CN114426492A - Arylamine organic compounds, mixtures, compositions and organic electronic devices - Google Patents

Abstract

The invention relates to an arylamine organic compound, a mixture, a composition and an organic electronic device. The arylamine organic compound has a structure formed by combining a chemical formula (1) and a chemical formula (2), wherein the condensed sites of the chemical formula (1) and the chemical formula (2) are represented. The arylamine organic compound has excellent hole transport property and stability, can be used as a novel electron blocking layer material for organic electronic devices, particularly Organic Light Emitting Diode (OLED) devices, and can improve the stability and the service life of the devices.

Description

Arylamine organic compounds, mixtures, compositions and organic electronic devices

The present application claims priority from the chinese patent application entitled "an aromatic amine-based compound and its uses" filed by the chinese patent office at 29/10/2020, application number 202011175887X, the entire contents of which are incorporated herein by reference.

Technical Field

The invention relates to the technical field of organic electroluminescent materials, in particular to an arylamine organic compound, a mixture, a composition and an organic electronic device.

Background

Organic electroluminescent display devices are self-luminous display devices that generate excitons by transfer and recombination of carriers between functional layers and emit light by means of organic compounds or metal complexes having high quantum efficiency. An organic electroluminescent element generally has a structure including a positive electrode and a negative electrode and an organic functional layer between them. 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 recent years, the luminous efficiency of organic electroluminescent diodes (OLEDs) has been greatly improved, but the internal quantum efficiency thereof has approached the theoretical limit. The difference in mobility between holes and electrons causes the recombination region not to be completely and uniformly dispersed in the light-emitting layer, which reduces the light-emitting efficiency of the device. By further improving the material structure and the device structure, the hole mobility can be improved, the difference between the hole mobility and the electron mobility can be reduced, and the deviation of a recombination region can be avoided, so that the luminous efficiency of the device can be improved, and the service life of the device can be prolonged.

Disclosure of Invention

Based on the above, the present invention aims to provide an arylamine organic compound, a mixture, a composition and an organic electronic device, which can improve the efficiency and the service life of the device.

The technical scheme is as follows:

an arylamine organic compound is structurally combined by a chemical formula (1) and a chemical formula (2):

wherein:

represents the fused site of chemical formula (1) and chemical formula (2);

n1 and n2 are respectively and independently selected from 0 or 1, and n1+ n2 is more than or equal to 1;

L₁and L₂Each independently selected from a single bond, or a substituted or unsubstituted aryl group having 6 to 40 ring atoms, or a substituted or unsubstituted heteroaryl group having 6 to 40 ring atoms;

Ar₁-Ar₄each independently selected from a substituted or unsubstituted aromatic group having 6 to 40 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 40 ring atoms;

ring a is a non-aromatic ring system having 5 to 20 ring atoms.

The invention also provides a mixture, which comprises the aromatic amine organic compound and at least one organic functional material, wherein the organic functional material is at least one of a hole injection material, a hole transport material, an electron injection material, an electron blocking material, a hole blocking material, a luminescent material, a main body material and an organic dye.

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

The invention also provides an organic electronic device which comprises a first electrode, a second electrode and one or more organic functional layers positioned between the first electrode and the second electrode, wherein the organic functional layers comprise the arylamine organic compound or the mixture or are prepared from the composition.

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

the arylamine organic compound provided by the invention has excellent hole transport property and stability, can be used as a hole transport material or an electron blocking layer material for an organic light-emitting electronic device, is particularly applied to a green light organic light-emitting electronic device, and obviously improves the light-emitting efficiency and the service life of the device.

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, "substituted" means that a hydrogen atom in a substituent is substituted by a substituent.

In the present invention, when the same substituent is present in multiple times, it may be independently selected from different groups. As shown in the general formula, the compound contains a plurality of R₁Then R is₁Can be independently selected from different groups.

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: c_1-30Alkyl, heterocyclic group containing 3 to 20 ring atoms, aryl group containing 5 to 20 ring atoms, heterocyclic group containing 3 to 20 ring atoms, heterocyclic group containingHeteroaryl of 5 to 20 ring atoms, silyl, carbonyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, haloformyl, formyl, -NRR', cyano, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxy, trifluoromethyl, nitro or halogen, and the above groups may also be further substituted with art-acceptable substituents; it is understood that R and R 'in-NRR' are each independently substituted with art-acceptable groups including, but not limited to, H, C _1-6An alkyl group, a cycloalkyl group having 3 to 8 ring atoms, a heterocyclic group having 3 to 8 ring atoms, an aryl group having 5 to 20 ring atoms or a heteroaryl group having 5 to 10 ring atoms; said C is_1-6Alkyl, cycloalkyl containing 3 to 8 ring atoms, heterocyclyl containing 3 to 8 ring atoms, aryl containing 5 to 20 ring atoms or heteroaryl containing 5 to 10 ring atoms are optionally further substituted by one or more of the following: c_1-6Alkyl, cycloalkyl having 3 to 8 ring atoms, heterocyclyl having 3 to 8 ring atoms, halogen, hydroxy, nitro or amino.

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.

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. Phrases containing the term, e.g., "C _1-9Alkyl "refers to an alkyl group containing 1 to 9 carbon atoms, each occurrence of which can be independently C₁Alkyl radical, C₂Alkyl radical, C₃Alkyl radical, C₄Alkyl radical, C₅Alkyl radical, C₆Alkyl radical, C₇Alkyl radical, C₈Alkyl or C₉An alkyl group. 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, 4-methylcyclohexyl, 4-tert-butylcyclohexyl, n-heptyl, 1-methylheptyl, 2-dimethylheptyl, 2-ethylheptyl, 2-butylheptyl, n-octyl, tert-octyl, 2-ethyloctyl, 2-butyloctyl, 2-hexyloctyl, tert-butyl, 2-isobutyl, 2-ethylbutyl, 3-dimethylbutyl, 2-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl, 4-butylcyclohexyl, 2-butylheptyl, 2-methylheptyl, 2-ethylheptyl, 2-ethyloctyl, 2-tert-butylhexyl, 2-butylhexyl, or a, 3, 7-dimethyloctyl, cyclooctyl, n-nonyl, n-decyl, adamantyl, 2-ethyldecyl, 2-butyldecyl, 2-hexyldecyl, 2-octyldecyl, n-undecyl, n-dodecyl, 2-ethyldodecyl, 2-butyldodecyl, 2-hexyldodecyl, 2-octyldodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, 2-ethylhexadecyl, 2-butylhexadecyl, 2-hexylhexadecyl, 2-octylhexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, 2-ethyleicosyl, 2-butyleicosyl, 2-hexyleicosyl, 2-octyleicosyl, N-heneicosyl, n-docosyl, n-tricosyl, n-tetracosyl, n-pentacosyl, n-hexacosyl, n-heptacosyl, n-octacosyl, n-nonacosyl, n-triacontyl, adamantane and the like.

"aryl, aryl or aromatic group" refers to a hydrocarbon group containing at least one aromatic ring. "heteroaryl or heteroaromatic group" refers to an aromatic hydrocarbon group that contains at least one heteroatom. The heteroatoms are preferably selected from Si, N, P, O, S and/or Ge, particularly preferably from Si, N, P, O and/or S. By fused ring aromatic group is meant that the rings of the aromatic group may have two or more rings in which two carbon atoms are shared by two adjacent rings, i.e., fused rings. The fused heterocyclic aromatic group means a fused ring aromatic hydrocarbon group containing at least one hetero atom. For the purposes of the present invention, aromatic or heteroaromatic radicals include not only aromatic ring systems but also non-aromatic ring systems. Thus, systems such as pyridine, thiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, pyrazine, pyridazine, pyrimidine, triazine, carbene, and the like are also considered aromatic or heterocyclic aromatic groups for the purposes of this invention. For the purposes of the present invention, fused-ring aromatic or fused-heterocyclic aromatic ring systems include not only systems of aromatic or heteroaromatic groups, but also systems in which a plurality of aromatic or heterocyclic aromatic groups may also be interrupted by short non-aromatic units (< 10% of non-H atoms, preferably less than 5% of non-H atoms, such as C, N or O atoms). Thus, for example, systems such as 9, 9' -spirobifluorene, 9, 9-diarylfluorene, triarylamines, diaryl ethers, etc., are also considered fused aromatic ring systems for the purposes of this invention.

In a certain preferred embodiment, said aromatic group is selected from: benzene, naphthalene, anthracene, fluoranthene, phenanthrene, triphenylene, perylene, tetracene, pyrene, benzopyrene, acenaphthene, fluorene, and derivatives thereof; the heteroaromatic group is selected from the group consisting of triazines, pyridines, pyrimidines, imidazoles, furans, thiophenes, benzothiophenes, indoles, carbazoles, pyrroloimidazoles, pyrrolopyrroles, thienopyrroles, thienothiophenes, furopyrroles, furofurans, thienofurans, benzisoxazoles, benzisothiazoles, benzimidazoles, quinolines, isoquinolines, phthalazines, quinoxalines, phenanthridines, primadines, quinazolines, quinazolinones, dibenzothiophenes, dibenzofurans, carbazoles, and derivatives thereof.

Non-aromatic ring systems refer to ring systems containing at least one non-aromatic ring, which in the present invention preferably contains only carbon-carbon single bonds forming the ring, such as adamantyl or cyclohexyl.

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 example

Wherein R is attached to any substitutable site of the phenyl ring.

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 example

6R on the benzene ring¹May be the same as or different from each other.

In the present invention, "ring formation" means a form in which an aliphatic ring, an aromatic ring, a heteroaromatic ring, an aliphatic heterocyclic ring, or a combination thereof is formed.

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

The technical scheme of the invention is as follows:

an arylamine organic compound is structurally combined by a chemical formula (1) and a chemical formula (2):

wherein:

represents a fused site of chemical formula (1) and chemical formula (2);

n1 and n2 are independently selected from 0 or 1, and n1+ n2 is greater than or equal to 1;

L₁and L₂Each independently selected from a single bond, or a substituted or unsubstituted aryl group having 6 to 40 ring atoms, or a substituted or unsubstituted heteroaryl group having 6 to 40 ring atoms;

Ar₁-Ar₄each independently selected from a substituted or unsubstituted aromatic group having 6 to 40 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 40 ring atoms;

ring a is a non-aromatic ring system having 5 to 20 ring atoms.

In one embodiment, n1 is selected from 1; in one embodiment, n2 is selected from 1. In one embodiment, both n1 and n2 are selected from 1.

Further, the arylamine organic compound of the present invention has a structure represented by any one of formulas (3-1) to (3-5):

Still further, the arylamine organic compound of the present invention is selected from the structures described in any one of formulas (4-1) to (4-4):

further, the arylamine organic compound has a structure shown in a formula (4-5) or (4-6):

in one embodiment, Ar of the present invention₁-Ar₄Each independently selected from a substituted or unsubstituted aromatic group having 6 to 30 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms.

Further, Ar₁-Ar₄Are respectively and independently selected from any one of groups (B-1) to (B-7):

wherein:

each occurrence of X is independently selected from N or CR₁；

Y is selected from O, S, S ═ O, SO₂、NR₂、PR₂、CR₃R₄Or SiR₃R₄；

Ar₅Selected from substituted or unsubstituted aromatic groups having 6 to 20 ring atoms, or selected from substituted or unsubstituted heteroaromatic groups having 6 to 20 ring atoms;

R₁-R₄each occurrence is independently selected from-H, -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 alkoxy having 3 to 20C atoms, or cyclicAlkoxy, 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, isocyanate, thiocyanate, isothiocyanate, hydroxy, nitro, CF ₃Cl, Br, F, a crosslinkable group, a substituted or unsubstituted aromatic group having 5 to 30 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms, an aryloxy group having 5 to 30 ring atoms, a heteroaryloxy group having 5 to 30 ring atoms, or a combination of these groups;

R₃and R₄With or without rings.

In a preferred embodiment, Ar₅Selected from (B-1) or (B-2) or

X and Y are as defined above.

In one embodiment, each occurrence of X in (B-1) - (B-7) is selected from CR₁(ii) a Further, R₁Each occurrence is independently selected from-H, -D, -F, a straight chain alkyl group having 1 to 10C atoms, a branched or cyclic alkyl group having 3 to 10C atoms, a substituted or unsubstituted aryl group having 5 to 10 ring atoms, a substituted or unsubstituted heteroaryl group having 5 to 10 ring atoms, or a combination of these groups;

further, Ar in the arylamine organic compound₁-Ar₄Are respectively and independently selected from (B-1) to (B-3). And X is selected from CR₁. More preferably, Ar₁-Ar₄Are respectively and independently selected from any one of (C-1) to (C-5):

wherein: indicates the attachment site; m1, m2, m3, m4 and m5 are each independently selected from 0, 1, 2, 3 or 4.

Particularly preferably, Ar₁-Ar₄Each independently selected from the group consisting of (C-1) and (C-2):

in one embodiment, m1 is selected from 1, 2, 3, or 4; further, m1 is selected from 1.

In one embodiment, m2 is selected from 0.

In one embodiment, Y in (C-2) is selected from O, S or CR₃R₄(ii) a Further, Y is selected from CR₃R₄。

In one embodiment, R in (C-1) - (C-5)₁Each occurrence is independently selected from-H, -D, -F, a straight chain alkyl group having 1 to 10C atoms, a branched or cyclic alkyl group having 3 to 10C atoms, a phenyl group, or a naphthyl group.

In one embodiment, R₃And R₄Each occurrence is independently selected from-H, -D, a straight chain alkyl group having 1 to 10C atoms, a branched or cyclic alkyl group having 3 to 10C atoms, a substituted or unsubstituted aryl group having 5 to 20 ring atoms, a substituted or unsubstituted heteroaryl group having 5 to 20 ring atoms, or a combination of these groups;

further, R₃And R₄Each occurrence is independently selected from-H, -D, a straight chain alkyl group having 1 to 8C atoms, a branched or cyclic alkyl group having 3 to 8C atoms, an aryl or heteroaryl group having 6 ring atoms.

In one embodiment, R₃And R₄Form no ring, further, R ₃And R₄Each occurrence is independently selected from-H, -D, methyl, ethyl or phenyl.

In one embodiment, R₃And R₄A ring system having 5 to 20 ring atoms; further, (C-2) may be selected from any one of the following groups:

in one embodiment, R in (C-1) and (C-2)₁Each occurrence is independently selected from-D, -F, a straight chain alkyl group having 1 to 10C atoms, a branched or cyclic alkyl group having 3 to 10C atoms, a substituted or unsubstituted aryl group having 5 to 20 ring atoms, a substituted or unsubstituted heteroaryl group having 5 to 20 ring atoms, or a combination thereof.

Preferably R in (C-1) or (C-2)₁Each occurrence is independently selected from-D, -F, a straight chain alkyl group having 1 to 8C atoms, a branched or cyclic alkyl group having 3 to 8C atoms, and a substituted or unsubstituted aromatic group having 5 to 20 ring atoms.

Further, R in (C-1) or (C-2)₁At each occurrence, is selected from-D, -F, phenyl, cyclohexyl, methyl, or adamantyl.

In one embodiment, Ar₁-Ar₂At least one of them is selected from (C-2). In one embodiment, Ar₃-Ar₄At least one of them is selected from (C-2).

Further, the aromatic amine-based organic compound has a structure represented by any one of formulas (5-1) to (5-8):

In one embodiment, L₁And L₂Each independently selected from a single bond, or a substituted or unsubstituted aromatic group having 6 to 20 ring atoms, or a substituted or unsubstituted heteroaromatic group having 6 to 20 ring atoms; further, L₁And L₂Each independently selected from a single bond, or an aromatic group having 6 to 13 ring atoms.

Further, L₁And L₂Each independently selected from a single bond, or any one of the following groups:

wherein:

each occurrence of X is independently selected from N or CR₁；

Each occurrence of Y is independently selected from O, S, S ═ O, SO₂、NR₂、PR₂、CR₃R₄Or SiR₃R₄；

R₁-R₄Each occurrence is independently selected from the group consisting of-H, -D, linear alkyl having 1 to 20C atoms, linear alkoxy having 1 to 20C atoms, linear 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, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, CF ₃Cl, Br, F, a crosslinkable group, a substituted or unsubstituted aromatic group having 5 to 30 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms, an aryloxy group having 5 to 30 ring atoms, a heteroaryloxy group having 5 to 30 ring atoms, or a combination of these groups;

R₃and R₄With or without rings formed therebetween.

In one embodiment, L₁And L₂X in (A) is independently selected from CR at each occurrence₁(ii) a Further, L₁And L₂R in (1)₁Each occurrence is independently selected from-H, -D, a straight chain alkyl group having 1 to 10C atoms, a branched or cyclic alkyl group having 3 to 10C atoms, a substituted or unsubstituted aryl group having 5 to 30 ring atoms, a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms, or a combination of these groups; further, L₁And L₂R in (1)₁At each occurrence, each occurrence is independently selected from H.

In one embodiment, L₁And L₂Each independently selected from a single bond, or a junctionStructurally having a benzene ring, pyridine, pyrimidine, triazine, naphthalene ring, quinoline, isoquinoline, dibenzofuran, dibenzothiophene, carbazole, fluorene or phenanthrene group.

In a preferred embodiment, L₁And L₂Are respectively and independently selected from single bond,

In a preferred embodiment, L ₁And L₂Are all selected from single bonds.

In the formulae (I-1) and (I-2)

And

each independently selected from any one of the following groups:

in one embodiment, the non-aromatic ring system is selected from cyclohexyl substituted or unsubstituted by R, adamantyl substituted or unsubstituted by R, cyclopentyl substituted or unsubstituted by R

Substituted or unsubstituted by R

Or substituted or unsubstituted by R

R is selected from-D, straight chain alkyl having 1 to 10C atoms, branched chain alkyl having 3 to 10C atoms.

In one embodiment, ring a of the present invention is selected from any one of the following groups:

wherein: the H atoms on the ring may be further substituted.

Further, in the present invention,

is selected from

The structures of the aromatic amine-based organic compounds according to the present invention are listed below, but not limited thereto:

the arylamine organic compound according to the present invention can be used as a functional material in a functional layer of an electronic device. The organic functional layers include, but are 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 arylamine organic compound according to the present invention is used in a hole transport layer or an electron blocking layer, and further, the arylamine organic compound according to the present invention is used in an electron blocking layer of a green organic electronic device.

The invention further relates to a mixture comprising at least one aromatic amine organic compound as described above, and another organic functional material selected from the group consisting of Hole Injection Materials (HIM), Hole Transport Materials (HTM), Electron Transport Materials (ETM), Electron Injection Materials (EIM), Electron Blocking Materials (EBM), Hole Blocking Materials (HBM), luminescent materials (Emitter), Host materials (Host) and organic dyes. Various organic functional materials are described in detail, for example, in WO2010135519A1, US20090134784A1 and WO 2011110277A1, the entire contents of which 3 are hereby incorporated by reference.

In one embodiment, the further organic functional material is selected from hole injection materials.

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

In one preferred embodiment, a composition according to the invention, said at least one organic solvent is chosen from aromatic-or heteroaromatic-based 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, diphenylbenzene, phenylpyridine, and 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;

in some preferred embodiments, the at least one organic solvent may be selected from: aliphatic ketones such as 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 2, 5-hexanedione, 2, 6, 8-trimethyl-4-nonanone, fenchylone, phorone, isophorone, di-n-amyl ketone, etc.; 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.

In other preferred embodiments, the at least one organic solvent may be selected from ester-based solvents: 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 organic 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 17.0 to 23.2MPa^1/2In particular in the range of 18.5 to 21.0MPa^1/2A range of (d);

δ p (pole)Sexual strength) of 0.2 to 12.5MPa^1/2In particular in the range of 2.0 to 6.0MPa^1/2A range of (d);

delta h (hydrogen bonding force) is 0.9-14.2 MPa^1/2In particular in the range of 2.0 to 6.0MPa^1/2The range of (1).

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 more than or equal to 275 ℃ or more than or equal to 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 composition of the embodiment of the present invention may contain 0.01 wt% to 10 wt% of the aromatic amine organic compound or mixture according to the present invention, preferably 0.1 wt% to 15 wt%, more preferably 0.2 wt% to 5 wt%, and most preferably 0.25 wt% to 3 wt%.

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

Suitable Printing or coating techniques include, but are not limited to, ink jet Printing, letterpress, 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 printing technology and the requirements related to the solution, such as solvent and concentration, viscosity, etc.

The present invention also provides a use of the aromatic amine Organic compound, mixture or composition as described above in an Organic electronic device, which may be selected from, but not limited to, Organic Light Emitting Diodes (OLEDs), Organic photovoltaic cells (OPVs), Organic light Emitting cells (OLEECs), Organic Field Effect Transistors (OFETs), Organic light Emitting field effect transistors (fets), Organic lasers, Organic spintronic devices, Organic sensors, and Organic Plasmon Emitting diodes (Organic plasma Emitting diodes), etc., and particularly preferably is an OLED. In the embodiment of the present invention, the organic compound is preferably used for a hole transport layer or an electron blocking layer of an OLED device.

The invention further relates to an organic electronic device comprising a first electrode, a second electrode, and one or more organic functional layers positioned between the first electrode and the second electrode, wherein the organic functional layers comprise the aromatic amine organic compound, the mixture or the composition. Further, the organic electronic device comprises a cathode, an anode and one or more organic functional layers positioned at the cathode and the anode.

The Organic electronic device can be selected from, but not limited to, Organic Light Emitting Diodes (OLEDs), Organic photovoltaic cells (OPVs), Organic light Emitting cells (OLEECs), Organic Field Effect Transistors (OFETs), Organic light Emitting field effect transistors (fets), Organic lasers, Organic spintronic devices, Organic sensors, Organic Plasmon Emitting diodes (Organic Plasmon Emitting diodes), and the like, and particularly preferred are Organic electroluminescent devices such as OLEDs, OLEECs, Organic light Emitting field effect transistors.

The organic functional layer according to the present invention may be selected from a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an emission layer (EML), an Electron Blocking Layer (EBL), an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), and a Hole Blocking Layer (HBL). Suitable materials for use in these functional layers are described in detail above and in WO2010135519a1, US20090134784a1 and WO2011110277a1, the entire contents of these 3 patent documents being hereby incorporated by reference.

In one embodiment, the organic functional layer at least comprises a hole transport layer or an electron blocking layer, and the hole transport layer or the electron blocking layer comprises the arylamine organic compound. The definition of the specific arylamine organic compound is as described above.

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 G11

Z1(11.58g, 30mmol) was dissolved in anhydrous tetrahydrofuran, cooled to-78 deg.C and butyllithium (1.6M, 18.7mL) was added slowly. After about 0.5 hour, a solution of adamantanone (5.4g, 30mmoL) in anhydrous tetrahydrofuran was added dropwise to the flask, and the reaction was continued at this temperature for half an hour, then warmed to room temperature, and continued for 8 hours. The solvent was removed under reduced pressure, hydrochloric acid and acetic acid were added, and reflux was continued for about 2 hours. Cooled to room temperature, and deionized water was added, followed by extraction with ethyl acetate. After concentration, the mixture was separated by a silica gel column, and the solvent was removed to obtain Z2 in an amount of 10g in a yield of 76%.

Z2(8.8g, 20mmol) was dissolved in anhydrous tetrahydrofuran, cooled to-78 deg.C and butyllithium (1.6M, 8.7mL) was added slowly. After about 0.5 hour, a solution of 4-bromofluorenone (5.18g, 20mmoL) in anhydrous tetrahydrofuran was added dropwise to the flask, and the reaction was continued at this temperature for half an hour, then warmed to room temperature, and continued for 8 hours. The solvent was removed under reduced pressure, hydrochloric acid and acetic acid were added, and reflux was continued for about 2 hours. Cooled to room temperature, and deionized water was added, followed by extraction with ethyl acetate. After concentration, the mixture was separated by a silica gel column, and the solvent was removed to obtain 9.75g in total of Z3 in a yield of 81%.

Compounds Z3(9g, 15mmol) and Z3-1(4.55g, 15mmol) were dissolved in anhydrous toluene, sodium tert-butoxide (1.73g, 18mmol) and tris-dibenzylideneacetone dipalladium (0.41g, 0.45mmol) were added thereto, nitrogen was replaced three times, tri-tert-butylphosphine (0.45mmol) was added thereto, the temperature was gradually raised to 80 ℃, the reaction was stirred for 12 hours, and the heat source was removed. After the system is cooled, deionized water is added, an organic layer is separated, ethyl acetate is used for extraction for three times, concentration is carried out under reduced pressure, and 8G of product G11 is obtained after the product is passed through a silica gel column, wherein the yield is 65%; MS:825[ M ]⁺]。

Example 2: synthesis of Compound G16

Compounds Z3(6.02g, 10mmol) and Z4-1(3.77g, 10mmol) were dissolved in anhydrous toluene, sodium tert-butoxide (1.15g, 12mmol) and tris-dibenzylideneacetone dipalladium (0.27g, 0.3mmol) were added, nitrogen was replaced three times, tri-tert-butylphosphine (0.3mmol) was added, the temperature was gradually raised to 80 ℃, the reaction was stirred for 12 hours, and the heat source was removed. After the system is cooled, deionized water is added, an organic layer is separated, ethyl acetate is used for extraction for three times, concentration is carried out under reduced pressure, and 6.83G of product G16 is obtained after the product is passed through a silica gel column, wherein the yield is 76%; MS 899[ M ] ⁺]。

Example 3: synthesis of Compound G23

Z1(11.58g, 30mmol) was dissolved in anhydrous tetrahydrofuran, cooled to-78 deg.C and butyllithium (1.6M, 18.7mL) was added slowly. After about 0.5 hour, a solution of cyclohexanone (2.94g, 30mmoL) in anhydrous tetrahydrofuran was added dropwise to the reaction flask, and the reaction was continued at this temperature for half an hour, then warmed to room temperature, and continued for 8 hours. The solvent was removed under reduced pressure, hydrochloric acid and acetic acid were added, and reflux was continued for about 2 hours. Cooled to room temperature, and deionized water was added, followed by extraction with ethyl acetate. After concentration, the mixture was separated by a silica gel column, and the solvent was removed to obtain 8.5g in total of Z4 in 73% yield.

Z4(7.76g, 20mmol) was dissolved in anhydrous tetrahydrofuran, cooled to-78 deg.C and butyllithium (1.6M, 12.5mL) was added slowly. After about 0.5 hour, a solution of 4-bromofluorenone (5.18g, 20mmoL) in anhydrous tetrahydrofuran was added dropwise to the flask, and the reaction was continued at this temperature for half an hour, then warmed to room temperature, and continued for 8 hours. The solvent was removed under reduced pressure, hydrochloric acid and acetic acid were added, and reflux was continued for about 2 hours. Cooled to room temperature, and deionized water was added, followed by extraction with ethyl acetate. After concentration, the mixture was separated by a silica gel column, and the solvent was removed to obtain 9.02g in total of Z5 in 82% yield.

Compounds Z5(8.25g, 15mmol) and Z6(4.35g, 15mmol) were dissolved in anhydrous toluene, sodium tert-butoxide (1.73g, 18mmol) and tris-dibenzylideneacetone dipalladium (0.41g, 0.45mmol) were added thereto, nitrogen was replaced three times, tri-tert-butylphosphine (0.45mmol) was added thereto, the temperature was gradually raised to 80 ℃, the reaction was stirred for 12 hours, and the heat source was removed. After the system is cooled, deionized water is added, an organic layer is separated, ethyl acetate is used for extraction for three times, concentration is carried out under reduced pressure, and 8.89G of a product G23 is obtained after the product G23 is passed through a silica gel column, wherein the yield is 78%; MS 760[ M ] ⁺]。

Example 4: synthesis of Compound G37

Compounds Z5(5.1g, 10mmol) and Z7(2.85g, 10mmol) were dissolved in anhydrous toluene, sodium tert-butoxide (1.15g, 12mmol) and tris-dibenzylideneacetone dipalladium (0.27g, 0.3mmol) were added, nitrogen was replaced three times, tri-tert-butylphosphine (0.3mmol) was added, the temperature was gradually raised to 80 ℃, the reaction was stirred for 12 hours, and the heat source was removed. After the system is cooled, deionized water is added, an organic layer is separated, ethyl acetate is used for extraction for three times, concentration is carried out under reduced pressure, and 6.28G of product G37 is obtained after the product is passed through a silica gel column, wherein the yield is 85%; MS 739[ M ]⁺]。

Example 5: synthesis of Compound G27

Compounds Z5(5.5g, 10mmol) and Z8(3.61g, 10mmol) were dissolved in anhydrous toluene, sodium tert-butoxide (1.15g, 12mmol) and tris-dibenzylideneacetone dipalladium (0.27g, 0.3mmol) were added thereto, nitrogen gas was replaced three times, tri-tert-butylphosphine (0.3mmol) was added thereto, the temperature was gradually raised to 80 ℃, the reaction was stirred for 12 hours, and the heat source was removed. After the system is cooled, deionized water is added, an organic layer is separated, ethyl acetate is used for extraction for three times, concentration is carried out under reduced pressure, and 5.9G of product G27 is obtained after the product is passed through a silica gel column, wherein the yield is 71%; MS:831[ M ]⁺]。

Example 6: synthesis of Compound G59

Z2(8.8g, 20mmol) was dissolved in anhydrous tetrahydrofuran, cooled to-78 deg.C and butyllithium (1.6M, 12.5mL) was added slowly. After about 0.5 hour, a solution of 3-bromofluorenone (5.18g, 20mmoL) in anhydrous tetrahydrofuran was added dropwise to the flask, and the reaction was continued at this temperature for half an hour, then warmed to room temperature, and continued for 8 hours. The solvent was removed under reduced pressure, hydrochloric acid and acetic acid were added, and reflux was continued for about 2 hours. Cooled to room temperature, and deionized water was added, followed by extraction with ethyl acetate. After concentration, the mixture was separated by means of a silica gel column, and the solvent was removed to obtain 9.51g in total of Z9 in a yield of 79%.

Compounds Z9(6.02g, 10mmol) and Z10(2.75g, 10mmol) were dissolved in anhydrous toluene, sodium tert-butoxide (1.15g, 12mmol) and tris-dibenzylideneacetone dipalladium (0.27g, 0.3mmol) were added, nitrogen was replaced three times, tri-tert-butylphosphine (0.3mmol) was added, the temperature was gradually raised to 80 ℃, the reaction was stirred for 12 hours, and the heat source was removed. After the system is cooled, deionized water is added, an organic layer is separated, ethyl acetate is used for extraction for three times, concentration is carried out under reduced pressure, and 6.53G of product G59 is obtained after the product is passed through a silica gel column, wherein the yield is 82%; MS 797[ M ]⁺]。

Example 7: synthesis of Compound G61

Z2(8.8g, 20mmol) was dissolved in anhydrous tetrahydrofuran, cooled to-78 deg.C and butyllithium (1.6M, 12.5mL) was added slowly. After about 0.5 hour, a solution of 2-bromofluorenone (5.18g, 20mmoL) in anhydrous tetrahydrofuran was added dropwise to the reaction flask, and the reaction was continued at this temperature for half an hour, then warmed to room temperature, and continued for 8 hours. The solvent was removed under reduced pressure, hydrochloric acid and acetic acid were added, and reflux was continued for about 2 hours. Cooled to room temperature, and deionized water was added, followed by extraction with ethyl acetate. After concentration, the mixture was separated by means of a silica gel column, and the solvent was removed to obtain 8.79g in total of Z11 in 73% yield.

Compounds Z11(6.02g, 10mmol) and Z12(2.85g, 10mmol) were dissolved in anhydrous toluene, sodium tert-butoxide (1.15g, 12mmol) and tris-dibenzylideneacetone dipalladium (0.27g, 0.3mmol) were added, nitrogen was replaced three times, tri-tert-butylphosphine (0.3mmol) was added, the temperature was gradually raised to 80 ℃, the reaction was stirred for 12 hours, and the heat source was removed. After the system is cooled, deionized water is added, an organic layer is separated, ethyl acetate is used for extraction for three times, concentration is carried out under reduced pressure, and 6.94G of product G61 is obtained after the product G61 is filtered through a silica gel column, wherein the yield is 86%; MS:807[ M ⁺]。

Example 8: synthesis of Compound G116

Z14(5.56g, 30mmol), methyl o-bromobenzoate (6.45g, 30mmol), potassium carbonate (12.42g, 90mmol) and tetrakis (triphenylphosphine) palladium (1.04g, 0.9mmol) were weighed into a 250mL two-necked flask, 120mL of a mixed solvent of toluene and methanol was added, nitrogen gas was purged three times, the temperature was raised to 90 ℃ and the mixture was stirred overnight. After the reaction liquid is cooled to room temperature, water is added, ethyl acetate is used for extraction, sodium sulfate is used for drying, the organic solvent is removed by reduced pressure distillation, and silica gel is used for column chromatography separation. And putting the intermediate into a methanesulfonic acid solution, heating to 130 ℃, continuing to react for 2 hours, cooling to room temperature, adding NaOH for neutralization, performing suction filtration, and performing silica gel sample mixing and column chromatography separation to obtain 4.13g of the target product Z15, wherein the yield is 41%.

Z16(3.72g, 12mmol) was dissolved in anhydrous tetrahydrofuran, cooled to-78 deg.C and butyllithium (1.6M, 7.5mL) was added slowly. After about 0.5 hour, a solution of Z15(4.03g, 12mmoL) in dry tetrahydrofuran was added dropwise to the flask, and the reaction was continued at this temperature for half an hour, then warmed to room temperature, and continued for 8 hours. The solvent was removed under reduced pressure, hydrochloric acid and acetic acid were added, and reflux was continued for about 2 hours. Cooled to room temperature, and deionized water was added, followed by extraction with ethyl acetate. After concentration, the mixture was separated by a silica gel column, and the solvent was removed to obtain 5.15g in total of Z17 in 78% yield.

Compound Z17(4.4g, 8mmol) and Z17-1(3.26g, 8mmol) were dissolved in anhydrous toluene, sodium tert-butoxide (0.92g, 9.6mmol) and tris-dibenzylideneacetone dipalladium (0.22g, 0.24mmol) were added, nitrogen was replaced three times, tri-tert-butylphosphine (0.24mmol) was added, the temperature was gradually raised to 80 ℃, the reaction was stirred for 12 hours, and the heat source was removed. After the system is cooled, deionized water is added, an organic layer is separated, ethyl acetate is used for extraction for three times, concentration is carried out under reduced pressure, and the product G116 of 5.61G is obtained after passing through a silica gel column, wherein the yield is 80%; MS 877[ M ]⁺]。

Example 9: synthesis of Compound G173

Z18(9.9g, 30mmol), Z19(10.77g, 30mmol), potassium carbonate (12.42g, 90mmol) and tetrakis (triphenylphosphine) palladium (1.04g, 0.9mmol) were weighed into a 250mL two-necked flask, 160mL of a mixed solvent of toluene and methanol was added, nitrogen gas was purged three times, the temperature was raised to 90 ℃, and the mixture was stirred overnight. After the reaction liquid is cooled to room temperature, water is added, ethyl acetate is used for extraction, sodium sulfate is used for drying, the organic solvent is removed through reduced pressure distillation, silica gel sample mixing column chromatography separation is carried out, 5.9g of the target product Z20 is obtained, and the yield is 38%.

Z20(5.18g, 10mmol) was dissolved in anhydrous tetrahydrofuran, cooled to-78 deg.C and butyllithium (1.6M, 6.3mL) was added slowly. After about 0.5 hour, a solution of fluorenone (1.8g, 10mmoL) in anhydrous tetrahydrofuran was added dropwise to the reaction flask, and the reaction was continued at this temperature for half an hour, then warmed to room temperature, and continued for 8 hours. The solvent was removed under reduced pressure, hydrochloric acid and acetic acid were added, and reflux was continued for about 2 hours. Cooled to room temperature, and deionized water was added, followed by extraction with ethyl acetate. After concentration, the mixture was separated by means of a silica gel column, and the solvent was removed to obtain 4.7g in total of Z21 in 78% yield.

Compound Z21(4.5g, 7.5mmol) and Z22(1.84g, 7.5mmol) were dissolved in anhydrous toluene, sodium tert-butoxide (0.86g, 9mmol) and tris-dibenzylideneacetone dipalladium (0.2g, 0.22mmol) were added, nitrogen was replaced three times, tri-tert-butylphosphine (0.22mmol) was added, the temperature was gradually raised to 80 ℃, the reaction was stirred for 12 hours, and the heat source was removed. After the system is cooled, deionized water is added, an organic layer is separated, ethyl acetate is used for extraction for three times, concentration is carried out under reduced pressure, and 4.95G of a product G173 is obtained after passing through a silica gel column, wherein the yield is 86%; MS:767[ M ]⁺]。

Example 10: synthesis of Compound G186

Compounds Z23(9.44g, 20mmol) and Z24(4.38g, 20mmol) were dissolved in anhydrous toluene, sodium tert-butoxide (2.3g, 24mmol) and tris-dibenzylideneacetone dipalladium (0.55g, 0.6mmol) were added thereto, nitrogen was replaced three times, tri-tert-butylphosphine (0.6mmol) was added thereto, the temperature was gradually raised to 80 ℃, the reaction was stirred for 12 hours, and the heat source was removed. After the system was cooled, deionized water was added, the organic layer was separated, extracted three times with ethyl acetate, concentrated under reduced pressure, and passed through a silica gel column to give 8.06g of product Z25 in 66% yield.

Z25(7.33g, 12mmol), o-bromobenzoic acid (2.4g, 12mmol), potassium carbonate (5g, 36mmol) and tetrakis (triphenylphosphine) palladium (0.42g, 0.36mmol) were taken and added to a 250mL two-necked flask, 150mL of a mixed solvent of toluene and methanol was added, nitrogen gas was purged three times, the temperature was raised to 90 ℃ and the mixture was stirred overnight. After the reaction solution was cooled to room temperature, water was added, and extraction was performed with ethyl acetate, drying was performed with sodium sulfate, the organic solvent was removed by distillation under the reduced pressure, and column chromatography was performed with silica gel to obtain 4.78g of product Z26 with a yield of 58%.

Z26(4.12g, 6mmol) was dissolved in anhydrous tetrahydrofuranTo the reaction mixture was cooled to-78 deg.C, butyl lithium (1.6M, 3.7mL) was added slowly. After about 0.5 hour, a solution of adamantanone (0.9g, 6mmoL) in anhydrous tetrahydrofuran was added dropwise to the flask, and the reaction was continued at this temperature for half an hour, then warmed to room temperature, and continued for 8 hours. The solvent was removed under reduced pressure, hydrochloric acid and acetic acid were added, and reflux was continued for about 2 hours. Cooled to room temperature, and deionized water was added, followed by extraction with ethyl acetate. After concentration, the mixture was separated by silica gel column, and the solvent was removed to obtain 3.65G in total of G186 in 82% yield. MS 741[ M ]⁺]。

Example 11: synthesis of Compound G113

Compounds Z17(4.4g, 8mmol) and Z27(2.6g, 8mmol) were dissolved in anhydrous toluene, sodium tert-butoxide (0.92g, 9.6mmol) and tris-dibenzylideneacetone dipalladium (0.22g, 0.24mmol) were added, nitrogen was replaced three times, tri-tert-butylphosphine (0.24mmol) was added, the temperature was gradually raised to 80 ℃, the reaction was stirred for 12 hours, and the heat source was removed. After the system is cooled, deionized water is added, an organic layer is separated, ethyl acetate is used for extraction for three times, concentration is carried out under reduced pressure, and 5.47G of a product G113 is obtained after the product G113 passes through a silica gel column, wherein the yield is 86%; MS 795[ M ]⁺]。

Example 12: synthesis of Compound G216

Z3(12.04g, 20mmol), p-chlorobenzoic acid (3.12g, 20mmol), potassium carbonate (8.28g, 60mmol) and tetrakis (triphenylphosphine) palladium (0.69g, 0.6mmol) were weighed into a 250mL two-necked flask, a mixed solvent of toluene and methanol was added, nitrogen gas was purged three times, the temperature was raised to 90 ℃ and the mixture was stirred overnight. After the reaction liquid is cooled to room temperature, water is added, ethyl acetate is used for extraction, sodium sulfate is used for drying, the organic solvent is removed through reduced pressure distillation, silica gel sample mixing column chromatography separation is carried out, 9.63g of the target product Z28 is obtained, and the yield is 76%.

Compound Z28(6.34g, 10mmol), Z29 (2.19)g, 10mmol) was dissolved in anhydrous toluene, sodium tert-butoxide (1.15g, 12mmol) and tris-dibenzylideneacetone dipalladium (0.27g, 0.3mmol) were added, nitrogen was replaced three times, tri-tert-butylphosphine (0.3mmol) was added, the temperature was gradually raised to 80 ℃, the reaction was stirred for 12 hours, and the heat source was removed. After the system is cooled, deionized water is added, an organic layer is separated, ethyl acetate is used for extraction for three times, concentration is carried out under reduced pressure, and 6.04G of product G216 is obtained after passing through a silica gel column, wherein the yield is 74%; MS:817[ M⁺]。

Example 13: synthesis of Compound G229

Z18(9.9g, 30mmol), Z30(9.45g, 30mmol), potassium carbonate (12.42g, 90mmol) and tetrakis (triphenylphosphine) palladium (1.04g, 0.9mmol) were weighed into a 250mL two-necked flask, a mixed solvent of toluene and methanol was added, nitrogen was purged three times, the temperature was raised to 90 ℃ and the mixture was stirred overnight. After the reaction liquid is cooled to room temperature, water is added, ethyl acetate is used for extraction, sodium sulfate is used for drying, the organic solvent is removed through reduced pressure distillation, silica gel sample mixing column chromatography separation is carried out, the total amount of the target product Z31 is 8.24g, and the yield is 58%.

Z31(7.11g, 15mmol) was dissolved in anhydrous tetrahydrofuran, cooled to-78 deg.C and butyl lithium (1.6M, 9.3mL) was added slowly. After about 0.5 hour, a solution of fluorenone (2.7g, 15mmoL) in anhydrous tetrahydrofuran was added dropwise to the reaction flask, and the reaction was continued at this temperature for half an hour, then warmed to room temperature, and continued for 8 hours. The solvent was removed under reduced pressure, hydrochloric acid and acetic acid were added, and reflux was continued for about 2 hours. Cooled to room temperature, and deionized water was added, followed by extraction with ethyl acetate. After concentration, the mixture was separated by a silica gel column, and the solvent was removed to obtain 4.52g in total of Z32 in 54% yield.

Compound Z32(4.18g, 7.5mmol) and Z32-1(3.04g, 7.5mmol) were dissolved in anhydrous toluene, sodium tert-butoxide (0.86g, 9mmol) and tris-dibenzylideneacetone dipalladium (0.2g, 0.22mmol) were added, nitrogen was replaced three times, tri-tert-butylphosphine (0.22mmol) was added, the temperature was gradually raised to 80 ℃, the reaction was stirred for 12 hours, and the heat source was removed. After the system is cooled, deionized water is added to separate the organic matterLayer, and extracted three times with ethyl acetate, concentrated under reduced pressure, and passed through a silica gel column to give 5.7G of product G229, 86% yield; MS 883M⁺]。

Example 14: synthesis of Compound G223

Z11(9.03g, 15mmol), m-chlorobenzeneboronic acid (2.34g, 15mmol), potassium carbonate (6.21g, 45mmol) and tetrakis (triphenylphosphine) palladium (0.52g, 0.45mmol) were weighed into a 250mL two-necked flask, a mixed solvent of toluene and methanol was added, nitrogen gas was purged three times, the temperature was raised to 90 ℃, and the mixture was stirred overnight. After the reaction liquid is cooled to room temperature, water is added, ethyl acetate is used for extraction, sodium sulfate is used for drying, the organic solvent is removed through reduced pressure distillation, silica gel sample mixing column chromatography separation is carried out, 6.56g of the target product Z33 is obtained, and the yield is 69%.

Compounds Z33(6.34g, 10mmol) and Z34(1.79g, 10mmol) were dissolved in anhydrous toluene, sodium tert-butoxide (1.15g, 12mmol) and tris-dibenzylideneacetone dipalladium (0.27g, 0.3mmol) were added thereto, nitrogen gas was replaced three times, tri-tert-butylphosphine (0.3mmol) was added thereto, the temperature was gradually raised to 80 ℃, the reaction was stirred for 12 hours, and the heat source was removed. After the system is cooled, deionized water is added, an organic layer is separated, ethyl acetate is used for extraction for three times, concentration is carried out under reduced pressure, and 6.6G of product G223 is obtained after passing through a silica gel column, wherein the yield is 85%; MS 777[ M ] ⁺]。

Example 15: synthesis of Compound G245

Z35(8.34g, 30mmol), Z19(10.77g, 30mmol), potassium carbonate (12.42g, 90mmol) and tetrakis (triphenylphosphine) palladium (1.04g, 0.9mmol) were weighed into a 250mL two-necked flask, a mixed solvent of toluene and methanol was added, nitrogen was purged three times, the temperature was raised to 90 ℃ and the mixture was stirred overnight. After the reaction liquid is cooled to room temperature, water is added, ethyl acetate is used for extraction, sodium sulfate is used for drying, the organic solvent is removed through reduced pressure distillation, and silica gel sample mixing column chromatography separation is carried out to obtain 5.73g of the target product Z36 totally, wherein the yield is 41%.

Z36(5.59g, 12mmol) was dissolved in anhydrous tetrahydrofuran, cooled to-78 deg.C and butyllithium (1.6M, 7.5mL) was added slowly. After about 0.5 hour, a solution of 4-bromofluorenone (3.1g, 12mmoL) in anhydrous tetrahydrofuran was added dropwise to the reaction flask, and the reaction was continued at this temperature for half an hour, then warmed to room temperature, and continued for 8 hours. The solvent was removed under reduced pressure, hydrochloric acid and acetic acid were added, and reflux was continued for about 2 hours. Cooled to room temperature, and deionized water was added, followed by extraction with ethyl acetate. After concentration, the mixture was separated by a silica gel column, and the solvent was removed to obtain 5.43g in total of Z37 in a yield of 72%.

Compounds Z37(5.02g, 8mmol) and Z29(3.5g, 16mmol) were dissolved in anhydrous toluene, sodium tert-butoxide (0.92g, 9.6mmol) and tris-dibenzylideneacetone dipalladium (0.22g, 0.24mmol) were added, nitrogen was replaced three times, tri-tert-butylphosphine (0.24mmol) was added, the temperature was gradually raised to 80 ℃, the reaction was stirred for 12 hours, and the heat source was removed. After the system is cooled, adding deionized water, separating an organic layer, extracting for three times by using ethyl acetate, concentrating under reduced pressure, and passing through a silica gel column to obtain 4.5G of a product G245 with the yield of 62%; MS 906[ M ] ⁺]。

Example 16: synthesis of Compound G248

Z1(11.58g, 30mmol) was dissolved in anhydrous tetrahydrofuran, cooled to-78 deg.C and butyllithium (1.6M, 18.7mL) was added slowly. After about 0.5 hour, a solution of cyclopentanone (2.52g, 30mmoL) in anhydrous tetrahydrofuran was added dropwise to the flask, and the reaction was continued at this temperature for half an hour, then warmed to room temperature, and continued for 8 hours. The solvent was removed under reduced pressure, hydrochloric acid and acetic acid were added, and reflux was continued for about 2 hours. Cooled to room temperature, and deionized water was added, followed by extraction with ethyl acetate. After concentration, the mixture was separated by a silica gel column, and the solvent was removed to obtain 8.41g in total of Z38 in a yield of 75%.

Z38(7.48g, 20mmol) was dissolved in anhydrous tetrahydrofuran, cooled to-78 deg.C and butyllithium (1.6M, 8.7mL) was added slowly. After about 0.5 hour, a solution of 4-bromofluorenone (5.18g, 20mmoL) in anhydrous tetrahydrofuran was added dropwise to the flask, and the reaction was continued at this temperature for half an hour, then warmed to room temperature, and continued for 8 hours. The solvent was removed under reduced pressure, hydrochloric acid and acetic acid were added, and reflux was continued for about 2 hours. Cooled to room temperature, and deionized water was added, followed by extraction with ethyl acetate. After concentration, the mixture was separated by a silica gel column, and the solvent was removed to obtain 7.72g in total of Z39 in a yield of 72%.

Compounds Z39(6.43g, 12mmol) and Z12(3.42g, 12mmol) were dissolved in anhydrous toluene, sodium tert-butoxide (1.34g, 14mmol) and tris-dibenzylideneacetone dipalladium (0.33g, 0.36mmol) were added thereto, nitrogen gas was replaced three times, tri-tert-butylphosphine (0.36mmol) was added thereto, the temperature was gradually raised to 80 ℃, the reaction was stirred for 12 hours, and the heat source was removed. After the system is cooled, adding deionized water, separating an organic layer, extracting for three times by using ethyl acetate, concentrating under reduced pressure, and passing through a silica gel column to obtain 5.33G of a product G248 with the yield of 60%; MS 741[ M ] ⁺]。

Example 17: synthesis of Compound G249

Z1(11.58g, 30mmol) was dissolved in anhydrous tetrahydrofuran, cooled to-78 deg.C and butyllithium (1.6M, 18.7mL) was added slowly. After about 0.5 hour, a solution of bicyclo [2.2.2] octan-2-one (3.72g, 30mmoL) in anhydrous tetrahydrofuran was added dropwise to the reaction flask, and the reaction was continued at this temperature for half an hour, then, the temperature was raised to room temperature, and the reaction was continued for 8 hours. The solvent was removed under reduced pressure, hydrochloric acid and acetic acid were added, and reflux was continued for about 2 hours. Cooled to room temperature, and deionized water was added, followed by extraction with ethyl acetate. After concentration, the mixture was separated by a silica gel column, and the solvent was removed to obtain 8.82g in total of Z40 in a yield of 71%.

Z40(8.28g, 20mmol) was dissolved in anhydrous tetrahydrofuran, cooled to-78 deg.C and butyllithium (1.6M, 8.7mL) was added slowly. After about 0.5 hour, a solution of 4-bromofluorenone (5.18g, 20mmoL) in anhydrous tetrahydrofuran was added dropwise to the flask, and the reaction was continued at this temperature for half an hour, then warmed to room temperature, and continued for 8 hours. The solvent was removed under reduced pressure, hydrochloric acid and acetic acid were added, and reflux was continued for about 2 hours. Cooled to room temperature, and deionized water was added, followed by extraction with ethyl acetate. After concentration, the mixture was separated by means of a silica gel column, and the solvent was removed to obtain 7.6g in total of Z41 in a yield of 66%.

Compounds Z41(5.76g, 10mmol) and Z22(2.45g, 10mmol) were dissolved in anhydrous toluene, sodium tert-butoxide (1.15g, 12mmol) and tris-dibenzylideneacetone dipalladium (0.27g, 0.3mmol) were added thereto, nitrogen gas was replaced three times, tri-tert-butylphosphine (0.3mmol) was added thereto, the temperature was gradually raised to 80 ℃, the reaction was stirred for 12 hours, and the heat source was removed. After the system is cooled, adding deionized water, separating an organic layer, extracting for three times by using ethyl acetate, concentrating under reduced pressure, and passing through a silica gel column to obtain 4.6G of a product G249, wherein the yield is 62%; MS is 741[ M⁺]。

2. Preparation and characterization of OLED device

The fabrication process of the OLED device using the above will be described in detail by specific examples.

The structures of the compounds involved in the devices are as follows:

device example 1 the preparation procedure was as follows:

and cleaning the ITO conductive glass anode layer, then ultrasonically cleaning the ITO conductive glass anode layer for 15 minutes by using deionized water, acetone and isopropanol, and then treating the ITO conductive glass anode layer in a plasma cleaner for 5 minutes to improve the work function of the electrode. Evaporating a hole injection layer material HATCN on the ITO anode layer by a vacuum evaporation mode, wherein the thickness is 5nm, and the evaporation rate is

On the hole injection layer, a hole transport material H1 was deposited by vacuum evaporation to a thickness of 80 nm. An electron blocking layer G11 was formed over the hole transport layer to a thickness of 20 nm. And a light-emitting layer is vapor-deposited on the electron blocking layer, GH1 is used as a host material, GD1 is used as a doping material, GD1 and GH1 have a mass ratio of 1:9, and the thickness is 30 nm. And (3) evaporating electron transport materials ET1 and LiQ on the light-emitting layer by a vacuum evaporation mode, wherein the ratio of the materials is 5: 5, the thickness is 30 nm. On the electron transport layer And an electron injection layer LiQ is formed by vacuum evaporation, and the thickness is 2 nm. And a cathode Al layer is evaporated in vacuum on the electron injection layer, and the thickness of the cathode Al layer is 80 nm.

Device examples 2 to 18 and device comparative examples 1 to 2 were prepared in substantially the same manner as device example 1, except that:

device example 2: the electron blocking layer of the organic electroluminescent device was changed to G16.

Device example 3: the electron blocking layer of the organic electroluminescent device becomes G23.

Device example 4: the electron blocking layer of the organic electroluminescent device becomes G37.

Device example 5: the electron blocking layer of the organic electroluminescent device was changed to G27.

Device example 6: the electron blocking layer of the organic electroluminescent device becomes G59.

Device example 7: the electron blocking layer of the organic electroluminescent device becomes G61.

Device example 8: the electron blocking layer of the organic electroluminescent device becomes G116.

Device example 9: the electron blocking layer of the organic electroluminescent device becomes G173.

Device example 10: the electron blocking layer of the organic electroluminescent device becomes G186.

Device example 11: the electron blocking layer of the organic electroluminescent device becomes G113.

Device example 12: the electron blocking layer of the organic electroluminescent device becomes G216.

Device example 13: the electron blocking layer of the organic electroluminescent device was changed to G229.

Device example 14: the electron blocking layer of the organic electroluminescent device becomes G223.

Device example 15: the electron blocking layer of the organic electroluminescent device becomes G245.

Device example 16: the electron blocking layer of the organic electroluminescent device becomes G248.

Device example 17: the electron blocking layer of the organic electroluminescent device becomes G249.

Device comparative example 1: the electron blocking layer of the organic electroluminescent device became C1.

Device comparative example 2: the electron blocking layer of the organic electroluminescent device became C2.

The luminous efficiency is that the current density is 10mA/cm²Relative values obtained when LT95 is a current density of 40mA/cm²The relative values obtained and the test results are shown in Table 1.

TABLE 1 device characterization results

It can be seen that, compared to device comparative examples 1 to 2, device examples 1 to 17 using the aromatic amine compound of the present invention as an electron blocking material can effectively improve the luminous efficiency and lifetime of an organic electroluminescent device. This is mainly because the non-aromatic rings in examples 17 have a large volume, and the interaction between the molecular groups can be effectively reduced. In addition, the freedom degree of the naphthenic base is small, the vibration in molecules is small, the molecular stability is high, and the stability of carrier transmission is improved.

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.

Claims (12)

1. An arylamine organic compound is characterized in that the structure of the arylamine organic compound is formed by combining a chemical formula (1) and a chemical formula (2):

wherein:

represents the fused site of chemical formula (1) and chemical formula (2);

n1 and n2 are respectively and independently selected from 0 or 1, and n1+ n2 is more than or equal to 1;

L₁and L₂Each independently selected from a single bond, or a substituted or unsubstituted aryl group having 6 to 40 ring atoms, or a substituted or unsubstituted heteroaryl group having 6 to 40 ring atoms;

Ar₁-Ar₄Each independently selected from a substituted or unsubstituted aromatic group having 6 to 40 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 40 ring atoms;

ring a is a non-aromatic ring system having 5 to 20 ring atoms.

2. An aromatic amine-based organic compound according to claim 1, having a structure represented by any one of formulas (3-1) to (3-5):

3. an arylamine organic compound according to claim 1, wherein Ar is Ar₁-Ar₄Are respectively and independently selected from any one of groups (B-1) to (B-7):

wherein:

each occurrence of X is independently selected from N or CR₁；

Y is selected from O, S, S ═ O, SO₂、NR₂、PR₂、CR₃R₄Or SiR₃R₄；

Ar₅Selected from an aromatic group having 6 to 20 ring atoms which may be substituted or unsubstituted, or a heteroaromatic group having 6 to 20 ring atoms which may be substituted or unsubstituted;

R₁-R₄each occurrence is independently selected from-H, -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, isocyanate, thiocyanate, isothiocyanate, hydroxy, nitro, CF ₃Cl, Br, F, a crosslinkable group, a substituted or unsubstituted aromatic group having 5 to 30 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms, an aryloxy group having 5 to 30 ring atoms, a heteroaryloxy group having 5 to 30 ring atoms, or a combination of these groups;

R₃and R₄With or without rings formed therebetween.

4. An arylamine organic compound according to claim 3, wherein Ar is Ar₁-Ar₄Are respectively and independently selected from any one of (C-1) to (C-5):

wherein: indicates the attachment site; m1, m2, m3, m4 and m5 are each independently selected from 0, 1, 2, 3 or 4.

5. The arylamine organic compound according to claim 4, wherein Ar is Ar₁-Ar₂At least one of them is selected from (C-2), and/or said Ar₃-Ar₄At least one of them is selected from (C-2).

6. The aromatic amine-based organic compound according to claim 1, wherein L is₁And L₂Independently selected from a single bond, or a group structurally having a benzene ring, naphthalene ring, pyridine, pyrimidine, triazine, quinoline, isoquinoline, dibenzofuran, dibenzothiophene, carbazole, fluorene or phenanthrene.

7. An arylamine organic compound according to any one of claims 1 to 6 wherein ring A is selected from any one of the following groups:

8. An arylamine organic compound according to claim 7,

is selected from

9. A mixture comprising the arylamine organic compound according to any one of claims 1 to 8 and at least one organic functional material selected from the group consisting of 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.

10. A composition comprising an arylamine organic compound according to any one of claims 1 to 8 or a mixture according to claim 9 and at least one organic solvent.

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

12. The organic electronic device according to claim 11, wherein 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 arylamine organic compound according to any one of claims 1 to 8, or the mixture according to claim 9, or is prepared from the composition according to claim 10.