5(19.72g, 68%). The purity of the solid is not less than 99.7 percent by HPLC detection. Mass spectrum m/z: 444.0105 (theoretical value: 444.0088).

Synthetic example 4: preparation of Compound 1-1

Step 1: synthesis of intermediate A-1

A toluene solvent (600mL), M-1(8.59g, 60mmol), N-1(17.48g, 60mol), palladium acetate (0.20g, 0.85mmol), sodium tert-butoxide (11.24g, 0.117mol), and tri-tert-butylphosphine (9.0mL of a 1.0M solution in toluene) were added sequentially to a 1L reaction flask under nitrogen atmosphere and reacted at 100 ℃ for 2 hours. After the reaction was stopped, the mixture was cooled to room temperature, filtered through celite, the filtrate was concentrated, recrystallized from methanol, filtered with suction and rinsed with methanol to give a recrystallized solid, intermediate a-1(16.54g, yield 78%), and purity ≧ 99.3% by HPLC.

Step 2: synthesis of Compound 1-1

Under nitrogen protection, a 1L reaction flask was charged with toluene solvent (600mL), L-1(5.62g, 18mmol), intermediate A-1(14.14g, 40mmol), and Pd in that order₂(dba)₃(0.50g, 0.54mmol), BINAP (1.12g, 1.8mmol) and sodium tert-butoxide (4.95g, 50.4mmol), dissolved with stirring, and reacted under reflux under a nitrogen atmosphere for 24 hours, after completion of the reaction, the reaction solution was washed with dichloromethane and distilled water, and subjected to extraction by separation. The organic layer was dried over anhydrous magnesium sulfate, filtered, and then the solvent was removed, followed by washing with cyclohexane: separating, purifying and refining ethyl acetate (10:1) by column chromatography as eluent to obtain solid compound 1-1(11.11g, yield 72%), and solid purity ≧ 99.7% by HPLC. Mass spectrum m/z: 856.4705 (theoretical value: 856.4756). Theoretical element content (%) C₆₄H₆₀N₂: c, 89.68; h, 7.06; and N, 3.27. Measured elemental content (%): c, 89.72; h, 7.04; and N, 3.26.¹H NMR(600MHz,CDCl₃) (delta, ppm) 8.08(dd,2H),7.86(dd,2H), 7.77-7.74 (m,2H), 7.61-7.57 (m,4H), 7.53-7.50 (m,2H), 7.48-7.45 (m,2H), 7.44-7.41 (m,2H), 7.20-7.15 (m,6H), 7.09-7.06 (m,8H), 2.12-2.08 (m,6H), 2.06-2.02 (m,6H),1.93(d,12H), 1.84-1.80 (m, 6H). The test results prove that the product is a target product.

Synthesis example 5: preparation of Compounds 1-2

Compound 1-2(10.80g) was synthesized by replacing M-1 in Synthesis example 4 with equimolar M-2 and carrying out HPLC analysis to obtain a solid having a purity of 99.6% or more. Mass spectrum m/z: 856.4790 (theoretical value: 856.4756). Theoretical element containsAmount (%) C₆₄H₆₀N₂: c, 89.68; h, 7.06; and N, 3.27. Measured elemental content (%): c, 89.70; h, 7.07; and N, 3.26. The test results prove that the product is a target product.

Synthetic example 6: preparation of Compounds 1-3

Compound 1-3(11.61g) was synthesized by replacing M-1 in Synthesis example 4 with equimolar M-3 and carrying out HPLC analysis with a solid purity of 99.8% or more. Mass spectrum m/z: 870.5672 (theoretical value: 870.5635). Theoretical element content (%) C₆₄H₄₆D₁₄N₂: c, 88.23; h, 8.56; and N, 3.22. Measured elemental content (%): c, 88.25; h, 8.55; and N, 3.23. The test results prove that the product is a target product.

Synthetic example 7: preparation of Compounds 1-5

Synthesizing N-2:

under the protection of nitrogen, raw materials N-2-1(20.49g, 100mmol), N-2-2(26.21g, 100mmol) and 500mL of toluene solvent are added into a three-neck flask, stirred and dissolved, and then K is added into the mixture₂CO₃(20.73g, 150mmol) followed by additional palladium tetrakistriphenylphosphine [ Pd (PPh)₃)₄](0.70g, 0.6mmol) and 100mL of distilled water, heating to 85 ℃ with stirring, refluxing for 6h, after completion of the reaction, cooling to room temperature naturally, filtering, separating the filtrate, collecting the organic phase, rotary evaporating the solvent under reduced pressure, using ethyl acetate and hexane (1: 10) as eluents, and separating by column chromatography to obtain N-2(25.10g, 85% yield). The purity of the solid is not less than 99.6 percent by HPLC detection.

Compound 1-5(10.75g) was synthesized by replacing N-1 in Synthesis example 4 with N-2 in an equimolar amount, and the purity of the solid was ≧ 99.9% by HPLC. Mass spectrum m/z: 864.5215 (theoretical value: 864.5259). Theoretical element content (%) C₆₄H₅₂D₈N₂: c, 88.84; h, 7.92; and N, 3.24. Measured elemental content (%): c, 88.81; h, 7.93; and N, 3.27. The test results prove that the product is a target product.

Synthesis example 8: preparation of Compounds 1-9

Compound 1-9(12.04g) was synthesized by replacing M-1 in Synthesis example 4 with an equimolar amount of M-4 and N-1 with an equimolar amount of N-3, and the purity of the solid was ≧ 99.3% by HPLC. Mass spectrum m/z: 856.4799 (theoretical value: 856.4756). Theoretical element content (%) C₆₄H₆₀N₂: c, 89.68; h, 7.06; and N, 3.27. Measured elemental content (%): c, 89.67; h, 7.07; and N, 3.28.¹H NMR(600MHz,CDCl₃) (delta, ppm) 8.07(dd,2H),8.03(dd,2H), 7.61-7.58 (m,4H),7.54(dd,2H), 7.43-7.38 (m,2H), 7.33-7.29 (m,4H), 7.17-7.15 (m,8H),7.10(dd,4H),7.01(d,2H), 2.12-2.09 (m,6H),2.01(d,12H), 1.87-1.83 (m,6H), 1.82-1.78 (m, 6H). The test results prove that the product is a target product.

Synthetic example 9: preparation of Compounds 1-16

Step1：

Synthesis of intermediate A-5:

synthesis of intermediate A-5(15.91g, 75% yield) by replacing M-1 in Step1 in Synthesis example 4 with M-4 in equimolar amount and replacing N-1 with N-3 in equimolar amount, and by carrying out the same procedure, the solid purity was 99.5% or more by HPLC.

Synthesis of intermediate A-6:

intermediate A-6(14.56g, 80% yield) was synthesized by replacing M-1 in Step1 in Synthesis example 4 with M-4 in an equimolar amount, and the purity of the solid was ≧ 99.8% by HPLC.

Step 2: synthesis of Compounds 1 to 16

Intermediate A-5(14.14g, 40mmol), L-2(14.00g, 40mmol) and sodium tert-butoxide (9.07g, 94mmol) were dissolved in 100mL of dehydrated toluene under nitrogen protection, and a toluene solution of palladium acetate (0.10g, 0.46mmol) and tri-tert-butylphosphine (0.15g, 0.76mmol) was added with stirring and the reaction was refluxed for 8 hours. After cooling, filtration through a celite/silica funnel, the filtrate was distilled under reduced pressure to remove the organic solvent, and the concentrate was recrystallized from toluene and ethanol (12: 1) and filtered to give intermediate B-1(15.90g, 68% yield). The purity of the solid is not less than 99.8 percent by HPLC detection.

Intermediate B-1(14.62g, 25mmol), intermediate A-6(7.59g, 25mmol) and sodium tert-butoxide (5.77g, 60mmol) were dissolved in 100mL of dehydrated toluene under nitrogen protection, and a toluene solution of palladium acetate (0.09g, 0.45mmol) and tri-tert-butylphosphine (0.36g, 1.8mmol) was added with stirring and the mixture was refluxed for 8 hours. After cooling, the mixture was filtered through a celite/silica gel funnel, the organic solvent was removed from the filtrate by distillation under reduced pressure, and the concentrated solution was recrystallized from toluene and ethanol (12: 1), followed by filtration to obtain compounds 1 to 16(12.91g, 64% yield). The purity of the solid is not less than 99.5 percent by HPLC detection. Mass spectrum m/z: 806.4652 (theoretical value: 806.4600). Theoretical element content (%) C₆₀H₅₈N₂: c, 89.29; h, 7.24; and N, 3.47. Measured elemental content (%): c, 89.31; h, 7.23; and N, 3.48. The test results prove that the product is a target product.

Synthetic example 10: preparation of Compounds 1-22

Compound 1-22(13.23g) was synthesized by replacing intermediate A-5 in Synthesis example 9 with an equimolar amount of intermediate A-3, and the purity of the solid was ≧ 99.7% by HPLC. Mass spectrum m/z: 813.5086 (theoretical value: 813.5039). Theoretical elementContent (%) C₆₀H₅₁D₇N₂: c, 88.51; h, 8.05; n, 3.44. Measured elemental content (%): c, 88.49; h, 8.07; and N, 3.45. The test results prove that the product is a target product.

Synthetic example 11: preparation of Compounds 1-29

Compounds 1 to 29(14.13g) were synthesized in the same manner as in the other steps except that intermediate A-5 in Synthesis example 9 was replaced with equimolar intermediate A-7 and intermediate A-6 was replaced with equimolar intermediate A-1. The purity of the solid is not less than 99.4 percent by HPLC detection. Mass spectrum m/z: 882.4986 (theoretical value: 882.4913). Theoretical element content (%) C₆₆H₆₂N₂: c, 89.75; h, 7.08; and N, 3.17. Measured elemental content (%): c, 89.75; h, 7.06; n, 3.19.¹H NMR(600MHz,CDCl₃) (delta, ppm) 8.08(dd,1H),7.86(dd,1H), 7.77-7.74 (m,1H),7.59(dd,8H),7.51(dd,1H), 7.48-7.37 (m,5H), 7.20-7.13 (m,7H), 7.10-7.06 (m,6H), 7.05-7.00 (m,2H), 2.12-2.08 (m,6H), 2.06-2.04 (m,6H),1.93(d,12H), 1.84-1.80 (m, 6H). The test results prove that the product is a target product.

Synthetic example 12: preparation of Compounds 1-44

Compound 1-44(10.82g) was synthesized by replacing L-1 in Synthesis example 4 with equimolar L-3 and carrying out HPLC analysis with a solid purity of 99.8% or higher. Mass spectrum m/z: 780.4485 (theoretical value: 780.4443). Theoretical element content (%) C₅₈H₅₆N₂: c, 89.19; h, 7.23; and N, 3.59. Measured elemental content (%): c, 89.21; h, 7.24; and N, 3.57. The test results prove that the product is a target product.

Synthetic example 13: preparation of Compounds 1-77

Compounds 1 to 77(15.02g) were synthesized in the same manner as in the other steps except that intermediate A-5 in Synthesis example 9 was replaced with equimolar intermediate A-8 and intermediate A-6 was replaced with equimolar intermediate A-9. The purity of the solid is not less than 99.7 percent by HPLC detection. Mass spectrum m/z: 882.4957 (theoretical value: 882.4913). Theoretical element content (%) C₆₆H₆₂N₂: c, 89.75; h, 7.08; and N, 3.17. Measured elemental content (%): c, 89.78; h, 7.09; and N, 3.15. The test results prove that the product is a target product.

Synthesis example 14: preparation of Compounds 1-81

Compound 1-81(11.68g) was synthesized by replacing L-1 in Synthesis example 4 with equimolar L-4 and detecting the solid purity ≧ 99.8% by HPLC. Mass spectrum m/z: 864.5213 theoretical value: 864.5259). Theoretical element content (%) C₆₄H₅₂D₈N₂: c, 88.84; h, 7.92; and N, 3.24. Measured elemental content (%): c, 88.82; h, 7.94; and N, 3.23. The test results prove that the product is a target product.

Synthetic example 15: preparation of Compounds 1-114

Compound No. 1 to 114(11.42g) was synthesized by the same procedure as in Synthesis example 4 except that N-1 was replaced with N-5 in an equimolar amount, and the purity of the solid was ≧ 99.9% by HPLC. Mass spectrum m/z: 856.4710 (theoretical value: 856.4756). Theoretical element content (%) C₆₄H₆₀N₂: c, 89.68; h, 7.06; and N, 3.27. Measured elemental content (%): c, 89.71; h, 7.04; and N, 3.28. The test results prove that the product is a target product.

Synthetic example 16: preparation of Compounds 1-186

Compound 1-186(15.77g) was synthesized by replacing intermediate a-5 and intermediate a-6 in synthesis example 9 with equal moles of intermediate a-8 and intermediate a-1, respectively, and the purity of the solid was ≧ 99.7% by HPLC. Mass spectrum m/z: 940.5737 (theoretical value: 940.5696). Theoretical element content (%) C₇₀H₇₂N₂: c, 89.31; h, 7.71; and N, 2.98. Measured elemental content (%): c, 89.33; h, 7.72; and N, 2.95.¹H NMR(600MHz,CDCl₃) (delta, ppm) 8.08(dd,1H),7.86(dd,1H), 7.77-7.74 (m,1H),7.59(dd,4H),7.51(dd,1H), 7.49-7.45 (m,1H), 7.44-7.41 (m,1H), 7.20-7.13 (m,5H), 7.10-7.06 (m,8H), 7.04-7.00 (m,4H), 2.12-2.08 (m,9H), 2.06-2.02 (m,9H),1.93(d,18H), 1.84-1.80 (m, 9H). The test results prove that the product is a target product.

Synthetic example 17: preparation of Compounds 1-191

Compound 1-191(12.13g) was synthesized by the same procedure except for replacing L-1 in Synthesis example 4 with equimolar L-5, and the purity of the solid was ≧ 99.1% by HPLC. Mass spectrum m/z: 990.5914 (theoretical value: 990.5852). Theoretical element content (%) C₇₄H₇₄N₂: c, 89.65; h, 7.52; n, 2.83. Measured elemental content (%): c, 89.64; h, 7.54; and N, 2.82. The test results prove that the product is a target product.

Synthetic example 18: preparation of Compounds 1-209

Replacement of N-1 in Synthesis example 4 by equimolar of N-Compound 1-209(11.57g) was synthesized by replacing 6, L-1 with equimolar L-6 and carrying out the same procedure, and the purity of the solid was ≧ 99.5% by HPLC. Mass spectrum m/z: 856.4788 (theoretical value: 856.4756). Theoretical element content (%) C₆₄H₆₀N₂: c, 89.68; h, 7.06; and N, 3.27. Measured elemental content (%): c, 89.69; h, 7.04; and N, 3.28.¹H NMR(600MHz,CDCl₃) (delta, ppm) 8.08(dd,2H),7.86(dd,2H), 7.77-7.74 (m,2H),7.51(dd,2H), 7.49-7.41 (m,6H), 7.33-7.28 (m,4H),7.18(dd,2H), 7.16-7.07 (m,8H),6.91(d,2H), 2.12-2.09 (m,6H),2.00(d,12H), 1.87-1.83 (m,6H), 1.82-1.78 (m, 6H). The test results prove that the product is a target product.

Synthetic example 19: preparation of Compounds 1-211

Compound 1-211(11.14g) was synthesized by replacing M-1 in Synthesis example 4 with an equimolar amount of M-3, N-1 with an equimolar amount of N-6, and replacing L-1 with an equimolar amount of L-6, and the purity of the solid was not less than 99.5% by HPLC. Mass spectrum m/z: 870.5690 (theoretical value: 870.5635). Theoretical element content (%) C₆₄H₄₆D₁₄N₂: c, 88.23; h, 8.56; and N, 3.22. Measured elemental content (%): c, 88.24; h, 8.53; and N, 3.25. The test results prove that the product is a target product.

Synthesis example 20: preparation of Compounds 1-152

Compound 1-152(9.79g) was synthesized by replacing N-1 in Synthesis example 4 with N-6 in an equimolar amount and L-1 with L-7 in an equimolar amount, and the purity of the solid was ≧ 99.8% by HPLC. Mass spectrum m/z: 776.4189 (theoretical value: 776.4130). Theoretical element content (%) C₅₈H₅₂N₂: c, 89.65; h, 6.75; and N, 3.61. Measured elemental content (%): c, 89.67; h, 6.73;and N, 3.61. The test results prove that the product is a target product.

The compounds involved in the inventive device examples, comparative device examples and tests are as follows:

and (3) testing the film morphology of the material:

the compounds 1 to 29, the compounds 1 to 186, the compound 191 and the comparative compound 2 of the invention are respectively evaporated on an ITO glass substrate to prepare a sample, the evaporation thickness is 60nm, and the film shapes of the compounds 1 to 29, the compounds 1 to 186 and the compound 191 of the invention are represented by an atomic force microscope. The morphology of each sample film is shown in fig. 6, and the resulting surface roughness values are shown in table 1:

table 1: surface Roughness (RMS) of the Compound

Sample (I)	Surface Roughness (RMS)
		Compounds 1 to 29	0.25
Compounds 1 to 186	0.21
		Compound 1-191	0.23
Comparative Compound 2	0.42

The results in table 1 show that the compounds of the present invention can form continuous and uniform thin films, and compared with comparative compound 2, the Roughness (RMS) of the compounds of the present invention is significantly lower than that of comparative compound 2, which indicates that the compounds of the present invention can obtain more uniform, stable and flat thin films by evaporation and have better film forming properties.

Device example 1: preparation of a single-carrier device 1

Firstly, an ITO glass substrate is placed in distilled water for cleaning for 2 times, ultrasonic cleaning is carried out for 30 minutes, then the ITO glass substrate is repeatedly cleaned for 2 times, ultrasonic cleaning is carried out for 10 minutes, after the cleaning of the distilled water is finished, isopropanol, acetone and methanol solvents are adopted for carrying out ultrasonic cleaning in sequence, then the ITO glass substrate is dried on a hot plate heated to 120 ℃, the dried substrate is transferred into a plasma cleaning machine, and after 5 minutes of cleaning, the substrate is transferred into an evaporation machine.

Evaporating MoO layer by layer on the ITO glass substrate₃(vapor deposition thickness: 10nm), Compound 1-1 of the present invention (vapor deposition thickness: 60nm), MoO₃(vapor deposition thickness: 10nm) and Al (vapor deposition thickness: 120 nm).

Device example 2: preparation of a single-carrier device 2

A single carrier device 2 was prepared in the same preparation method as in device example 1, substituting compounds 1 to 1 of the present invention in device example 1 for compounds 1 to 9 of the present invention.

Device example 3: preparation of a single-carrier device 3

A single carrier device 3 was produced in the same production method as in device example 1, except that the present compounds 1 to 1 in device example 1 were replaced with the present compounds 1 to 29.

Comparative example 1: preparation of comparative Single Carrier device 1

A comparative single carrier device 1 was prepared in the same manner as in device example 1, except that the inventive compound 1-1 in device example 1 was replaced with the comparative compound 2.

Fig. 7 is a current-voltage curve diagram of a single-carrier device prepared according to an embodiment of the invention. As can be seen from fig. 7, in the region having the diode effect, the slopes of the curves corresponding to the compounds 1 to 1,1 to 9, and 1 to 29 according to the present invention are significantly greater than the slope of the curve corresponding to the comparative compound 2, and thus it can be demonstrated that the compounds according to the present invention have high hole mobility and are advantageous for the injection and transport of holes.

Device example 4: preparation of organic electroluminescent device 4

2-TNATA is sequentially evaporated on an ITO glass substrate to be used as a hole injection layer, the evaporation thickness is 60nm, the compound 1-1 of the invention is evaporated on the hole injection layer to be used as a hole transport layer, the evaporation thickness is 60nm, alpha, beta-AND AND BD are evaporated on the hole transport layer in a vacuum co-evaporation mode, a luminescent layer is formed on the hole injection layer AND the hole transport layer according to the doping ratio of 95:5, the evaporation thickness is 30nm, TPBi is evaporated on the luminescent layer to be used as an electron transport layer, the evaporation thickness is 40nm, lithium fluoride is evaporated on the electron transport layer to be used as an electron injection layer, the evaporation thickness is 0.5nm, then Al is evaporated on the electron injection layer in a vacuum evaporation mode to be used as a cathode, AND the evaporation thickness is 120 nm.

Device embodiments 5 to 20: preparation of organic electroluminescent device 5-20

Organic electroluminescent devices 5 to 20 were produced by the same production method as in device example 4, except that compounds 1 to 2, compounds 1 to 3, compounds 1 to 5, compounds 1 to 9, compounds 1 to 16, compounds 1 to 22, compounds 1 to 29, compounds 1 to 44, compounds 1 to 77, compounds 1 to 81, compounds 1 to 114, compounds 1 to 186, compounds 1 to 191, compounds 1 to 209, compounds 1 to 211, and compounds 1 to 152 of the present invention were used instead of compound 1 to 1 in device example 4.

Comparative example 2: preparation of comparative device 1

Comparative device 1 was prepared in the same manner as in device example 4, except that NPB was used instead of compound 1-1 in device example 4.

Comparative example 3: preparation of comparative device 2

Comparative device 2 was prepared in the same manner as in device example 4, except that compound 1-1 in device example 4 was replaced with comparative compound 1.

Comparative example 4: preparation of comparative device 3

Comparative device 3 was prepared in the same manner as in device example 4, except that compound 1-1 in device example 4 was replaced with comparative compound 2.

Comparative example 5: preparation of comparative device 4

Comparative device 4 was prepared in the same manner as in device example 4, except that compound 1-1 in device example 4 was replaced with comparative compound 3.

Comparative example 6: preparation of comparative device 5

Comparative device 5 was prepared in the same manner as in device example 4, except that compound 1-1 in device example 4 was replaced with comparative compound 4.

Device example 21: preparation of organic electroluminescent device 21

Firstly, an ITO glass substrate with the thickness of 150nm is put into distilled water for cleaning for 2 times, ultrasonic cleaning is carried out for 30 minutes, then the ITO glass substrate is repeatedly cleaned for 2 times, ultrasonic cleaning is carried out for 10 minutes, after the cleaning of the distilled water is finished, isopropanol, acetone and methanol are adopted for carrying out ultrasonic cleaning in sequence, then the ITO glass substrate is dried on a hot plate heated to 120 ℃, the dried substrate is transferred into a plasma cleaning machine, and the substrate is transferred into an evaporation machine after 5 minutes of cleaning.

2-TNATA is sequentially evaporated on the glass substrate to be used as a hole injection layer, the evaporation thickness is 60nm, NPB is evaporated on the hole injection layer to be used as a hole transport layer, the evaporation thickness is 60nm, the compound 1-1 of the invention is evaporated on the hole transport layer to be used as an electron blocking layer, the evaporation thickness is 30nm, alpha, beta-AND AND BD is evaporated on the electron blocking layer in a vacuum co-evaporation mode, a light emitting layer is formed on the electron blocking layer according to a doping ratio of 95:5, the evaporation thickness is 30nm, TPBi is evaporated on the light emitting layer to be used as an electron transport layer, the evaporation thickness is 40nm, lithium fluoride is evaporated on the electron transport layer to be used as an electron injection layer, the evaporation thickness is 0.5nm, then Al is evaporated on the electron injection layer in a vacuum mode to be used as a cathode, AND the evaporation thickness is.

Device examples 22 to 28: preparation of organic electroluminescent devices 22-28

Organic electroluminescent devices 22 to 28 were produced by the same production method as in device example 21, using compounds 1 to 3, compounds 1 to 9, compounds 1 to 29, compounds 1 to 81, compounds 1 to 186, compounds 1 to 191, compounds 1 to 209, and the compounds 1 to 1 in device example 21 of the present invention instead of using the compounds 1 to 1 in device example 21.

Comparative example 7: preparation of comparative device 6

Comparative device 6 was prepared in the same manner as in device example 21, except that TPD was used instead of Compound 1-1 in device example 21.

Comparative example 8: preparation of comparative device 7

Comparative device 7 was prepared in the same manner as in device example 21, except that compound 1-1 in device example 21 was replaced with comparative compound 2.

Comparative example 9: preparation of comparative device 8

Comparative device 8 was prepared in the same manner as in device example 21, except that comparative compound 3 was used instead of compounds 1 to 1 in device example 21.

In the invention, the preparation of the device is completed by adopting a vacuum evaporation system and continuously evaporating under the vacuum uninterrupted condition. The materials are respectively arranged in different evaporation source quartz crucibles, and the temperatures of the evaporation sources can be independently controlled. The thermal evaporation rate of the organic material or the doped parent organic material is generally set at 0.1nm/s, and the evaporation rate of the doped material is adjusted according to the doping ratio; the evaporation rate of the electrode metal is 0.4-0.6 nm/s. Placing the processed glass substrate into an OLED vacuum coating machine, wherein the vacuum degree of the system should be maintained at 5 x 10 in the film manufacturing process^-5And (3) evaporating an organic layer and a metal electrode respectively by replacing a mask plate under Pa, detecting the evaporation speed by using an inficon SQM160 quartz crystal film thickness detector, and detecting the film thickness by using a quartz crystal oscillator. The driving voltage, the luminous efficiency and the CIE color coordinate of the organic electroluminescent device are tested by combining test software, a computer, a K2400 digital source meter manufactured by Keithley of the United states and a PR788 spectral scanning luminance meter manufactured by PhotoResearch of the United states into a combined IVL test system. The lifetime was measured using the M6000OLED lifetime test system from McScience. The environment of the test is atmospheric environment, and the temperature is room temperature. Examples 4 to 20 of the device of the present invention,The results of the test of the light emitting characteristics of the organic electroluminescent devices obtained in comparative examples 2 to 6 are shown in table 2; the structures of the organic electroluminescent devices obtained in the device examples 21 to 28 and the comparative examples 7 to 9 of the present invention for testing the light emitting characteristics are shown in table 3.

Table 2: test result of luminescence property of organic electroluminescent device

According to the test results in table 2, in the case that the compounds of the present invention are used as the hole transport layer of the blue light device in device examples 4 to 20, compared with comparative examples 2 and 3, the organic electroluminescent device prepared by using the compounds of the present invention has the advantages of significantly reduced driving voltage, significantly improved luminous efficiency, and significantly improved service life, when tested under the same current density. Compared with comparative examples 4-6, the driving voltage is improved to a certain extent, the luminous efficiency is improved, and the service life is prolonged.

Table 3: test result of luminescence property of organic electroluminescent device

As can be seen from the test results in table 3, in the case where the compounds of the present invention were used as electron blocking layers of blue devices in device examples 21 to 28, the driving voltage was significantly reduced, and the light emitting efficiency and the service life were significantly improved when the test was performed at the same current density as in comparative example 7. Compared with comparative examples 8 and 9, the organic electroluminescent device prepared by the compound of the invention has the advantages of improved driving voltage, improved luminous efficiency and longer service life when tested under the same current density.

In conclusion, the organic electroluminescent device using the compound of the present invention as a hole transport layer or an electron blocking layer has a lower driving voltage, higher luminous efficiency, and a better lifetime.

It should be noted that while the invention has been particularly described in terms of particular embodiments, it will be apparent to those skilled in the art that numerous changes and modifications can be made without departing from the principles of the invention, and it is intended to cover such changes and modifications as fall within the scope of the invention.