阅读说明：本技术 芳香胺化合物、混合物、组合物及有机电子器件 (Aromatic amine compound, mixture, composition and organic electronic device ) 是由 张晨 何锐锋 李灿楷 宋晶尧 于 2021-01-20 设计创作，主要内容包括：本发明涉及一种芳香胺化合物、混合物、组合物及有机电子器件。该芳香胺化合物具有式(1)所示结构,表现出优异的空穴传输性质及稳定性,可作为有机电致发光器件中的空穴传输层材料既可降低驱动电压,也可提高电致发光效率,以及延长器件的寿命。此外,还可以降低滚降效应、降低制造成本。(The invention relates to an aromatic amine compound, a mixture, a composition and an organic electronic device. The aromatic amine compound has the structure shown in the formula (1), shows excellent hole transport property and stability, can be used as a hole transport layer material in an organic electroluminescent device, can reduce the driving voltage, can improve the electroluminescent efficiency, and can prolong the service life of the device. In addition, the roll-off effect and the manufacturing cost can be reduced.)

1. An aromatic amine compound characterized by having a structure represented by general formula (1):

wherein:

L₁、L₂independently selected from a single bond, or a substituted or unsubstituted aromatic or heteroaromatic group having 6 to 40 ring atoms;

Ar₁、Ar₂independently selected from an aromatic group having 6 to 40 ring atoms which may be substituted or unsubstituted, or a heteroaromatic group or non-aromatic ring system having 5 to 40 ring atoms which may be substituted or unsubstituted;

Ar₃、Ar₄independently selected from the group consisting of absent, or having the structure shown below:

x is selected from N or CR₁；

Y is selected from O, S, S ═ O, SO₂、NR₂、PR₂、CR₂R₃Or SiR₂R₃；

R₁-R₃At each occurrence, is independently selected from: hydrogen, D, straight-chain alkyl having 1 to 20C atoms, straight-chain alkoxy having 1 to 20C atoms, straight-chain thioalkoxy having 1 to 20C atoms, branched or cyclic alkyl having 3 to 20C atoms, branched or cyclic alkoxy having 3 to 20C atoms, branched or cyclic thioalkoxy having 3 to 20C atoms, silylA keto group having 1 to 20C atoms, an alkoxycarbonyl group having 2 to 20C atoms, an aryloxycarbonyl group having 7 to 20C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, CF₃Cl, Br, F, a crosslinkable group, a substituted or unsubstituted aromatic group having 6 to 60 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, a substituted or unsubstituted aryloxy group having 6 to 60 ring atoms, a substituted or unsubstituted heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups;

denotes the attachment site.

2. The aromatic amine compound according to claim 1, having a structure represented by any one of general formula (2) or (3-1) to (3-4):

3. the aromatic amine compound of claim 1, wherein Ar is₁、Ar₂Each independently selected from any one of (B-1) to (B-6):

wherein:

X₁selected from N or CR₄；

Y₁Selected from O, S, S ═ O, SO₂、NR₅、PR₅、CR₅R₆Or SiR₅R₆；

R₄-R₆At each occurrence, is independently selected from: each independently selected from: hydrogen, D, straight-chain alkyl having 1 to 20C atoms, straight-chain alkoxy having 1 to 20C atoms, having 1 to 20C atomsLinear thioalkoxy groups of (a), branched alkyl groups or cyclic alkyl groups having 3 to 20C atoms, branched alkoxy groups or cyclic alkoxy groups having 3 to 20C atoms, branched thioalkoxy groups or cyclic thioalkoxy groups having 3 to 20C atoms, silyl groups, keto groups having 1 to 20C atoms, alkoxycarbonyl groups having 2 to 20C atoms, aryloxycarbonyl groups having 7 to 20C atoms, cyano groups, carbamoyl groups, haloformyl groups, formyl groups, isocyano groups, isocyanate groups, thiocyanate groups, isothiocyanate groups, hydroxyl groups, nitro groups, CF groups₃Cl, Br, F, a crosslinkable group, a substituted or unsubstituted aromatic group having 6 to 60 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, a substituted or unsubstituted aryloxy group having 6 to 60 ring atoms, a substituted or unsubstituted heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups;

Ar₆independently selected from an aromatic or heteroaromatic group having 6 to 20 ring atoms which may be substituted or unsubstituted;

adjacent R₅And R₆With or without a ring of interconnects.

4. The aromatic amine compound of claim 3, wherein Ar is Ar₁、Ar₂Each independently selected from one of the following groups:

n is selected from 0, 1,2,3 or 4.

5. The aromatic amine compound according to claim 4, wherein the aromatic amine compound represented by the general formula (1)Selected from any one of structures (C-1) to (C-11):

6. the aromatic amine compound of claim 4 or 5, wherein n is present in multiple instances, at least one n is selected from 1, and at least one R is present₄Selected from cyclohexyl or adamantyl.

7. The aromatic amine compound according to any one of claims 1 to 5, wherein L is₁、L₂Independently selected from a single bond, or the group shown below:

8. a mixture comprising an aromatic amine compound according to any one of claims 1 to 7, and at least another organic functional material selected from at least one of a hole injecting material, a hole transporting material, an electron injecting material, an electron blocking material, a hole blocking material, a light emitting material, a host material, and an organic dye.

9. A composition comprising at least one aromatic amine compound according to any one of claims 1 to 7, or a mixture according to claim 8, and at least one organic solvent.

10. An organic electronic device comprising a first electrode, a second electrode, one or more organic functional layers disposed between the first electrode and the second electrode, wherein the organic functional layers comprise an aromatic amine compound according to any one of claims 1 to 7, or a mixture according to claim 8, or are prepared from a composition according to claim 9.

11. The organic electronic device according to claim 10, wherein the organic functional layer comprises at least one hole transport layer or electron blocking layer comprising the aromatic amine compound according to any one of claims 1 to 7, or the mixture according to claim 8, or prepared from the composition according to claim 9.

12. The organic electronic device according to claim 11, wherein the organic functional layer further comprises a light-emitting layer, and a material of the light-emitting layer comprises a metal complex represented by general formula (6):

wherein:

q is selected from 1 or 2;

Ar₇when occurring multiple times, is independently selected from substituted or unsubstituted heteroaromatic groups with 5 to 40 ring atoms;

Ar₈when occurring multiple times, is independently selected from an aromatic group with 6 to 40 substituted or unsubstituted ring atoms, or a heteroaromatic group with 5 to 40 substituted or unsubstituted ring atoms;

R₇-R₈at each occurrence, is independently selected from: hydrogen, D, a straight-chain alkyl group having 1 to 20C atoms, a branched or cyclic alkyl group having 3 to 20C atoms, a substituted or unsubstituted aromatic group having 6 to 60 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, or a combination of these groups.

13. The organic electronic device according to claim 12, wherein the general formula (6) is selected from any one of general formulae (7-1) to (7-3):

wherein:

a is selected from 0, 1,2,3,4, 5 or 6, b is selected from 0, 1,2,3 or 4;

R₉-R₁₀at each occurrence, is independently selected from: d, a straight-chain alkyl group having 1 to 20C atoms, a branched or cyclic alkyl group having 3 to 20C atoms, a substituted or unsubstituted aromatic group having 6 to 30 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms, or a combination of these groups.

Technical Field

The invention relates to the technical field of organic electroluminescence, in particular to an aromatic amine compound, a mixture, a composition and an organic electronic device.

Background

The organic photoelectric material has diversity in synthesis, relatively low manufacturing cost and excellent optical and electrical properties. Organic Light Emitting Diodes (OLEDs) have the advantages of wide viewing angle, fast response time, low operating voltage, thin panel thickness, etc., in the application of optoelectronic devices, such as flat panel displays and lighting, and thus have a wide potential for development.

The organic electroluminescence phenomenon refers to a phenomenon of converting electric energy into light energy using an organic substance. An organic electroluminescent element utilizing an organic electroluminescent phenomenon generally has a structure including a positive electrode and a negative electrode and an organic functional layer therebetween. In order to improve the efficiency and lifetime of the organic electroluminescent element, the organic functional layer has a multi-layer structure, each layer containing a different organic substance. Specifically, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like may be included. In such an organic electroluminescent element, when a voltage is applied between the two electrodes, holes are injected from the positive electrode into the organic functional layer, electrons are injected from the negative electrode into the organic functional layer, and when the injected holes and electrons meet, excitons are formed, and light is emitted when the excitons transition back to the ground state. The organic electroluminescent element has the characteristics of self-luminescence, high brightness, high efficiency, low driving voltage, wide viewing angle, high contrast and the like.

In order to realize an efficient organic electroluminescent device, development of a transport material is important in addition to development of a high-performance light emitting material. At present, most of transmission materials are micromolecular materials based on carbazole derivatives, and the defects of unbalanced hole and electron transmission still exist, so that the service life of devices using the compounds is short.

In order to realize color display, red, green and blue devices are generally required, and a red device has a light-emitting layer material with HOMO and LUMO orbital energy levels different from those of green and blue devices, and a red light-emitting layer material with a triplet energy level significantly lower than those of green and blue devices, and a red device generally has a hole transport material with an energy level different from that of the green and blue devices. In order to allow the positive negative carriers to sufficiently recombine in the light emitting layer, the hole transport material immediately adjacent to the light emitting layer should also have a suitable LUMO energy level to block the flow of electrons from the light emitting layer to the hole transport material.

In order to improve the efficiency and lifetime of organic electroluminescent devices, especially red OLED devices, new hole transport materials are in urgent need to be developed.

Disclosure of Invention

Based on this, it is an object of the present invention to provide an aromatic amine compound, a mixture, a composition and an organic electronic device, which improve the efficiency and lifetime of the device.

The technical scheme is as follows:

an aromatic amine compound having a structure represented by general formula (1):

wherein:

L₁、L₂independently selected from a single bond, or a substituted or unsubstituted aromatic or heteroaromatic group having 6 to 40 ring atoms;

Ar₃、Ar₄independently selected from the group consisting of absent, or having the structure shown below:

wherein:

x is selected from N or CR₁；

Y is selected from O, S, S ═ O, SO₂、NR₂、PR₂、CR₂R₃Or SiR₂R₃；

R₁-R₃At each occurrence, is independently selected from: hydrogen, D, straight-chain alkyl having 1 to 20C atoms, straight-chain alkoxy having 1 to 20C atoms, straight-chain thioalkoxy having 1 to 20C atoms, branched or cyclic alkyl having 3 to 20C atoms, branched or cyclic alkoxy having 3 to 20C atoms, branched or cyclic thioalkoxy having 3 to 20C atoms, silyl, keto having 1 to 20C atoms, alkoxycarbonyl having 2 to 20C atoms, aryloxycarbonyl having 7 to 20C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanato, thiocyanate, isothiocyanate, hydroxyl, nitro, CF, and isocyano₃Cl, Br, F, a crosslinkable group, a substituted or unsubstituted aromatic group having 6 to 60 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, a substituted or unsubstituted aryloxy group having 6 to 60 ring atoms, a substituted or unsubstituted heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups.

Ar₁、Ar₂Independently selected from an aromatic group having 6 to 40 ring atoms which may be substituted or unsubstituted, or a heteroaromatic group or non-aromatic ring system having 5 to 40 ring atoms which may be substituted or unsubstituted;

denotes the attachment site.

The invention also provides a mixture, which comprises the aromatic amine compound and at least one other organic functional material, wherein the other organic functional material is at least one selected from a hole injection material, a hole transport material, an electron injection material, an electron blocking material, a hole blocking material, a light emitting material, a host material and an organic dye.

The invention also provides a composition which comprises the aromatic amine compound or the mixture and at least one organic solvent.

The invention also provides an organic electronic device comprising a first electrode, a second electrode, one or more organic functional layers positioned between the first electrode and the second electrode, the organic functional layers comprising the aromatic amine compound, or the mixture, or prepared from the composition.

Compared with the prior art, the invention has the following beneficial effects:

the aromatic amine compound provided by the invention has excellent hole transport property, and when the aromatic amine compound is used as a hole transport material in an OLED device, the OLED device with high luminous efficiency and long service life can be obtained, and in addition, the driving voltage can be reduced, and the roll-off effect and the manufacturing cost can be reduced.

The reason is that:

1) two substituents (phenanthrene and arylamine) throughThe two substituents are connected in position, so that the two substituents have larger steric hindrance, the rotation of the substituents is limited, and the molecules have larger rigidity, thereby improving the accumulation of the molecules, and increasing the efficiency, stability and service life of the device;

2) phenanthrene has a large pi-conjugated plane and generates a resonance effect, and thus can suppress side reactions that may occur in a solid phase and improve the performance of an organic light emitting diode. Further, phenanthrene contains three six-membered rings, and has a larger volume than naphthalene and a benzene ring, compared to naphthalene, which contains two six-membered rings, and benzene, which has one six-membered ring. When phenanthrene is linked to arylamine via ortho-positionWhen the steric hindrance of the two substituents is obviously higher than that of the naphthalene or the benzene ring which is connected with the arylamine through the ortho-positionThe steric hindrance of the structure enables molecules containing phenanthrene to have higher molecular rigidity than molecules with naphthalene and benzene rings at corresponding positions, thereby being beneficial to improving the glass transition temperature of the molecules and improving the stability of devices. Meanwhile, due to the steric hindrance of the phenanthrene and the adjacent groups, the conjugated plane of the phenanthrene and the arylamine has a larger dihedral angle, so that the HOMO orbit of the molecule has a tendency of being reduced, the injection efficiency of holes to the light-emitting layer is improved, and the light-emitting efficiency of the device is improved.

Drawings

Fig. 1 is a structural view of a light emitting device according to an embodiment of the present invention, in fig. 1,1 is a substrate, 2 is an anode, 3 is a hole injection layer, 4 is a first hole transport layer, 5 is a second hole transport layer, 6 is a light emitting layer, 7 is an Electron Transport Layer (ETL), 8 is an electron injection layer, and 9 is a cathode.

FIG. 2 is a mass spectrum of Compound 1.

FIG. 3 is a mass spectrum of Compound 14.

FIG. 4 is a mass spectrum of Compound 16.

FIG. 5 is a mass spectrum of Compound 17.

Fig. 6 is a mass spectrum of compound 23.

Fig. 7 is a mass spectrum of compound 24.

Figure 8 is a mass spectrum of compound 28.

Fig. 9 is a mass spectrum of compound 31.

Fig. 10 is a mass spectrum of compound 44.

Detailed Description

The present invention will be described in further detail with reference to specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

In the present invention, the composition and the printing ink, or ink, have the same meaning and may be interchanged.

In the present invention, the aromatic groups, aromatic groups and aromatic ring systems have the same meaning and are interchangeable.

In the context of the present invention, heteroaromatic groups, heteroaromatic and heteroaromatic ring systems have the same meaning and are interchangeable.

In the present invention, "substituted" means that a hydrogen atom in a substituent is substituted by a substituent.

In the present invention, "substituted or unsubstituted" means that the defined group may or may not be substituted. When a defined group is substituted, it is understood to be optionally substituted with art-acceptable groups including, but not limited to: deuterium atom, cyano group, isocyano group, nitro group, halogen atom, C_1-10Alkyl of (C)_1-10Alkoxy group of (C)_1-10Alkylthio of, C_6-30Aryl of (C)_6-30Aryloxy group of (A), C_6-30Arylthio group of (A), C_3-30Heteroaryl of (A), C_1-30Silane group of (C)_2-10Alkylamino group of (2), C_6-30Or a combination of the foregoing groups, and the like.

In the present invention, the "number of ring atoms" represents the number of atoms among atoms constituting the ring itself of a structural compound (for example, a monocyclic compound, a condensed ring compound, a crosslinked compound, a carbocyclic compound, and a heterocyclic compound) in which atoms are bonded in a ring shape. When the ring is substituted with a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The "number of ring atoms" described below is the same unless otherwise specified. For example, the number of ring atoms of the benzene ring is 6, the number of ring atoms of the naphthalene ring is 10, and the number of ring atoms of the thienyl group is 5.

"aryl or aromatic group" means an aromatic hydrocarbon group derived by removing one hydrogen atom from an aromatic ring compound, and may be a monocyclic aromatic group, or a fused ring aromatic group, or a polycyclic aromatic group, at least one of which is an aromatic ring system for polycyclic ring species. For example, "substituted or unsubstituted aryl group having 6 to 40 ring atoms" means an aryl group containing 6 to 40 ring atoms, preferably a substituted or unsubstituted aryl group having 6 to 30 ring atoms, more preferably a substituted or unsubstituted aryl group having 6 to 18 ring atoms, particularly preferably a substituted or unsubstituted aryl group having 6 to 14 ring atoms, and the aryl group is optionally further substituted; suitable examples include, but are not limited to: benzene, biphenyl, terphenyl, naphthalene, anthracene, fluoranthene, phenanthrene, triphenylene, perylene, tetracene, pyrene, benzopyrene, acenaphthylene, fluorene and derivatives thereof. It will be appreciated that a plurality of aryl groups may also be interrupted by short non-aromatic units (e.g. < 10% of non-H atoms, such as C, N or O atoms), such as in particular acenaphthene, fluorene, or 9, 9-diarylfluorene, triarylamine, diarylether systems should also be included in the definition of aryl groups.

"heteroaryl or heteroaromatic group" means that on the basis of an aryl group at least one carbon atom is replaced by a non-carbon atom which may be a N atom, an O atom, an S atom, etc. For example, "substituted or unsubstituted heteroaryl having 5 to 40 ring atoms" refers to heteroaryl having 5 to 40 ring atoms, preferably substituted or unsubstituted heteroaryl having 6 to 30 ring atoms, more preferably substituted or unsubstituted heteroaryl having 6 to 18 ring atoms, particularly preferably substituted or unsubstituted heteroaryl having 6 to 14 ring atoms, and heteroaryl is optionally further substituted, suitable examples including but not limited to: triazines, pyridines, pyrimidines, imidazoles, furans, thiophenes, benzofurans, benzothiophenes, indoles, carbazoles, pyrroloimidazoles, pyrrolopyrroles, thienopyrroles, thienothiophenes, furopyrroles, furofurans, thienofurans, benzisoxazoles, benzisothiazoles, benzimidazoles, quinolines, isoquinolines, phthalazines, quinoxalines, phenanthridines, primates, quinazolines, quinazolinones, dibenzothiophenes, dibenzofurans, carbazoles, and derivatives thereof.

In the present invention, "alkyl" may mean a linear, branched and/or cyclic alkyl group. The carbon number of the alkyl group may be 1 to 50, 1 to 30, 1 to 20, 1 to 10, or 1 to 6. Non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl, adamantyl and the like.

"halogen" or "halo" refers to F, Cl, Br, or I.

"alkylamino" refers to an amino group substituted with at least one alkyl group. Suitable examples include, but are not limited to: -NH₂、-NH(CH₃)、-N(CH₃)₂、-NH(CH₂CH₃)、-N(CH₂CH₃)₂。

The term "alkoxy" refers to a group having an-O-alkyl group, i.e., an alkyl group as defined above attached to the parent core structure via an oxygen atom. Phrases encompassing this term, suitable examples include, but are not limited to: methoxy (-O-CH)₃or-OMe), ethoxy (-O-CH)₂CH₃or-OEt) and tert-butoxy (-O-C (CH)₃)₃or-OtBu).

In the present invention, "-" denotes a connection site.

In the present invention, when the same group contains a plurality of substituents of the same symbol, the substituents may be the same or different from each other, for example6R on the benzene ring¹May be the same as or different from each other.

In the context of the present invention, a single bond to which a substituent is attached extends through the corresponding ring, meaning that the substituent may be attached at an optional position on the ring, for exampleIn which R is bound to a benzene ringAny of the substitutable sites are linked; such asTo representCan be combined withThe optional position on the middle benzene ring forms a combined ring.

Preferably, the cycloalkyl groups of the present invention are selected from cyclohexane.

The cyclic alkyl or cycloalkyl groups according to the invention have the same meaning and are interchangeable. Preferably, the cycloalkyl group of the present invention is preferably selected from cyclohexane.

In the embodiment of the present invention, the energy level structure of the organic material, the triplet state energy level E_THOMO, LUMO play a key role. These energy levels are described below.

The HOMO and LUMO energy levels can be measured by the photoelectric effect, for example XPS (X-ray photoelectron spectroscopy) and UPS (ultraviolet photoelectron spectroscopy) or by cyclic voltammetry (hereinafter referred to as CV). Recently, quantum chemical methods, such as the density functional theory (hereinafter abbreviated as DFT), have become effective methods for calculating the molecular orbital level.

Triplet energy level E of organic material_T1Can be measured by low temperature Time resolved luminescence spectroscopy, or can be obtained by quantum simulation calculations (e.g., by Time-dependent DFT), such as by commercial software Gaussian 09W (Gaussian Inc.), specific simulation methods can be found in WO2011141110 or as described in the examples below.

Note that HOMO, LUMO, E_T1The absolute value of (c) depends on the measurement method or calculation method used, and even for the same method, different methods of evaluation, for example starting point and peak point on the CV curve, can give different HOMO/LUMO values. Thus, a reasonably meaningful comparison should be made with the same measurement method and the same evaluation method. In the description of the embodiments of the present invention, HOMO, LUMO, E_T1Is based onSimulation of the Time-dependent DFT, but does not affect the application of other measurement or calculation methods.

In the present invention, (HOMO-1) is defined as the second highest occupied orbital level, (HOMO-2) is defined as the third highest occupied orbital level, and so on. (LUMO +1) is defined as the second lowest unoccupied orbital level, (LUMO +2) is the third lowest occupied orbital level, and so on.

The invention aims to provide an aromatic amine compound and application thereof, which improve the efficiency and the service life of a device.

The technical scheme is as follows:

an aromatic amine compound having a structure represented by general formula (1):

wherein:

L₁、L₂independently selected from a single bond, or a substituted or unsubstituted aromatic or heteroaromatic group having 6 to 40 ring atoms;

Ar₃、Ar₄independently selected from the group consisting of absent, or having the structure shown below:

wherein:

x is selected from N or CR₁；

Y is selected from O, S, S ═ O, SO₂、NR₂、PR₂、CR₂R₃Or SiR₂R₃；

R₁-R₃At each occurrence, is independently selected from: hydrogen, D, straight-chain alkyl having 1 to 20C atoms, straight-chain alkoxy having 1 to 20C atoms, straight-chain thioalkoxy having 1 to 20C atoms, branched or cyclic alkyl having 3 to 20C atoms, branched or cyclic alkoxy having 3 to 20C atoms, branched thioalkoxy having 3 to 20C atomsThioalkoxy radicals or cyclic, silyl radicals, keto radicals having 1 to 20C atoms, alkoxycarbonyl radicals having 2 to 20C atoms, aryloxycarbonyl radicals having 7 to 20C atoms, cyano radicals, carbamoyl radicals, haloformyl radicals, formyl radicals, isocyano radicals, isocyanato radicals, thiocyanato radicals, isothiocyanato radicals, hydroxyl radicals, nitro radicals, CF radicals₃Cl, Br, F, a crosslinkable group, a substituted or unsubstituted aromatic group having 6 to 60 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, a substituted or unsubstituted aryloxy group having 6 to 60 ring atoms, a substituted or unsubstituted heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups;

Ar₁、Ar₂independently selected from an aromatic group having 6 to 40 ring atoms which may be substituted or unsubstituted, or a heteroaromatic group or non-aromatic ring system having 5 to 40 ring atoms which may be substituted or unsubstituted; denotes the attachment site.

In one embodiment, R₁-R₃At each occurrence, is independently selected from: hydrogen, D, a straight-chain alkyl group having 1 to 10C atoms, a branched or cyclic alkyl group having 3 to 10C atoms, an aromatic group having 6 to 20 substituted or unsubstituted ring atoms, and a heteroaromatic group having 5 to 20 substituted or unsubstituted ring atoms.

Further, said (A-2) is selected from

In one embodiment, Ar in formula (1)₃、Ar₄Are selected from absent, i.e. formula (1) has the structure shown in formula (2):

further, the general formula (2) has any one of the structures shown by the general formulae (2-1) to (2-5):

preferably, the general formula (2) has a structure as shown in the general formula (2-1).

In one embodiment, Ar in formula (1)₃、Ar₄At least one selected from (A-2); further, Ar in the general formula (1)₃Or Ar₄Is selected from (A-2); further, the general formula (1) is selected from structures represented by any one of general formulas (3-1) to (3-4):

in one embodiment, Ar₁、Ar₂Independently selected from aromatic groups with 6-30 substituted or unsubstituted ring atoms, or heteroaromatic groups with 5-30 substituted or unsubstituted ring atoms or non-aromatic ring systems.

Further, Ar₁、Ar₂At least one of them is selected from a fused ring aromatic group or a heteroaromatic group having 10 to 20 ring atoms which may be substituted or unsubstituted.

In one embodiment, there is at least one Ar₁Or Ar₂The hydrogen atoms of the ring are substituted by R, which is selected from D, a linear alkyl group having 1 to 20C atoms or a branched or cyclic alkyl group having 3 to 20C atoms. Further, R is selected from cycloalkyl having 3 to 20C atoms. Preferably, R is each independently selected fromAny one of them.

In one embodiment, the aromatic amine compound, Ar, according to the present invention₁、Ar₂Each independently selected from any one of (B-1) to (B-6):

wherein:

X₁selected from N or CR₄；

Y₁Selected from O, S, S ═ O, SO₂、NR₅、PR₅、CR₅R₆Or SiR₅R₆；

R₄-R₆At each occurrence, is independently selected from: each independently selected from: hydrogen, D, straight-chain alkyl having 1 to 20C atoms, straight-chain alkoxy having 1 to 20C atoms, straight-chain thioalkoxy having 1 to 20C atoms, branched or cyclic alkyl having 3 to 20C atoms, branched or cyclic alkoxy having 3 to 20C atoms, branched or cyclic thioalkoxy having 3 to 20C atoms, silyl, keto having 1 to 20C atoms, alkoxycarbonyl having 2 to 20C atoms, aryloxycarbonyl having 7 to 20C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanato, thiocyanate, isothiocyanate, hydroxyl, nitro, CF, and isocyano₃Cl, Br, F, a crosslinkable group, a substituted or unsubstituted aromatic group having 6 to 60 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, a substituted or unsubstituted aryloxy group having 6 to 60 ring atoms, a substituted or unsubstituted heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups;

Ar₆independently selected from an aromatic or heteroaromatic group having 6 to 20 ring atoms which may be substituted or unsubstituted;

adjacent R₅And R₆With or without a ring of interconnects.

When X is present₁For the attachment site is X₁Is selected from C.

Preferably, Ar₆Is selected from

Further, (B-3) is selected from the group consisting of:

n is selected from 0, 1,2,3 or 4.

In one embodiment, R₄-R₆At each occurrence, is independently selected from: hydrogen, D, a straight-chain alkyl group having 1 to 10C atoms, a branched or cyclic alkyl group having 3 to 10C atoms, an aromatic group having 6 to 20 substituted or unsubstituted ring atoms, and a heteroaromatic group having 5 to 20 substituted or unsubstituted ring atoms.

In one embodiment, adjacent R₅And R₆Not forming a ring, or connecting the ring systems with the ring atom number of 6 to 20; further, R₅And R₆Form an adamantyl group or a cyclohexyl group with each other.

In one embodiment, Ar is₁、Ar₂Each independently selected from one of the following groups:

n is selected from 0, 1,2,3 or 4.

In one embodiment, when n ≧ 1, at least one R₄Selected from cycloalkyl groups having 3 to 20C atoms.

In one embodiment, Ar₁、Ar₂At least one selected from

In one embodiment of the present invention, the substrate is,selected from any one of structures (C-1) to (C-11):

in one embodiment, the aromatic amine compound according to the present invention, formula (2-1) is selected from any one of the following structures:

in one embodiment, the aromatic amine compound according to the present invention, formula (1) is selected from any one of the following structures:

preferably, n in (C-1) - (C-11), (4-1) - (4-6) or (5-1) - (5-5) is independently selected from 0 or 1 at each occurrence; further, when n occurs multiple times, at least one n is selected from 1.

Preferably, at least one R of (C-1) - (C-11), (4-1) - (4-6) or (5-1) - (5-5)₄Selected from D, straight chain alkyl having 1 to 10C atoms or branched or cyclic alkyl having 3 to 10C atoms. Further, R₄Selected from cycloalkyl groups having 3 to 20C atoms. Preferably, R₄Selected from cyclohexyl or adamantyl.

Preferably Y in (C-1) - (C-11), (4-1) - (4-6) or (5-1) - (5-5)₁Selected from O, S, NR₅Or CR₅R₆(ii) a Further, Y₁Is selected from C (CH)₃)₂、

In one embodiment, L₁、L₂Independently selected from a single bond, or a substituted or unsubstituted aromatic or heteroaromatic group having 6 to 20 ring atoms;

in one embodiment, L₁、L₂Independently selected from single bond, or substituted or unsubstituted benzene, naphthalene, anthracene, phenanthrene, perylene, tetracene, pyrene, benzopyrene, triphenylene, acenaphthene, fluorene, dibenzofuran, dibenzothiophene ring structure.

Further, L₁、L₂Independently selected from a single bond, or substituted or unsubstituted phenyl.

In one embodiment, L₁、L₂Independently selected from a single bond, or the group shown below:

wherein: denotes the attachment site.

According to one compound of the present invention, preferably selected from, but not limited to, the following structures, the ring hydrogens may be further substituted:

the aromatic amine compound according to the present invention can be used as a functional material in an organic functional layer of an electronic device. The organic functional layer includes, but is not limited to, a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Transport Layer (ETL), an Electron Injection Layer (EIL), an Electron Blocking Layer (EBL), a Hole Blocking Layer (HBL), and an emission layer (EML).

In one embodiment, the aromatic amine compound according to the present invention is used in a hole transport layer.

The invention further relates to a mixture comprising at least one aromatic amine compound as described above, and at least one further organic functional material, which may be selected from hole injection materials, hole transport materials, electron injection materials, electron blocking materials, hole blocking materials, light emitting materials, host materials and organic dyes. Details of various organic functional materials are described in WO2010135519a1, US20090134784a1 and WO 2011110277a 1.

In one embodiment, the further organic functional material is selected from electron transport materials, which are used as co-hosts in electronic devices.

The invention also relates to a composition comprising at least one aromatic amine compound or mixture as described above, and at least one organic solvent; the at least one organic solvent is selected from aromatic or heteroaromatic, ester, aromatic ketone or aromatic ether, aliphatic ketone or aliphatic ether, alicyclic or olefinic compound, or boric acid ester or phosphoric acid ester compound, or a mixture of two or more solvents.

Examples of aromatic or heteroaromatic based solvents suitable for the present invention are, but not limited to: p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1, 4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, dipentylbenzene, tripentylbenzene, pentyltoluene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2,3, 4-tetramethylbenzene, 1,2,3, 5-tetramethylbenzene, 1,2,4, 5-tetramethylbenzene, butylbenzene, dodecylbenzene, dihexylbenzene, dibutylbenzene, p-diisopropylbenzene, cyclohexylbenzene, benzylbutylbenzene, dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, 1-methylnaphthalene, 1,2, 4-trichlorobenzene, 4-difluorodiphenylmethane, 1, 2-dimethoxy-4- (1-propenyl) benzene, diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, α -dichlorodiphenylmethane, 4- (3-phenylpropyl) pyridine, benzyl benzoate, 1-bis (3, 4-dimethylphenyl) ethane, 2-isopropylnaphthalene, quinoline, isoquinoline, methyl 2-furancarboxylate, ethyl 2-furancarboxylate, and the like;

examples of aromatic ketone-based solvents suitable for the present invention are, but not limited to: 1-tetralone, 2- (phenylepoxy) tetralone, 6- (methoxy) tetralone, acetophenone, propiophenone, benzophenone, and derivatives thereof, such as 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylpropiophenone, 3-methylpropiophenone, 2-methylpropiophenone, and the like;

examples of aromatic ether-based solvents suitable for the present invention are, but not limited to: 3-phenoxytoluene, butoxybenzene, p-anisaldehyde dimethylacetal, tetrahydro-2-phenoxy-2H-pyran, 1, 2-dimethoxy-4- (1-propenyl) benzene, 1, 4-benzodioxan, 1, 3-dipropylbenzene, 2, 5-dimethoxytoluene, 4-ethylphenetole, 1, 3-dipropoxybenzene, 1,2, 4-trimethoxybenzene, 4- (1-propenyl) -1, 2-dimethoxybenzene, 1, 3-dimethoxybenzene, glycidylphenyl ether, dibenzyl ether, 4-t-butylanisole, trans-p-propenylanisole, 1, 2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, methyl ether, 2-phenoxytetrahydrofuran, ethyl-2-naphthyl ether;

examples of aliphatic ketone-based solvents suitable for the present invention are, but not limited to: 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 2, 5-hexanedione, 2,6, 8-trimethyl-4-nonanone, fenchone, phorone, isophorone, di-n-amyl ketone, and the like; or aliphatic ethers such as amyl ether, hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and the like.

Examples of ester-based solvents suitable for the present invention are, but not limited to: alkyl octanoates, alkyl sebacates, alkyl stearates, alkyl benzoates, alkyl phenylacetates, alkyl cinnamates, alkyl oxalates, alkyl maleates, alkyl lactones, alkyl oleates, and the like. Octyl octanoate, diethyl sebacate, diallyl phthalate, isononyl isononanoate are particularly preferred.

The solvents mentioned may be used alone or as a mixture of two or more organic solvents.

In certain preferred embodiments, a composition according to the present invention comprises at least one aromatic amine compound or mixture as described above and at least one organic solvent, and may further comprise another organic solvent. Examples of another organic solvent include (but are not limited to): methanol, ethanol, 2-methoxyethanol, methylene chloride, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1, 4-dioxane, acetone, methyl ethyl ketone, 1, 2-dichloroethane, 3-phenoxytoluene, 1,1, 1-trichloroethane, 1,1,2, 2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydronaphthalene, decalin, indene, and/or mixtures thereof.

In some preferred embodiments, particularly suitable solvents for the present invention are those having Hansen (Hansen) solubility parameters within the following ranges:

delta d (dispersion force) is within the range of 17.0-23.2 MPa1/2, especially within the range of 18.5-21.0 MPa 1/2;

δ p (polar force) is in the range of 0.2-12.5 MPa1/2, especially in the range of 2.0-6.0 MPa 1/2;

delta h (hydrogen bonding force) is in the range of 0.9-14.2 MPa1/2, especially in the range of 2.0-6.0 MPa 1/2.

The compositions according to the invention, in which the organic solvent is selected taking into account its boiling point parameter. In the invention, the boiling point of the organic solvent is more than or equal to 150 ℃; preferably equal to or more than 180 ℃; more preferably more than or equal to 200 ℃; more preferably more than or equal to 250 ℃; most preferably at least 300 ℃. Boiling points in these ranges are beneficial for preventing nozzle clogging in inkjet print heads. The organic solvent may be evaporated from the solvent system to form a thin film comprising the functional material.

In a preferred embodiment, the composition according to the invention is a solution.

In another preferred embodiment, the composition according to the invention is a suspension.

The compositions of the embodiments of the present invention may comprise from 0.01 wt% to 10 wt% of the compound or mixture according to the present invention, preferably from 0.1 wt% to 15 wt%, more preferably from 0.2 wt% to 5 wt%, and most preferably from 0.25 wt% to 3 wt%.

The invention also relates to the use of said composition as a coating or printing ink for the production of organic electronic devices, particularly preferably by a printing or coating production process.

Suitable printing or coating techniques include, but are not limited to, ink jet printing, letterpress printing, screen printing, dip coating, spin coating, doctor blade coating, roll printing, twist roll printing, lithographic printing, flexographic printing, rotary printing, spray coating, brush or pad printing, slot die coating, and the like. Gravure printing, jet printing and ink jet printing are preferred. The solution or suspension may additionally include one or more components such as surface active compounds, lubricants, wetting agents, dispersants, hydrophobing agents, binders, and the like, for adjusting viscosity, film forming properties, enhancing adhesion, and the like.

The invention also provides the application of the aromatic amine compound, the mixture or the composition in the organic electronic device. The technical scheme is as follows:

an organic electronic device comprising a first electrode, a second electrode, one or more organic functional layers disposed between the first electrode and the second electrode, the organic functional layers comprising an aromatic amine compound, mixture or composition as described above.

In the present invention, the organic electronic device can be selected from, but not limited to, Organic Light Emitting Diodes (OLEDs), organic photovoltaic cells, organic light emitting cells, organic field effect transistors, organic light emitting field effect transistors, organic lasers, organic spintronic devices, organic sensors, organic plasmon emitting diodes, and the like, and particularly preferably is an OLED.

The organic functional layer according to the present invention may be selected from the group consisting of a hole injection layer, a hole transport layer, a light emitting layer, an electron blocking layer, an electron injection layer, an electron transport layer, a hole blocking layer.

In the embodiment of the present invention, the aromatic amine compound is preferably used for a hole transport layer of an OLED device.

In one embodiment, the organic functional layer comprises at least one hole transport layer or electron blocking layer, and the hole transport layer or electron blocking layer comprises the aromatic amine compound as described above. Specific aromatic amine compounds are defined as hereinbefore.

In some more preferred embodiments, the organic electronic device comprises a first electrode, a second electrode, a light-emitting layer between the first electrode and the second electrode, a first hole transport layer between the first electrode and the light-emitting layer, and a second hole transport layer between the first hole transport layer and the light-emitting layer, the second hole transport layer comprising an aromatic amine compound as described above.

In one embodiment, the organic electronic device according to the present invention is a red organic electronic device.

In one embodiment, the organic electronic device according to the present invention comprises a first electrode, a second electrode, one or more organic functional layers between the first electrode and the second electrode, the functional layers comprising at least two functional layers: one of which is a hole transport layer or an electron blocking layer, the functional layer containing the aromatic amine compound as described above; the other functional layer is a light-emitting layer, and a material of the light-emitting layer contains a metal complex represented by general formula (6):

wherein:

q is selected from 1 or 2;

Ar₇when occurring multiple times, is independently selected from substituted or unsubstituted heteroaromatic groups with 5 to 40 ring atoms;

Ar₈when occurring multiple times, is independently selected from an aromatic group with 6 to 40 substituted or unsubstituted ring atoms, or a heteroaromatic group with 5 to 40 substituted or unsubstituted ring atoms;

R₇-R₈at each occurrence, is independently selected from: hydrogen, D, straight-chain alkyl having 1 to 20C atoms, straight-chain alkyl having 3 to 20C atomsA branched or cyclic alkyl group, a substituted or unsubstituted aromatic group having 5 to 60 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, or a combination of these groups.

In one embodiment, Ar₇When occurring for multiple times, the derivative is independently selected from quinoline or isoquinoline and derivatives thereof.

In one embodiment, Ar₈And when occurring multiple times, is independently selected from phenyl and its derivatives.

Preferably, the general formula (6) is selected from any one of the structures of general formulae (7-1) to (7-3):

wherein:

a is selected from 0, 1,2,3,4, 5 or 6, b is selected from 0, 1,2,3 or 4;

R₉-R₁₀at each occurrence, is independently selected from: d, a straight-chain alkyl group having 1 to 20C atoms, a branched or cyclic alkyl group having 3 to 20C atoms, a substituted or unsubstituted aromatic group having 6 to 30 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms, or a combination of these groups.

In one embodiment, at least one R₉Or R₁₀Selected from linear alkyl groups having 1 to 20C atoms or branched alkyl groups or cyclic alkyl groups having 3 to 20C atoms.

In one embodiment, at least one R₉Selected from linear alkyl groups having 1 to 20C atoms or branched or cyclic alkyl groups having 3 to 20C atoms. Further, at least one R₁₀Selected from linear alkyl groups having 1 to 20C atoms or branched alkyl groups or cyclic alkyl groups having 3 to 20C atoms.

The metal complex according to the general formula (6), preferably selected from, but not limited to, the following structures, the ring hydrogen of which may be optionally substituted:

the light-emitting device according to the present invention emits light at a wavelength of 600 to 700nm, preferably 600 to 650nm, more preferably 600 to 630 nm.

The invention also relates to the use of the electroluminescent device according to the invention in various electronic devices, including, but not limited to, display devices, lighting devices, light sources, sensors, etc.

The present invention will be described in connection with preferred embodiments, but the present invention is not limited to the following embodiments, and it should be understood that the appended claims outline the scope of the present invention and those skilled in the art, guided by the inventive concept, will appreciate that certain changes may be made to the embodiments of the invention, which are intended to be covered by the spirit and scope of the appended claims.

DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION

1. Synthesis of Compounds

EXAMPLE 1 Synthesis of Compound 1

Synthesis of intermediates 1-2: intermediate 1-1(10.0g) was dissolved in dichloromethane (100 ml). Triethylamine (8.1g) was slowly added dropwise at 0 ℃ under nitrogen and stirred for 30 min; trifluoromethanesulfonic anhydride (22.5g) was then added dropwise and stirred at 0 ℃ for 5 h. Then washing with saturated sodium carbonate solution, separating liquid and collecting organic phase. And (4) carrying out rotary evaporation on an organic phase to remove the solvent, and carrying out column chromatography to obtain an intermediate 1-2. Ms (asap): 321.

synthesis of intermediates 1 to 4: intermediate 1-2(14.8g) and intermediate 1-3(10.2g) were dissolved in a mixed solvent of 1, 4-dioxane and water (210/20ml), and Pd (PPh) was added₃)₄(0.5g) and potassium carbonate (19.1 g). Stirring was carried out at 100 ℃ for 6h under a nitrogen atmosphere. Cooling, and removing by rotary evaporationMost of the solvent is removed, then dichloromethane is used for extraction, liquid separation is washed, an organic phase is collected, the solvent is removed by rotary evaporation of the organic phase, and the obtained crude product is subjected to column chromatography and recrystallization to obtain the intermediate 1-4. Ms (asap): 350.

synthesis of intermediates 1 to 5: a mixture of intermediates 1 to 4(11.8g), iron powder (9.4g), ammonium chloride (8.9g), hydrochloric acid (7.0ml) and a mixed solvent of methanol/THF/water (100/100/40ml) was warmed to 70 ℃ and stirred. After the reaction was complete, it was cooled and filtered, most of the solvent was removed by rotary evaporation, then extracted with dichloromethane and washed with weak base water to neutrality. Collecting an organic phase, removing the solvent by rotary evaporation, and carrying out column chromatography on the obtained crude product to obtain an intermediate 1-5. Ms (asap): 320.

synthesis of intermediates 1 to 7: mixing intermediates 1-5(4.7g), intermediates 1-6(4.0g), Pd (dba)₂(0.10g), TTBP (tri-tert-butylphosphine, 0.18g) and sodium tert-butoxide (2.9g) were dissolved in toluene and stirred at 75 ℃ for 4h under a nitrogen atmosphere. And cooling, washing with water, separating liquid, collecting an organic phase, removing the solvent by rotary evaporation, and performing column chromatography on the obtained crude product to obtain the intermediate 1-7. Ms (asap): 512.

synthesis of Compound 1: intermediates 1-7(6.0g), intermediates 1-8(2.7g), Pd (dba)₂(0.10g), TTBP (0.18g) and sodium t-butoxide (2.3g) were dissolved in toluene and stirred at 100 ℃ under a nitrogen atmosphere. And (3) after the reaction is complete, cooling, washing with water, separating liquid, collecting an organic phase, removing the solvent by rotary evaporation, and carrying out column chromatography and recrystallization on the obtained crude product to obtain the compound 1. Ms (asap): 663 mass spectrum is shown in FIG. 2.

Example 2 Synthesis of Compound 2

Synthesis of Compound 2: mixing the intermediate 1-7(4.70g), the compound 2-1(2.34g), Pd (dba)₂(0.10g), TTBP (0.18g) and sodium tert-butoxide (1.50g) were dissolved in toluene and stirred at 75 ℃ for 4h under a nitrogen atmosphere. And cooling, washing with water, separating liquid, collecting an organic phase, performing rotary evaporation on the organic phase to remove the solvent, and performing column chromatography and recrystallization on the obtained crude product to obtain the compound 2. Ms (asap): 670.

example 3 Synthesis of Compound 3

Synthesis of intermediate 3-2: compound 3-1(6.0g) and o-bromoiodobenzene (8.0g) were dissolved in a mixed solvent of 1, 4-dioxane and water (150/30ml), and Pd (PPh) was added₃)₄(0.20g) and potassium carbonate (7.8 g). Stirring was carried out at 100 ℃ for 6h under a nitrogen atmosphere. And (3) cooling, performing rotary evaporation to remove most of the solvent, extracting the product with dichloromethane, washing with water for three times, separating liquid, collecting an organic phase, and performing column chromatography and recrystallization on the crude product obtained after the solvent is removed by the organic phase rotary evaporation to obtain an intermediate 3-2. Ms (asap): 323.

synthesis of intermediates 3-3 reference was made to the synthesis of compound 2 of example 2, except that intermediates 1-7 were replaced with intermediates 1-5. Ms (asap): 478.

synthesis of Compound 3 reference was made to the synthesis of Compound 2, except that 1-7 was replaced with 3-3 and 2-1 was replaced with 3-2. Ms (asap): 720.

EXAMPLE 4 Synthesis of Compound 7

Synthesis of intermediate 7-2 reference was made to the synthesis of intermediate 1-2, except that 1-1 was replaced with 7-1. Ms (asap): 388.

synthesis of intermediate 7-3 reference was made to the synthesis of intermediate 1-4, except that 1-2 was replaced with 7-2. Ms (asap): 418.

synthesis of intermediate 7-5 reference was made to the synthesis of intermediate 1-4, except that 1-2 was replaced with 7-3 and 1-3 was replaced with 7-4. Ms (asap): 477.

synthesis of intermediates 7-6: adding the compound 7-5(10.0g), phosphorus pentoxide (5.9g) and 60mL of trifluoromethanesulfonic acid into a 250mL three-necked flask, stirring at room temperature for 24 hours, finishing the reaction, slowly inverting the reaction solution into 300 g of ice water, performing suction filtration, washing filter residues with water, a sodium bicarbonate aqueous solution and water for several times, collecting the filter residues, drying, placing the filter residues into 50mL of pyridine, performing reflux reaction for 12 hours, cooling to room temperature, pouring the reaction solution into ice water, adding a proper amount of hydrochloric acid, extracting with dichloromethane for 3 times, and washing the organic phase with a saturated sodium chloride aqueous solution. The organic phase was collected and purified by column chromatography over silica gel. Ms (asap): 445.

synthesis of intermediates 7 to 7: mixing compound 7-8(5.0g), compound 2-1(5.7g), Pd (dba)₂(0.2g), TTBP (0.36g) and sodium tert-butoxide (4.6g) were dissolved in toluene and stirred at 100 ℃ for 6h under a nitrogen atmosphere. And (3) cooling, performing rotary evaporation to remove the solvent, extracting with dichloromethane, washing the separated liquid with water, collecting an organic phase, and performing column chromatography on the organic phase to obtain an intermediate 7-7. Ms (asap): 367.

synthesis of compound 7: mixing compound 7-6(7.30g), compound 7-7(3.8g), Pd (dba)₂(0.2g), TTBP (0.36g) and sodium tert-butoxide (3.2g) were dissolved in toluene and stirred at 100 ℃ for 6h under a nitrogen atmosphere. And (3) cooling, performing rotary evaporation to remove the solvent, extracting, washing the separated liquid with water, collecting an organic phase, and performing column chromatography on the organic phase to obtain a compound 7. Ms (asap): 776.

EXAMPLE 5 Synthesis of Compound 8

Synthesis of intermediate 8-2 reference was made to the synthesis of intermediate 1-2, except that 1-1 was replaced with 8-1. Ms (asap): 388.

synthesis of intermediate 8-3 reference was made to the synthesis of intermediate 1-4, except that 1-2 was replaced with 8-2. Ms (asap): 418.

synthesis of intermediate 8-4 reference was made to the synthesis of intermediate 1-4 except that 1-2 was replaced with 8-3 and 1-3 was replaced with o-nitrophenylboronic acid. Ms (asap): 460.

synthesis of intermediates 8 to 5: compound 8-4(10.0g) was dissolved in 80ml of triethyl phosphite under a nitrogen atmosphere and stirred at 140 ℃ for 8 h. And after cooling, distilling under reduced pressure to remove the solvent, and carrying out column chromatography and recrystallization on the residual substance to obtain an intermediate 8-5. Ms (asap): 428.

synthesis of intermediates 8 to 6: mixing compound 8-5(8.2g), iodobenzene (3.9g), Pd (dba)₂(0.2g), TTBP (0.36g) and sodium tert-butoxide (3.7g) were dissolved in toluene and stirred at 75 ℃ for 4h under a nitrogen atmosphere. And (3) cooling, performing rotary evaporation to remove the solvent, extracting, washing the separated liquid with water, collecting an organic phase, and performing column chromatography on the organic phase to obtain an intermediate 8-6. Ms (asap): 504.

synthesis of compound 8: mixing 8-6(7.6g) of the compound, 8-7(5.8g) of the compound, Pd (dba)₂(0.2g), TTBP (0.36g) and sodium tert-butoxide (3.2g) were dissolved in toluene and stirred at 100 ℃ for 8h under a nitrogen atmosphere. And (3) cooling, performing rotary evaporation to remove the solvent, extracting, washing the separated liquid with water, collecting an organic phase, and performing column chromatography on the organic phase to obtain the compound 8. Ms (asap): 825.

EXAMPLE 6 Synthesis of Compound 9

Synthesis of intermediate 9-2 reference was made to the synthesis of intermediate 1-2, except that 1-1 was replaced with 9-1. Ms (asap): 388.

synthesis of intermediate 9-4 reference was made to the synthesis of intermediate 1-4, except that 1-2 was replaced with 9-2. Ms (asap): 418.

synthesis of intermediates 9-6: mixing the compound 9-4(11.3g), 9-5(9.7g), Pd (dba)₂(0.3g), TTBP (0.5g) and sodium tert-butoxide (5.2g) were dissolved in toluene and stirred at 75 ℃ for 4h under a nitrogen atmosphere. And (3) cooling, performing rotary evaporation to remove the solvent, extracting, washing the separated liquid with water, and performing organic phase column chromatography to obtain an intermediate 9-6. Ms (asap): 688.

synthesis of intermediates 9-8 reference was made to the synthesis of intermediates 1-4, except that 1-2 was replaced with 9-6 and 1-3 was replaced with 9-7. Ms (asap): 788.

synthesis of compound 9: compound 9-8(6mmol) was dissolved in dry THF (80mL), cooled to 0 deg.C under a nitrogen atmosphere, and methylmagnesium bromide solution (12mmol) was slowly added dropwise and stirred for 2 hours. The unreacted methylmagnesium bromide was carefully quenched with saturated ammonium chloride solution at 0 ℃. Washing the separated liquid with water, extracting and collecting an organic phase. The organic phase was spin dried and the resulting solid was dissolved in a mixed solution of acetic acid/hydrochloric acid (volume ratio 3:1,60ml) and stirred at 80 ℃ for 4 h. After cooling, the reaction was slowly poured into a large amount of water and filtered. And repeatedly washing the filter cake for several times by using water, a sodium bicarbonate solution and water in sequence, and then recrystallizing to obtain the compound 9. Ms (asap): 770.

EXAMPLE 7 Synthesis of Compound 10

Synthesis of intermediate 10-2 reference was made to the synthesis of intermediate 1-2, except that 1-1 was replaced with 10-1. Ms (asap): 390.

synthesis of intermediate 10-3 reference was made to the synthesis of intermediate 1-4, except that 1-2 was replaced with 10-2. Ms (asap): 418.

synthesis of intermediate 10-4 reference was made to the synthesis of intermediate 1-4, except that 1-2 was replaced with 10-3 and 1-3 was replaced with 7-4. Ms (asap): 477.

synthesis of intermediate 10-5 reference was made to the synthesis of intermediate 7-6, except that 7-5 was replaced with 10-4. Ms (asap): 445.

synthesis of compound 10: mixing compound 10-5(7.6g), compound 10-6(5.8g), Pd (dba)₂(0.2g), TTBP (0.36g) and sodium tert-butoxide (3.2g) were dissolved in toluene and stirred at 100 ℃ for 12h under a nitrogen atmosphere. And (3) cooling, performing rotary evaporation to remove the solvent, extracting, washing the separated liquid with water, collecting an organic phase, and performing column chromatography on the organic phase to obtain the compound 10. Ms (asap): 776.

EXAMPLE 8 Synthesis of Compound 11

Synthesis of intermediate 11-2: mixing intermediate 1-5(10.0g), compound 11-1(6.4g), Pd (dba)₂(0.4g), TTBP (0.7g) and sodium t-butoxide (6.1g) were placed in toluene and stirred at 75 ℃ for 4h under a nitrogen atmosphere. And (3) cooling, performing rotary evaporation to remove the solvent, extracting, washing the separated liquid with water, and performing organic phase column chromatography to obtain the compound 11-2. Ms (asap): 446.

synthesis of compound 11: mixing compound 11-2(8.0g), compound 11-3(7.1g), Pd (dba)₂(0.2g), TTBP (0.36g) and sodium tert-butoxide (3.4g) were dissolved in toluene and stirred at 80 ℃ for 5h under a nitrogen atmosphere. And (3) cooling, performing rotary evaporation to remove the solvent, extracting, washing the separated liquid with water, collecting an organic phase, and performing column chromatography on the organic phase to obtain the compound 11. Ms (asap): 720.

EXAMPLE 9 Synthesis of Compound 12

Synthesis of compound 12: mixing intermediate 1-5(5.1g), compound 12-1(10.2g), Pd (dba)₂(0.2g), TTBP (0.36g) and sodium tert-butoxide (3.1g) were dissolved in toluene and stirred at 80 ℃ for 8h under a nitrogen atmosphere. And (3) cooling, performing rotary evaporation to remove the solvent, extracting with dichloromethane, washing the separated liquid with water, collecting an organic phase, and performing column chromatography on the organic phase to obtain the compound 12. Ms (asap): 740.

EXAMPLE 10 Synthesis of Compound 13

Synthesis of intermediate 13-2: intermediate 1-5(7.3g), compound 13-1(8.6g), Pd (dba)₂(0.2g), TTBP (0.36g) and sodium t-butoxide (4.4g) were placed in toluene and stirred at 75 ℃ for 4h under a nitrogen atmosphere. And (3) cooling, performing rotary evaporation to remove the solvent, extracting with dichloromethane, washing the separated liquid with water, collecting an organic phase, and performing column chromatography on the organic phase to obtain an intermediate 13-2. Ms (asap): 618.

synthesis of compound 13: intermediate 13-2(8.5g), Compound 2-1(3.6g), Pd (dba)₂(0.2g), TTBP (0.36g) and sodium tert-butoxide (3.3g) were dissolved in 180ml of toluene and stirred at 80 ℃ for 5 hours under a nitrogen atmosphere. And (3) cooling, performing rotary evaporation to remove the solvent, extracting with dichloromethane, washing the separated liquid with water, collecting an organic phase, and performing column chromatography on the organic phase to obtain a compound 13. Ms (asap): 776.

EXAMPLE 11 Synthesis of Compound 14

Synthesis of Compound 14 reference was made to the synthesis of Compound 12, except that 12-1 was replaced with 1-8. Ms (asap): 623, mass spectrum as shown in figure 3.

EXAMPLE 12 Synthesis of Compound 15

Synthesis of intermediate 15-2 reference was made to the synthesis of intermediate 1-4, except that 1-3 was replaced with 15-1. Ms (asap): 350.

synthesis of intermediate 15-3 reference was made to the synthesis of intermediates 1-5, except that 1-4 was replaced with 15-2. Ms (asap): 320.

synthesis of intermediate 15-5: mixing intermediate 15-3(6.4g), compound 15-4(8.0g), Pd (dba)₂(0.2g), TTBP (0.36g) and sodium t-butoxide (3.9g) were placed in 150ml toluene and stirred at 75 ℃ for 4h under a nitrogen atmosphere. And (3) cooling, performing rotary evaporation to remove the solvent, extracting by using dichloromethane, washing the separated liquid, and performing organic phase column chromatography to obtain an intermediate 15-5. Ms (asap): 638.

synthesis of compound 15: intermediate 15-5(8.5g), compound 2-1(3.2g), Pd (dba)₂(0.1g), TTBP (0.18g) and sodium t-butoxide (2.6g) were placed in toluene and stirred at 100 ℃ for 6h under a nitrogen atmosphere. And (3) cooling, performing rotary evaporation to remove the solvent, extracting by using dichloromethane, washing the separated liquid, collecting an organic phase, performing rotary evaporation to remove the solvent from the organic phase, and performing column chromatography and recrystallization purification on the obtained crude product to obtain the compound 15. Ms (asap): 796.

EXAMPLE 13 Synthesis of Compound 16

Synthesis of compound 16: mixing the intermediates 1-7(4.70g), the compound 16-1(2.95g), Pd (dba)₂(0.10g), TTBP (0.18g) and sodium t-butoxide (1.50g) were dissolved in toluene,stirring was carried out for 8h at 100 ℃ under a nitrogen atmosphere. And (3) cooling, washing with water, separating liquid, removing the solvent by rotary evaporation of an organic phase, and carrying out column chromatography and recrystallization on the obtained crude product to obtain the compound 16. Ms (asap): 745, the mass spectrum is shown in figure 4.

EXAMPLE 14 Synthesis of Compound 17

Synthesis of compound 17: mixing the intermediates 1-7(8.0g), the compound 17-1(3.7g), Pd (dba)₂(0.10g), TTBP (0.18g) and sodium tert-butoxide (3.1g) were dissolved in 180ml of toluene and stirred at 100 ℃ for 8h under a nitrogen atmosphere. And (3) cooling, performing rotary evaporation to remove the solvent, extracting the product with dichloromethane, washing with water for three times, collecting the organic phase, performing rotary evaporation to remove the solvent, and performing column chromatography and recrystallization on the obtained crude product in sequence to obtain the compound 17. Ms (asap): 663 mass spectrum is shown in FIG. 5.

EXAMPLE 15 Synthesis of Compound 18

Synthesis of Compound 18 reference was made to the synthesis of Compound 17 except that 17-1 was replaced with 18-1. Ms (asap): 663.

EXAMPLE 16 Synthesis of Compound 19

Synthesis of intermediate 19-2 reference was made to the synthesis of intermediates 1-7, except that 1-6 was replaced with 19-1. Ms (asap): 502.

synthesis of Compound 19 reference was made to the synthesis of Compound 17, except intermediates 1-7 were replaced with 19-2 and 17-1 was replaced with 18-1. Ms (asap): 654.

EXAMPLE 17 Synthesis of Compound 20

Synthesis of Compound 20 reference was made to the synthesis of Compound 17, except that 1-7 was replaced with 19-2. Ms (asap): 654.

EXAMPLE 18 Synthesis of Compound 21

Synthesis of intermediate 21-2 reference was made to the synthesis of intermediates 1-7, except that 1-6 was replaced with 21-1. Ms (asap): 486.

synthesis of Compound 21 reference was made to the synthesis of Compound 17, except intermediates 1-7 were replaced with 21-2 and 17-1 was replaced with 18-1. Ms (asap): 638.

EXAMPLE 19 Synthesis of Compound 22

Synthesis of Compound 22 reference was made to the synthesis of Compound 17, except that 1-7 was replaced with 21-2. Ms (asap): 638.

EXAMPLE 20 Synthesis of Compound 23

Synthesis of intermediate 23-2 reference was made to the synthesis of intermediates 1-7, except that 1-6 was replaced with 23-1. Ms (asap): 552.

synthesis of Compound 23 reference was made to the synthesis of Compound 17, except intermediates 1-7 were replaced with 23-2 and 17-1 was replaced with 1-8. Ms (asap): 703 and the mass spectrum is shown in FIG. 6.

EXAMPLE 21 Synthesis of Compound 24

Synthesis of intermediate 24-2 reference was made to the synthesis of 1-7, except that 1-6 was replaced with 24-1. Ms (asap): 604.

synthesis of Compound 24 reference was made to the synthesis of Compound 17 except that 1-7 was replaced with 24-2 and 17-1 was replaced with 1-8. Ms (asap): 755, the mass spectrum is shown in FIG. 7.

EXAMPLE 22 Synthesis of Compound 25

Synthesis of compound 25: mixing compound 1-5(7.0g), compound 18-1(10.3g), Pd (dba)₂(0.2g), TTBP (0.36g) and sodium tert-butoxide (6.4g) were dissolved in 180ml of toluene and stirred at 100 ℃ for 6 hours under a nitrogen atmosphere. And (3) cooling, performing rotary evaporation to remove the solvent, extracting by using dichloromethane, washing the separated liquid by using water, collecting an organic phase, and performing column chromatography on the organic phase to obtain a compound 25. Ms (asap): 623.

EXAMPLE 23 Synthesis of Compound 26

Synthesis of 26-1: mixing compound 1-5(7.0g), compound 1-8(5.1g), Pd (dba)₂(0.2g), TTBP (0.36g) and sodium tert-butoxide (3.2g) were dissolved in 160ml toluene and stirred at 75 ℃ for 4h under a nitrogen atmosphere. And (3) cooling, performing rotary evaporation to remove the solvent, extracting by using dichloromethane, washing the separated liquid, collecting an organic phase, performing rotary evaporation to remove the solvent from the organic phase, and performing column chromatography on the obtained crude product to obtain the intermediate 26-1. Ms (asap): 472.

synthesis of Compound 26 reference was made to the synthesis of Compound 17, except that 1-7 was replaced with 26-1. Ms (asap): 623.

EXAMPLE 24 Synthesis of Compound 27

Synthesis of Compound 27 reference was made to the synthesis of Compound 17 except that 1-7 was replaced with 26-1 and 17-1 was replaced with 18-1. Ms (asap): 623.

EXAMPLE 25 Synthesis of Compound 28

Synthesis of Compound 28 reference was made to the synthesis of Compound 17 except that 1-7 was replaced with 19-2 and 17-1 was replaced with 1-8. Ms (asap): 654, mass spectrum as shown in FIG. 8.

EXAMPLE 26 Synthesis of Compound 29

Synthesis of Compound 29 reference was made to the synthesis of Compound 17, except that 1-7 was replaced with 21-2 and 17-1 was replaced with 1-8. Ms (asap): 638.

EXAMPLE 27 Synthesis of Compound 30

Synthesis of intermediate 30-1 reference was made to the synthesis of 1-7, except that 1-6 was replaced with 30-1. Ms (asap): 502.

synthesis of Compound 30 reference was made to the synthesis of Compound 17 except that 1-7 was replaced with 30-2 and 17-1 was replaced with 1-8. Ms (asap): 654.

EXAMPLE 28 Synthesis of Compound 31

The synthetic route for compound 31 was referenced to the synthesis of compound 25, except that 18-1 was replaced with 21-1. Ms (asap): 651, mass spectrum as shown in fig. 9.

EXAMPLE 29 Synthesis of Compound 32

Synthesis of Compound 32 reference was made to the synthesis of Compound 17 except that 1-7 was replaced with 30-2 and 17-1 was replaced with 1-6. Ms (asap): 694.

EXAMPLE 30 Synthesis of Compound 33

Synthesis of Compound 33 reference was made to the synthesis of Compound 17 except that 1-7 was replaced with 30-2. Ms (asap): 654.

EXAMPLE 31 Synthesis of Compound 34

Synthesis of Compound 34 reference was made to the synthesis of Compound 17 except that 1-7 was replaced with 30-2 and 17-1 was replaced with 18-1. Ms (asap): 654.

EXAMPLE 32 Synthesis of Compound 35

Synthesis of intermediate 35-1 reference was made to the synthesis of 1-7, except that 1-6 was replaced with 35-1. Ms (asap): 486.

synthesis of Compound 35 reference was made to the synthesis of Compound 17, except that 1-7 was replaced with 35-2 and 17-1 was replaced with 1-8. Ms (asap): 638.

EXAMPLE 33 Synthesis of Compound 36

Synthesis of Compound 36 reference was made to the synthesis of Compound 17 except that 1-7 was replaced with 35-2. Ms (asap): 638.

EXAMPLE 34 Synthesis of Compound 37

Synthesis of Compound 37 reference was made to the synthesis of Compound 17 except that 1-7 was replaced with 35-2 and 17-1 was replaced with 18-1. Ms (asap): 638.

EXAMPLE 35 Synthesis of Compound 38

Synthesis of Compound 38 reference was made to the synthesis of Compound 17 except that 1-7 was replaced with 35-2 and 17-1 was replaced with 1-6. Ms (asap): 678.

EXAMPLE 36 Synthesis of Compound 39

Synthesis of Compound 39 reference was made to the synthesis of Compound 17 except that 1-7 was replaced with 19-2 and 17-1 was replaced with 1-6. Ms (asap): 694.

EXAMPLE 37 Synthesis of Compound 40

Synthesis of Compound 40 reference was made to the synthesis of Compound 17, except that 1-7 was replaced with 21-2 and 17-1 was replaced with 1-6. Ms (asap): 678.

EXAMPLE 38 Synthesis of Compound 41

Synthesis of Compound 41 reference was made to the synthesis of Compound 25, except that 18-1 was replaced with 30-1. Ms (asap): 683.

EXAMPLE 39 Synthesis of Compound 42

Synthesis of Compound 42 reference was made to the synthesis of Compound 25, except that 18-1 was replaced with 1-6. Ms (asap): 703.

EXAMPLE 40 Synthesis of Compound 43

Synthesis of Compound 43 reference was made to the synthesis of Compound 25, except that 18-1 was replaced with 43-1. Ms (asap): 703.

EXAMPLE 41 Synthesis of Compound 44

Synthesis of Compound 44 reference was made to the synthesis of Compound 25, except that 18-1 was replaced with 19-1. Ms (asap): 683 mass spectrum is shown in FIG. 10.

2. Device preparation and performance detection

Device example 1

The structure of the device is ITO/hole injection layer (10 nm)/first hole transport layer (60 nm)/second hole transport layer (60 nm)/host material RH1 red light guest RD2/ETM Liq/LiF/Al. Wherein the mass ratio of the main material RH1 to RD2 is 95: 5. The specific preparation process is as follows:

a. cleaning the conductive glass substrate, namely cleaning the conductive glass substrate by using various solvents such as chloroform, ketone and isopropanol when the conductive glass substrate is used for the first time, and then carrying out ultraviolet ozone plasma treatment;

b. the hole injection layer is formed by thermal evaporation of HT1/HATCN (97/3, w/w) on the ITO layer in high vacuum (1 x 10-6 mbar);

c. evaporating 60 nm-thick HT1 as a first hole transport layer on the hole injection layer;

d. evaporating the compound 1 of the invention with the thickness of 60nm as a second hole transport layer on the first hole transport layer;

e. vacuum evaporating a 40nm light-emitting layer on the second hole transport layer; the luminescent layer comprises RH1 as a host material and RD2 as a guest material, and the two materials are co-evaporated by adopting multiple sources; wherein the evaporation rate of RD2 is controlled to be 5% of RH 1;

f. on the light-emitting layer, an ETM/Liq (1:1 mass ratio) mixture with a thickness of 25nm is evaporated to be used as an electron transport layer; on the electron transport layer, LiF of 0.5nm is used as an electron injection layer; al with the thickness of 150nm is used as a cathode;

g. encapsulation the devices were encapsulated with uv curable resin in a nitrogen glove box.

Preparation of OLED devices 2 to 46 and comparative example devices 1 to 3 reference device example 1, except that the second hole transport layer material (compound 1) or the red guest material RD2 was changed to the compound shown in table 2.

The current-voltage (J-V) characteristics of each OLED device were characterized by a characterization device, while recording important parameters such as efficiency, lifetime, and external quantum efficiency. Table 2 shows the OLED device lifetime and external quantum efficiency comparison, where lifetime LT95 is the time at which the luminance drops to 95% of the initial luminance @1000nits at constant current. Here LT95, the external quantum efficiency, is calculated relative to comparative device example 1 (corresponding to comparative material 1), i.e. 100% external quantum efficiency with a lifetime of 1 for comparative device example 1.

Table 2: OLED device Performance comparison

Device example 1-example 43 had significantly higher external quantum efficiencies and lifetimes than comparative device example 1 (for RD2 and comparative example 1), comparative device example 2 (for RD1 and comparative example 1), comparative device example 3 (for RD2, without the second hole transport layer), comparative device example 4 (for RD1 and comparative example 2). This is illustrated for at least two points: 1) the existence of the second hole transport layer is beneficial to improving the performance of the device, which is probably because the existence of the second hole transport layer improves the injection efficiency of holes to the luminescent layer, simultaneously blocks electrons from diffusing from the luminescent layer to the hole transport layer, and has the function of an electron blocking layer, thereby improving the utilization efficiency of excitons; 2) the device performance of the material of the invention is better than that of the comparative device examples 1 and 2, and the fact that the combination of the hole transport material and the red light object based on the invention is obviously better than that of the hole transport material and the red light object shown in the comparative examples is shown. This is probably because the structure of the compound provided by the present invention not only retains naphthalene and phenanthrene having a larger pi-conjugated plane than the comparative example molecule, but also the present invention provides a molecule in which the steric structure of the molecule is largely changed with respect to the comparative example molecule due to the large steric hindrance between the two substituents on naphthalene, and the molecule has a large rigidity, thereby improving the stacking of the molecules and increasing the efficiency, stability and lifetime of the device. Therefore, the OLED device prepared by the organic mixture provided by the invention has obviously improved luminous efficiency and service life.

The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.