CN115028623B

CN115028623B - Arylamine compound and application thereof in organic electronic device

Info

Publication number: CN115028623B
Application number: CN202210889852.5A
Authority: CN
Inventors: 杨曦; 肖立清
Original assignee: Guangzhou Zhuoguang Technology Co ltd
Current assignee: Guangzhou Zhuoguang Technology Co ltd
Priority date: 2022-07-27
Filing date: 2022-07-27
Publication date: 2024-01-05
Anticipated expiration: 2042-07-27
Also published as: CN115028623A

Abstract

The invention relates to an arylamine compound and application thereof. The compound introduces specific arylamine groups into the spiro structure, so that the hole transport property is enhanced; when the polymer is used as a hole transport material to be applied to an organic electroluminescent device, the luminous efficiency and the service life of the device can be improved.

Description

Arylamine compound and application thereof in organic electronic device

Technical Field

The invention relates to the field of organic photoelectric materials, in particular to an arylamine compound and application thereof in an organic electronic device.

Background

The OLED is called an organic light emitting diode, also called an organic laser display or an organic light emitting semiconductor, and the OLED display technology is a new generation flat panel display technology subsequent to the LCD, and compared with the LCD display, the OLED display technology has the advantages of power saving, light weight, large visual angle, flexibility and the like, and gradually becomes a mainstream scheme of a display panel with a medium or small size.

OLEDs are organic light emitting devices fabricated based on a variety of organic materials that convert electrical energy directly into light energy. The OLED material basic structure comprises a cathode, an anode, a hole transmission layer, an electron transmission layer and a luminescent layer, wherein electrons are injected from the cathode, holes are injected from the anode, and the injected electrons and holes respectively migrate from the electron transmission layer and the hole transmission layer to the luminescent layer under the action of an external electric field; after electrons and holes are injected into the light-emitting layer, electron-hole pairs, namely excitons, are formed, and the exciton radiation transitions to de-excite, and photons are emitted to make the OLED emit light. It can be seen that the OLED materials directly determine the light emitting characteristics of the panel, including the light emitting efficiency, the lifetime, etc., so the development of the key materials of the OLED core is of great importance.

In an OLED, the basic role of the hole transport layer is to increase the transport efficiency of holes in the device and to block electrons in the light emitting layer, achieving maximum recombination of carriers. The existence of the hole transmission layer can reduce potential barrier of holes in the injection process, increase hole injection efficiency, and improve brightness and service life of the device. The search for novel hole transport materials with excellent performance is a hot spot of research, and currently, the hole transport materials prepared based on triarylamine have TBD, NPB and the like, but the prepared device has low luminous efficiency and short service life due to the problems of poor film forming property, low thermal stability or low hole mobility and the like of the existing small molecular triarylamine compound.

Therefore, new high-performance hole transport materials are further developed.

Disclosure of Invention

The invention aims to provide an aromatic amine compound which can be used as a hole transport material in a functional layer of an organic electronic device, and the luminous efficiency of the device is prolonged, and the service life of the device is prolonged.

In order to achieve the technical scheme of the aim, the invention provides an arylamine compound, which is shown as a general formula (I):

wherein;

w is selected from O, S, siR ₄ R ₅ ；

Z is selected from O or S;

R ₁ 、R ₂ 、R ₃ independently selected from-H, -D, or a straight chain alkyl group having 1 to 20C atoms, or a branched alkyl group having 3 to 20C atoms, or a cyclic alkyl group having 3 to 20C atoms, or a cyano group, or a nitro group, or-CF ₃ or-Cl, or-Br, or-F, or phenyl, or a combination of these groups;

m, n, t are independently selected from 0,1,2,3 or 4;

R ₄ 、R ₅ each occurrence of a singleA member selected from the group consisting of-H, -D, or a linear alkyl group having 1 to 20 carbon atoms, or a linear alkoxy group having 1 to 20 carbon atoms, or a linear thioalkoxy group having 1 to 20 carbon atoms, or a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 3 to 20 carbon atoms, or a branched alkoxy group having 3 to 20 carbon atoms, or a cyclic alkoxy group having 3 to 20 carbon atoms, or a branched thioalkoxy group having 3 to 20 carbon atoms, or a cyclic thioalkoxy group having 3 to 20 carbon atoms, or an aromatic group having 6 to 60 ring atoms, or a substituted aromatic group having 6 to 60 ring atoms, or a combination of these groups;

Ar ₁ independently selected from a substituted or unsubstituted aromatic group having a ring atom number of 6 to 60, and a substituted or unsubstituted heteroaromatic group having a ring atom number of 5 to 60.

Correspondingly, the invention also provides a hole transport material which comprises at least one aromatic amine compound.

Correspondingly, the invention also provides a mixture which comprises at least one aromatic amine compound and at least one other organic functional material, wherein the at least one other organic functional material is selected from a Hole Injection Material (HIM), a Hole Transport Material (HTM), an Electron Transport Material (ETM), an Electron Injection Material (EIM), an Electron Blocking Material (EBM), a Hole Blocking Material (HBM), a light emitting guest material (Emitter), a light emitting Host material (Host) or an organic dye.

Accordingly, the present invention also provides a composition comprising at least one aromatic amine compound or mixture as described above, and at least one organic solvent.

Correspondingly, the invention also provides an organic electronic device, which comprises at least one functional layer, wherein the functional layer comprises at least one aromatic amine compound or a mixture or is prepared from the composition.

Accordingly, the functional layer of the organic electronic device according to the present invention is selected from hole transport layers.

Compared with the prior art, the invention has the remarkable advantages that:

the arylamine compound of the invention combines a spiro ring with an arylamine groupAre linked together and are designated to be linked at +.>Thereby enhancing the stability and hole transport property of molecules, and improving the luminous efficiency and the service life of the device when the polymer is used as a hole transport material in an organic luminous device.

Drawings

FIG. 1 is a schematic view of an OLED structure according to the present invention

Wherein 101 is an anode; 102 is a hole injection layer; 103 is a hole transport layer; 104 is an electron blocking layer; 105 is a light emitting layer; 106 is an electron transport layer; 107 is an electron injection layer; 108 is the cathode.

Detailed Description

The following description of the embodiments of the present application will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all, of the embodiments of the present application. All other embodiments, based on the embodiments herein, which are obtained by a person skilled in the art without making any inventive effort, are intended to be within the scope of the present application. Furthermore, it should be understood that the detailed description is presented herein for purposes of illustration and explanation only and is not intended to limit the present application. In this application, unless otherwise indicated, terms of orientation such as "upper" and "lower" are used to generally refer to upper and lower positions of the device in actual use or operation. In addition, in the description of the present application, the term "comprising" means "including but not limited to," the term "plurality" means "two or more," and the term "and/or" includes any and all combinations of one or more of the associated listed items. Various embodiments of the present application may exist in a range format; it should be understood that the description in a range format is merely for convenience and brevity and should not be interpreted as a rigid limitation on the scope of the application. It is therefore to be understood that the range description has specifically disclosed all possible sub-ranges and individual values within that range. For example, it should be considered that a description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5, and 6, wherever applicable. In addition, whenever a numerical range is referred to herein, it is meant to include any reference number (fractional or integer) within the indicated range.

The term "and/or," "and/or," as used herein, includes any one of two or more of the listed items in relation to each other, as well as any and all combinations of the listed items in relation to each other, including any two of the listed items in relation to each other, any more of the listed items in relation to each other, or all combinations of the listed items in relation to each other. It should be noted that, when at least three items are connected by a combination of at least two conjunctions selected from "and/or", "or/and", "and/or", it should be understood that, in this application, the technical solutions certainly include technical solutions that all use "logical and" connection, and also certainly include technical solutions that all use "logical or" connection. For example, "a and/or B" includes three parallel schemes A, B and a+b. For another example, the technical schemes of "a, and/or B, and/or C, and/or D" include any one of A, B, C, D (i.e., the technical scheme of "logical or" connection), and also include any and all combinations of A, B, C, D, i.e., any two or three of A, B, C, D, and also include four combinations of A, B, C, D (i.e., the technical scheme of "logical and" connection).

In the present invention, aromatic groups and aromatic ring systems have the same meaning and can be interchanged.

In the present invention, the heteroaromatic groups, heteroaromatic groups and heteroaromatic ring systems have the same meaning and can be interchanged.

In the present invention, the "heteroatom" is a non-carbon atom, and may be an N atom, an O atom, an S atom, or the like.

In the present invention, "substituted" means that one or more hydrogen atoms in the substituted group are substituted with the substituent.

In the present invention, "monosubstituted" means substituted with one substituent, "disubstituted" means substituted with two substituents, "trisubstituted" means substituted with three substituents, "tetrasubstituted" means substituted with four substituents, "pentasubstituted" means substituted with five substituents.

In the present invention, the same substituent may be independently selected from different groups when it appears multiple times. If the general formula contains a plurality of R, R can 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 that the defined group may be substituted with one or more substituents R selected from, but not limited to: deuterium, cyano, isocyano, nitro or halogen, alkyl containing 1 to 20C atoms, heterocyclyl containing 3 to 20 ring atoms, aromatic containing 6 to 20 ring atoms, heteroaromatic containing 5 to 20 ring atoms, -NR' R ", silane, carbonyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, haloformyl, formyl, isocyanate, thiocyanate, isothiocyanate, hydroxyl, trifluoromethyl, and which may be further substituted with substituents acceptable in the art; it is understood that R 'and R "in-NR' R" are each independently selected from, but not limited to: H. deuterium atoms, cyano groups, isocyano groups, nitro groups or halogen groups, alkyl groups containing 1 to 10C atoms, heterocyclic groups containing 3 to 20 ring atoms, aromatic groups containing 6 to 20 ring atoms, heteroaromatic groups containing 5 to 20 ring atoms. Preferably, R is selected from, but not limited to: deuterium atoms, cyano groups, isocyano groups, nitro groups or halogen groups, alkyl groups containing 1 to 10C atoms, heterocyclic groups containing 3 to 10 ring atoms, aromatic groups containing 6 to 20 ring atoms, heteroaromatic groups containing 5 to 20 ring atoms, silane groups, carbonyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, carbamoyl groups, haloformyl groups, formyl groups, isocyanate groups, thiocyanate groups, isothiocyanate groups, hydroxyl groups, trifluoromethyl groups, and which may be further substituted with substituents acceptable in the art.

In the present invention, the "number of ring atoms" means 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, a heterocyclic compound) in which atoms are bonded to form a ring. When the ring is substituted with a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The same applies to the "number of ring atoms" described below, 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" refers to an aromatic hydrocarbon group derived from an aromatic ring compound by removal of one hydrogen atom, which may be a monocyclic aryl group, or a fused ring aryl group, or a polycyclic aryl group, at least one of which is an aromatic ring system for a polycyclic species. For example, "substituted or unsubstituted aryl group having 6 to 40 ring atoms" means an aryl group having 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: phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, fluoranthryl, triphenylenyl, pyrenyl, perylenyl, tetracenyl, fluorenyl, perylenyl, acenaphthylenyl 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 acenaphthene, fluorene, or 9, 9-diaryl fluorene, triarylamine, diaryl ether systems in particular should also be included in the definition of aryl groups.

"heteroaryl or heteroaromatic group" means that at least one carbon atom is replaced by a non-carbon atom on the basis of an aryl group, which may be an N atom, an O atom, an S atom, or the like. 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 the heteroaryl is optionally further substituted, suitable examples include, but are not limited to: thienyl, furyl, pyrrolyl, diazolyl, triazolyl, imidazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, benzothienyl, benzofuranyl, indolyl, pyrroloimidazolyl, pyrrolopyrrolyl, thienopyrrolyl, thienothiophenoyl, furopyrrolyl, furofuranyl, thienofuranyl, benzisoxazolyl, benzisothiazolyl, benzimidazolyl, phthalazinyl, phenanthridinyl, primary pyridyl, quinazolinonyl, dibenzothienyl, dibenzofuranyl, carbazolyl, and derivatives thereof.

In the present invention, "alkyl" may denote 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 this term, e.g., "C ₁ -C ₉ Alkyl "means an alkyl group containing 1 to 9 carbon atoms, and each occurrence may be, independently of the other, C ₁ Alkyl, C ₂ Alkyl, C ₃ Alkyl, C ₄ Alkyl, C ₅ Alkyl, C ₆ Alkyl, C ₇ Alkyl, C ₈ Alkyl or C ₉ An 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, 3, 7-di-octylMethyloctyl, 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, 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, and the like.

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

In the present invention "×" associated with a single bond represents a linking or fusing site;

in the present invention, when no linking site is specified in the group, an optionally-ligatable site in the group is represented as a linking site;

in the present invention, when the same group contains a plurality of substituents of the same symbol, each substituent may be the same or different from each other, for exampleThe 6R groups on the benzene ring may be the same or different from each other.

In the present invention, a single bond to which a substituent is attached extends through the corresponding ring, meaning that the substituent may be attached to an optional position on the ring, e.gR in (C) is connected with any substitutable site of benzene ring.

As used in the present invention, "a combination thereof", "any combination thereof", "a combination of groups", "a combination", and the like include all suitable combinations of any two or more of the listed groups.

In the present invention, "further", "still further", "particularly" and the like are used for descriptive purposes to indicate differences in content but should not be construed as limiting the scope of the invention.

In the present invention, "optional" means optional or not, that is, means any one selected from two parallel schemes of "with" or "without". If multiple "alternatives" occur in a technical solution, if no particular description exists and there is no contradiction or mutual constraint, then each "alternative" is independent.

In the invention, the technical characteristics described in an open mode comprise a closed technical scheme composed of the listed characteristics and also comprise an open technical scheme comprising the listed characteristics.

An arylamine compound is shown as a general formula (I):

wherein;

w is selected from O, S, siR ₄ R ₅ ；

Z is selected from O or S;

m, n, t are independently selected from 0,1,2,3 or 4;

R ₄ 、R ₅ independently at each occurrence selected from-H, -D, or a linear alkyl group having 1 to 20 carbon atoms,Or a linear alkoxy group having 1 to 20 carbon atoms, or a linear thioalkoxy group having 1 to 20 carbon atoms, or a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 3 to 20 carbon atoms, or a branched alkoxy group having 3 to 20 carbon atoms, or a cyclic alkoxy group having 3 to 20 carbon atoms, or a branched thioalkoxy group having 3 to 20 carbon atoms, or a cyclic thioalkoxy group having 3 to 20 carbon atoms, or an aromatic group having 6 to 60 ring atoms, or a substituted aromatic group having 6 to 60 ring atoms, or a combination of these groups;

In one embodiment, the compound of formula (I) is selected from formula (II-1) or formula (II-2):

in one embodiment, ar ₁ Independently selected from a substituted or unsubstituted aromatic group having a ring atom number of 6 to 26, and a substituted or unsubstituted heteroaromatic group having a ring atom number of 5 to 26. Further, ar ₁ Independently selected from a substituted or unsubstituted aromatic group having a ring atom number of 6 to 13, or a substituted or unsubstituted heteroaromatic group having a ring atom number of 6 to 13.

In one embodiment, ar ₁ Independently selected from the following groups:

wherein: x is independently selected from CR for each occurrence ₆ Or N;

y is independently selected from CR for each occurrence ₇ R ₈ 、NR ₉ 、SiR ₇ R ₈ 、O、S、Se、S＝O、S(＝O) ₂ Or PR (PR) ₉ ；

R ₆ -R ₉ Each occurrence is independently selected from the group consisting of-H, -D, or a linear alkyl group having 1 to 20 carbon atoms, or a linear alkoxy group having 1 to 20 carbon atoms, or a linear thioalkoxy group having 1 to 20 carbon atoms, or a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 3 to 20 carbon atoms, or a branched alkoxy group having 3 to 20 carbon atoms, or a cyclic alkoxy group having 3 to 20 carbon atoms, or a branched thioalkoxy group having 3 to 20 carbon atoms, or a cyclic thioalkoxy group having 3 to 20 carbon atoms, or a silyl group, or a keto group having 1 to 20 carbon atoms, or an alkoxycarbonyl group having 2 to 20 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate or isothiocyanate groups, hydroxyl, nitro, -CF ₃ -Cl, -Br, -F, -I, or an aromatic group having 6 to 60 ring atoms, or a substituted aromatic group having 6 to 60 ring atoms, or a heteroaromatic group having 5 to 60 ring atoms, or a substituted heteroaromatic group having 5 to 60 ring atoms, or an aryloxy group having 6 to 60 ring atoms, or a heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups; adjacent R ₆ With or without each other being cyclic;

when X is a linking site, X is selected from C atoms; when Y is a linking site, X is selected from N atoms.

In a particular embodiment, ar ₁ Independently selected from the following groups:

wherein: * Expression of the ligation site.

In one embodiment, the compound of formula (I) is selected from the group consisting of formula (III-1) or formula (III-2) or formula (III-3) or formula (III-4):

preferably, Z, W in formula (III-1) or formula (III-2) is selected from O or S, Y is selected from O or S or-C (CH) ₃ ) ₂ . More preferably, Z, W and Y are selected from O or S.

In one embodiment, each occurrence of X is independently selected from CR ₆ Or N; wherein: r is R ₆ Each occurrence is independently selected from-H, -D, or a straight chain alkyl group having 1 to 10 carbon atoms, or a branched alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms, or phenyl, or biphenyl, or pyridinyl, or pyrimidinyl, or naphthyl, or quinolinyl, or isoquinolinyl, or a combination of these groups.

In one embodiment, R ₁ 、R ₂ 、R ₃ Independently selected from-H, -D, or a straight chain alkyl group having 1 to 10C atoms, or a branched alkyl group having 3 to 10C atoms, or a cyclic alkyl group having 3 to 10C atoms, or a combination of these groups.

In one embodiment, triarylamine compounds according to the present application include, but are not limited to, the following:

/>

the arylamine compound according to the present invention can be used as a functional material in a functional layer of an organic electronic device. Organic functional layers include, but are not limited to, hole Injection Layers (HIL), hole Transport Layers (HTL), electron Transport Layers (ETL), electron Injection Layers (EIL), electron Blocking Layers (EBL), hole Blocking Layers (HBL), light emitting layers (EML).

Preferably, the arylamine compound according to the present invention is used as a hole transport material in an organic electronic device.

The invention further relates to a hole transport material comprising at least one arylamine compound as described above.

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 selected from the group consisting of a Hole Injection Material (HIM), a Hole Transport Material (HTM), an Electron Transport Material (ETM), an Electron Injection Material (EIM), an Electron Blocking Material (EBM), a Hole Blocking Material (HBM), a luminescent material (Emitter), a Host material (Host) and an organic dye. Various organic functional materials are described in detail in, for example, CN109336834 (a), KR2022006923 (a) WO2014072017a, the entire contents of which 3 patent documents are hereby incorporated by reference.

In an embodiment, the further organic functional material is selected from electron transport materials, and is used as a co-host in an organic electronic device.

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, borate or phosphate compound, or mixture of two or more solvents.

In a preferred embodiment, a composition according to the invention, said at least one organic solvent is chosen from solvents based on aromatic or heteroaromatic groups.

Examples of aromatic or heteroaromatic-based solvents suitable for the present invention are, but are not limited to: para-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1, 4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, dipentylbenzene, tripentylbenzene, pentyltoluenes, 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-difluorodiphenyl methane, 1, 2-dimethoxy-4- (1-propenyl) benzene, diphenyl methane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, α -dichlorodiphenyl methane, 4- (3-phenylpropyl) pyridine, benzyl benzoate, 1-bis (3, 4-dimethylphenyl) ethane, 2-isopropylnaphthalene, 2-quinolinecarboxylic acid, ethyl ester, 2-methylfuran, etc.;

Examples of aromatic ketone-based solvents suitable for the present invention are, but are 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-methylpropionophenone, 3-methylpropionophenone, 2-methylpropionophenone, and the like;

examples of aromatic ether-based solvents suitable for the present invention are, but are not limited to: 3-phenoxytoluene, butoxybenzene, p-anisaldehyde dimethyl acetal, tetrahydro-2-phenoxy-2H-pyran, 1, 2-dimethoxy-4- (1-propenyl) benzene, 1, 4-benzodioxane, 1, 3-dipropylbenzene, 2, 5-dimethoxytoluene, 4-ethylben-ther, 1, 3-dipropoxybenzene, 1,2, 4-trimethoxybenzene, 4- (1-propenyl) -1, 2-dimethoxybenzene, 1, 3-dimethoxybenzene, glycidyl phenyl ether, dibenzyl ether, 4-t-butyl anisole, trans-p-propenyl anisole, 1, 2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran, ethyl-2-naphthyl ether;

in some preferred embodiments, the composition according to the invention, said at least one solvent may be chosen from: aliphatic ketones such as 2-nonene, 3-nonene, 5-nonene, 2-decanone, 2, 5-adipone, 2,6, 8-trimethyl-4-nonene, fenchyl ketone, 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.

In other preferred embodiments, the at least one solvent according to the compositions of the present invention may be chosen 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. Particular preference is given to octyl octanoate, diethyl sebacate, diallyl phthalate and isononyl isononanoate.

The solvent 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 polymer or mixture as described above and at least one organic solvent, and may further comprise another organic solvent. Examples of other organic solvents 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-trichloroethane, 1, 2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethylsulfoxide, tetrahydronaphthalene, decalin, indene and/or mixtures thereof.

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

δd (dispersion force) is in the range of 17.0 to 23.2MPa1/2, particularly in the range of 18.5 to 21.0MPa 1/2;

δp (polar force) is in the range of 0.2 to 12.5MPa1/2, particularly in the range of 2.0 to 6.0MPa 1/2;

δh (hydrogen bonding force) is in the range of 0.9 to 14.2MPa1/2, particularly in the range of 2.0 to 6.0MPa 1/2.

The composition according to the invention, wherein the organic solvent is selected taking into account its boiling point parameters. In the invention, the boiling point of the organic solvent is more than or equal to 150 ℃; preferably not less than 180 ℃; more preferably not less than 200 ℃; more preferably not less than 250 ℃; and most preferably at a temperature of 275 ℃ or more or 300 ℃ or more. Boiling points in these ranges are beneficial in preventing nozzle clogging of inkjet printheads. The organic solvent may be evaporated from the solvent system to form a 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 according to embodiments of the present invention may comprise from 0.01 to 10% by weight of a compound or mixture according to the present invention, preferably from 0.1 to 8% by weight, more preferably from 0.2 to 5% by weight, most preferably from 0.25 to 3% by weight.

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 printing or coating.

Suitable Printing or coating techniques include, but are not limited to, ink jet Printing, spray Printing (nozle Printing), letterpress Printing, screen Printing, dip coating, spin coating, doctor blade coating, roller Printing, twist roller Printing, lithographic Printing, flexography, rotary Printing, spray coating, brush or pad Printing, slot die coating, and the like. Gravure printing, inkjet printing and inkjet 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, etc., for adjusting viscosity, film forming properties, improving adhesion, etc. The printing technology and the related requirements of the solution, such as solvent, concentration, viscosity and the like.

The invention also provides an application of the arylamine compound, the mixture or the composition in an organic electronic device, wherein the organic electronic device can be selected from, but not limited to, an organic light-emitting diode (OLED), an organic photovoltaic cell (OPV), an organic light-emitting cell (OLEEC), an Organic Field Effect Transistor (OFET), an organic light-emitting field effect transistor, an organic laser, an organic spintronic device, an organic sensor, an organic plasmon emitting diode (Organic Plasmon Emitting Diode) and the like, and particularly preferably an OLED. In the embodiment of the invention, the arylamine compound is preferably used for a hole transport layer of an OLED device. More preferably, the arylamine compound according to the present invention is used in a hole transport layer of a green organic electronic device.

The invention further relates to 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, said organic functional layers comprising or being prepared from an organic compound, mixture or composition as described above. Further, the organic electronic device comprises a cathode, an anode, and one or more organic functional layers located at the cathode and the anode.

The organic electronic device may be selected from, but not limited to, organic Light Emitting Diode (OLED), organic photovoltaic cell (OPV), organic light emitting cell (OLEEC), organic Field Effect Transistor (OFET), organic light emitting field effect transistor, organic laser, organic spintronic device, organic sensor and organic plasmon emitting diode (Organic Plasmon Emitting Diode), etc., and particularly preferably organic electroluminescent devices such as OLED, OLEEC, organic light emitting field effect transistor.

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), a Hole Blocking Layer (HBL). Suitable materials for use in these functional layers are described in detail above and in CN109336834 (a), KR2022006923 (a), WO2014072017a, the entire contents of which 3 patent documents are hereby incorporated by reference.

In one embodiment the organic functional layer comprises at least one hole transporting layer comprising an arylamine compound as described above. The definition of specific aromatic amine compounds is as described above.

In one embodiment, an organic electronic device according to the present invention includes a cathode, an anode, a light-emitting layer between the cathode and the anode, and a hole-transporting layer between the anode and the light-emitting layer.

Further, the organic electronic device according to the present invention comprises a cathode, an anode, a light emitting layer between the cathode and the anode, a hole transporting layer between the anode and the light emitting layer, and an electron transporting layer between the cathode and the light emitting layer.

Further, the organic electronic device further comprises a hole injection layer between the anode and the hole transport layer.

Further, the organic electronic device further comprises an electron injection layer between the cathode and the electron transport layer.

Further, the organic electronic device further comprises an electron blocking layer between the hole transporting layer and the light emitting layer.

In particular, the substrate may be transparent or opaque. A transparent substrate may be used to fabricate a transparent light emitting device. See, for example, bulovic et al Nature 1996,380, p29, and Gu et al, appl. Phys. Lett.1996,68, p2606. The substrate may also be rigid or elastic. In one embodiment, the substrate is plastic, metal, semiconductor wafer, or glass. Preferably, the substrate has a smooth surface, and a substrate free of surface defects is a particularly desirable choice. In a preferred embodiment, the substrate is flexible, optionally in a polymer film or plastic, having a glass transition temperature Tg of 150℃or higher, preferably over 200℃and more preferably over 250℃and most preferably over 300 ℃. Examples of suitable flexible substrates are poly (ethylene terephthalate) (PET) and polyethylene glycol (2, 6-naphthalene) (PEN).

The anode is an electrode that injects holes, and the anode can easily inject holes into the hole injection layer, or the hole transport layer, or the light emitting layer. The anode may comprise a conductive metal, conductive metal oxide, or conductive polymer. In one embodiment, the absolute value of the difference between the work function of the anode and the HOMO level or valence band level of the emitter in the light emitting layer or of the p-type semiconductor material as HIL or HTL or Electron Blocking Layer (EBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2eV. Examples of anode materials include, but are not limited to: al, cu, au, ag, mg, fe, co, ni, mn, pd, pt, ITO aluminum doped zinc oxide (AZO), and the like. Other suitable anode materials are known and can be readily selected for use by one of ordinary skill in the art. The anode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam) induced evaporation, and the like. In certain embodiments, the anode is patterned. Patterned ITO conductive substrates are commercially available and can be used to prepare devices according to the present application.

The cathode is an electrode that injects electrons, and the cathode can easily inject electrons into the electron injection layer, or the electron transport layer, or the light emitting layer. The cathode may comprise a conductive metal or conductive metal oxide. In one embodiment, the absolute value of the difference between the work function of the cathode and the LUMO or conduction band level of the light-emitting body in the light-emitting layer or of the n-type semiconductor material as an Electron Injection Layer (EIL) or Electron Transport Layer (ETL) or Hole Blocking Layer (HBL) is less than 0.5eV, preferably less than 0.3eV, and most preferably less than 0.2eV. In principle, all materials that can be used as cathodes of the organic electronic devices are possible as cathode materials for the organic electronic devices of the present application. Examples of cathode materials include, but are not limited to: al, au, ag, ca, ba, mg, liF/Al, mgAg alloy, baF2/Al, cu, fe, co, ni, mn, pd, pt, ITO, etc. The cathode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam) induced evaporation, and the like.

The hole injection layer is a layer for promoting injection of holes from the anode to the light emitting layer, and the hole injection material is a material that can efficiently receive holes injected from the positive electrode at a low voltage, and it is preferable that the Highest Occupied Molecular Orbital (HOMO) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metalloporphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material (HATCN), and the like, but are not limited thereto.

An electron blocking layer may be disposed between the hole transport layer and the light emitting layer. As the electron blocking layer, an aromatic amine-based compound or a material known in the art may be used.

The light emitting layer may emit red light, green light, or blue light, and may be composed of a phosphorescent material or a fluorescent material. The light emitting material is a material that can receive holes and electrons from the hole transporting layer and the electron transporting layer, respectively, and combine the holes and the electrons to excite light in the visible light region, and is preferably a fluorescent or phosphorescent material having good quantum efficiency.

Examples of the host material for the light-emitting layer include a condensed aromatic ring derivative or a heterocyclic ring-containing compound, and the like. Specifically, examples of the condensed aromatic ring derivative include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, and the like, and examples of the heterocycle-containing compound include carbazole derivatives, dibenzofuran derivatives, ladder-type furan compounds, pyrimidine derivatives, and the like, but examples thereof are not limited thereto.

In order to make the light emitting layer emit red light, the following may be used as a light emitting guest material: phosphorescent materials, such as iridium bis (1-phenylisoquinoline) acetylacetonate (PIQIr (acac)), iridium bis (1-phenylquinoline) acetylacetonate (PQIr (acac)), iridium tris (1-phenylquinoline) acetylacetonate (PQIr) or platinum octaethylporphyrin (PtOEP); or a fluorescent material such as tris (8-hydroxyquinoline) aluminum (Alq 3), but is not limited thereto. For the light emitting layer to emit green light, a phosphorescent material such as planar tris (2-phenylpyridine) iridium (Ir (ppy) 3), GD1, or a fluorescent material such as tris (8-hydroxyquinoline) aluminum (Alq 3) may be used as a light emitting dopant, but is not limited thereto. In order for the light emitting layer to emit blue light, the following may be used as a light emitting dopant: phosphorescent materials, e.g. (4, 6-F) ₂ ppy) ₂ Irpic; or a fluorescent material such as spiro-DPVBi, spiro-6P, biphenyl vinyl benzene (DSB), biphenyl vinyl arylene (DSA), pyrene-based arylamine compound, boron nitride compound, PFO-based polymer, or PPV-based polymer, but not limited thereto.

The electron transport layer may be used to transport electrons smoothly. Suitable electron transport materials are materials having high electron mobility that can efficiently receive electrons injected from the negative electrode and transfer the electrons to the light emitting layer. Specific examples thereof may include, but are not limited to: at least one of Al complexes of 8-hydroxyquinoline, complexes comprising Alq3, organic radical compounds, hydroxyflavone-metal complexes, lithium 8-hydroxyquinoline (LiQ), ET1 and benzimidazole-based compounds.

The electron injection layer may be used to smoothly inject electrons. The electron injection material is preferably: including fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, oxazole, diazole, triazole, imidazole, perylene tetracarboxylic acid, fluorenylidene methane, anthrone and the like and derivatives thereof, metal complex compounds, nitrogen-containing 5-membered ring derivatives and the like, but are not limited thereto.

The emission wavelength of the organic electronic device is between 300 and 1000nm, preferably between 350 and 900nm, more preferably between 400 and 800 nm.

In one embodiment the organic functional layer comprises at least one hole transporting layer comprising an arylamine compound 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 invention will be described in connection with preferred embodiments, but the invention is not limited to the embodiments described below, it being understood that the appended claims outline the scope of the invention and those skilled in the art, guided by the inventive concept, will recognize that certain changes made to the embodiments of the invention will be covered by the spirit and scope of the claims.

The compounds were prepared as follows:

example 1: synthesis of Compound 14

Synthesis of Compound 1-1:

1-bromo-2 naphthol (22.3 g,100 mmol), o-fluorobenzeneboronic acid (14 g,100 mmol), pd-132 (3.6 g,5 mmol) and potassium carbonate (27.6 g,200 mmol) are accurately weighed, sequentially added into a 1000mL three-necked flask, about 400mL of toluene and about 100mL of water are added, the temperature is raised to 80 ℃ for reaction for 4 hours after three times of pumping-in nitrogen, the raw materials are cooled to room temperature after complete reaction, diluted by water, extracted by ethyl acetate, dried by anhydrous sodium sulfate and distilled under reduced pressure to remove redundant solvent, and silica gel is stirred for column chromatography, wherein the eluent is PE: EA=3:1 (volume ratio). About 19.8g of compound 1-1 was obtained in yield: 83.1%. Ms 239.26

Synthesis of Compounds 1-2:

accurately weighing compound 1-1 (19.1 g,80 mmol), adding cesium carbonate (52.3 g,160 mmol) into a 1000mL three-necked flask in sequence, adding about 500mL of DMF, pumping nitrogen three times, and heating to 140 ℃ for reaction for 12 hours. After the raw materials are completely reacted, cooling to room temperature, diluting with water, extracting with ethyl acetate, drying with anhydrous sodium sulfate, pressurizing and distilling to remove redundant solvent, pulping the crude product with methanol, and obtaining about 15.2g of compound 1-2. Yield: 87.1%. Ms 219.26

Synthesis of Compounds 1-3:

Accurately weighing compound 1-2 (15.2 g,70 mmol), adding into a 500mL three-necked flask, adding about 200mL of chloroform, pumping and ventilating for three times, cooling to about-10 ℃ in an ice salt bath, slowly adding dropwise bromine (11.1 g,70 mmol) into the system, naturally heating to room temperature, and reacting overnight. After the reaction of the raw materials is completed, the raw materials are directly washed with water, extracted by methylene dichloride, the redundant solvent is removed by merging the organic phases through reduced pressure distillation, and the compound 1-3 of about 18.8g is obtained after pulping by methanol, and the yield is: 90.4%. Ms 298.15

Synthesis of Compounds 1-4:

accurately weighing 1-3 (5.9 g,20 mmol), 2-aminodibenzothiophene (4.0 g,20 mmol), dipalladium tris (dibenzylideneacetone) (0.58 g,1 mmol), sodium tert-butoxide (3.8 g,40 mmol) were sequentially added into a 500mL three-neck flask, about 100mL of anhydrous toluene was added, three nitrogen-filled reaction systems were purged, and tri-tert-butylphosphine (plastid ratio 10%4.1 mL) was added dropwise, followed by heating to 100℃for reaction for 6 hours. After the raw materials are completely reacted, cooling to room temperature, adding water for dilution, extracting with ethyl acetate for three times, combining organic phases, spin-drying, and performing silica gel column chromatography, wherein the eluting agent is PE (polyethylene) with DCM=5:1 (volume ratio). About 6.8g of compound 1-4 was obtained in yield: 81.8%. Ms 416.51

Synthesis of Compound 14:

accurately weighing compound 1-4 (6.6 g,16 mmol) and compound A (6.8 g,16 mmol) as well as tris (dibenzylideneacetone) dipalladium (0.46 g,0.8 mmol), sequentially adding sodium tert-butoxide (3.8 g,40 mmol) into a 500mL three-neck flask, adding about 150mL of anhydrous toluene, pumping and charging nitrogen gas, dropwise adding tri-tert-butylphosphine (plastid ratio of 10% to 3.2 mL) into the reaction system, and then heating to 100 ℃ for reaction for 6 hours. After the raw materials are completely reacted, cooling to room temperature, adding water for dilution, extracting with ethyl acetate for three times, combining organic phases, spin-drying, and performing silica gel column chromatography, wherein the eluting agent is PE, DCM=10:1 (volume ratio). Compound 14 was obtained at about 8.5. Yield: 69.7%. Ms 762.96.

Example 2: synthesis of Compound 23

Synthesis of Compound 2-1:

accurately weighing 1-bromo-2 fluoronaphthalene (22.5 g,100 mmol), 2-mercaptophenylboronic acid (15.4 g,100 mmol) Pd-132 (3.55 g,5 mmol), potassium carbonate (27.6 g,200 mmol) sequentially adding into a 1000mL three-necked flask, adding about 400mL of toluene and about 100mL of water, pumping and charging nitrogen gas for three times, heating to 90 ℃ for reaction for 4 hours, cooling to room temperature after complete reaction of raw materials, adding water for dilution, extracting with ethyl acetate for three times, merging organic phases, drying with anhydrous sodium sulfate, removing redundant solvent by reduced pressure distillation, and recrystallizing with toluene petroleum ether to obtain 2-1 about 21.5g of the compound with the yield of 84.6%. Ms 255.32

Synthesis of Compound 2-2:

accurately weighing compound 2-1 (20.3 g,80 mmol), cesium carbonate (52.2 g,160 mmol), sequentially adding into a 1000mL three-necked flask, adding about 500mL anhydrous DMF, pumping nitrogen three times, and heating to 140 ℃ for reaction for 12 hours. After the raw materials are completely reacted, adding water for dilution, then extracting for a plurality of times by using a small amount of ethyl acetate, combining organic phases, drying by using anhydrous sodium sulfate, and removing redundant solvents by reduced pressure distillation. The crude product is pulped with methanol to obtain compound 2-2 about 15.2g, yield: 81.1%. Ms 235.32

Synthesis of Compound 2-3:

Accurately weighing compound 2-2 (14.1 g,60 mmol), adding into a 500mL three-necked flask, adding 100mL chloroform, pumping in nitrogen three times, cooling to about-10 ℃ in an ice salt bath, slowly adding dropwise a chloroform solution (about 100 mL) of bromine (9.6 g,60 mmol) into the system, and naturally heating to room temperature for reaction for 4 hours. After the raw materials are completely reacted, washing with sodium sulfite aqueous solution, separating liquid, drying the aqueous phase with anhydrous sodium sulfate, and removing redundant solvent by reduced pressure distillation to obtain a crude product, and pulping with ethyl acetate and methanol. About 15.2g of compound 2-3 was obtained in yield: 80.9%. Ms 314.21.

Synthesis of Compounds 2-4:

accurately weighing 2-3 (6.2 g,20 mmol), 4-amino-9, 9-dimethylfluorene (4.2 g,20 mmol), tris (dibenzylideneacetone) dipalladium (0.58 g,1 mmol), sodium tert-butoxide (5.76 g,60 mmol) were sequentially added to a 250mL three-necked flask, anhydrous toluene was added in an amount of about 100mL, and after three times of nitrogen purging, a toluene solution of tri-tert-butylphosphine was slowly added dropwise to the reaction system in an amount of 4.1mL. Then slowly heating to 90 ℃ for reaction for 4 hours, adding ethyl acetate for dilution after the raw materials are completely reacted, filtering the silica gel, and then leaching the silica gel by using 200mL of ethyl acetate. The organic phases were combined and distilled under reduced pressure to remove excess solvent, and the crude product was recrystallized from petroleum ether. About 6.8g of compound 2-4 was obtained in yield: 77%. Ms 442.59.

Synthesis of Compound 23:

accurately weighing 2-4 (6.6 g,15 mmol) and C (6.2 g,15 mmol) of tris (dibenzylideneacetone) dipalladium (0.43 g,0.75 mmol), adding sodium tert-butoxide (4.3 g,45 mmol) into a 250mL three-necked flask in sequence, adding about 100mL of anhydrous toluene, pumping nitrogen three times, and slowly dropwise adding 3mL of toluene solution of tri-tert-butylphosphine into the reaction system. Then the temperature is raised to 90 ℃ for reaction for 4 hours. After the raw materials are completely reacted, adding water for dilution, separating liquid, extracting three times by using ethyl acetate, combining organic phase anhydrous sodium sulfate for drying, and then decompressing and distilling to remove redundant solvent. The crude product is heated and dissolved by toluene, filtered by heat and then cooled and separated out by adding petroleum ether. About 7.5g of compound 23 was obtained in a yield of 64.8%. Ms 772.98.

Example 3: synthesis of Compound 42

Synthesis of Compound 3-1:

accurately weighing 2-3 (6.2 g,20 mmol), 2-amino-dibenzofuran (3.7 g,20 mmol), dipalladium tris (dibenzylideneacetone) (0.58 g,1 mmol), sodium tert-butoxide (5.76 g,60 mmol) were sequentially added into a 250mL three-neck flask, anhydrous toluene was added about 100mL, and after three times of nitrogen gas was pumped in, 4.1mL of a toluene solution of tri-tert-butylphosphine was slowly added dropwise to the reaction system. Then slowly heating to 90 ℃ for reaction for 4 hours, adding ethyl acetate for dilution after the raw materials are completely reacted, filtering the silica gel, and then leaching the silica gel by using 200mL of ethyl acetate. The organic phases were combined and distilled under reduced pressure to remove excess solvent, and the crude product was recrystallized from petroleum ether. About 6.8g of compound 3-1 was obtained in yield: 81.8%. Ms 416.51

Synthesis of Compound 42:

accurately weighing compound 3-1 (6.2 g,15 mmol), compound A (6.4 g,15 mmol) of tris (dibenzylideneacetone) dipalladium (0.43 g,0.75 mmol), sodium tert-butoxide (4.3 g,45 mmol) were sequentially added to a 250mL three-necked flask, anhydrous toluene was added about 100mL, and after three times of nitrogen-charging, 3mL of toluene solution of tri-tert-butylphosphine was slowly added dropwise to the reaction system. Then the temperature is raised to 90 ℃ for reaction for 4 hours. After the raw materials are completely reacted, adding water for dilution, separating liquid, extracting three times by using ethyl acetate, combining organic phase anhydrous sodium sulfate for drying, and then decompressing and distilling to remove redundant solvent. The crude product is heated and dissolved by toluene, filtered by heat and then cooled and separated out by adding petroleum ether. About 5.9g of compound 42 was obtained in a yield of 51.6%. Ms 762.96.

Example 4: synthesis of Compound 50

Synthesis of Compound 4-1:

accurately weighing 1-3 (5.9 g,20 mmol), 4-amino-pyridine (1.9 g,20 mmol), dipalladium tris (dibenzylideneacetone) (0.58 g,1 mmol), sodium tert-butoxide (5.76 g,60 mmol) were sequentially added to a 250mL three-necked flask, anhydrous toluene was added about 100mL, and after three times of nitrogen-charging, 4.1mL of a toluene solution of tri-tert-butylphosphine was slowly added dropwise to the reaction system. Then slowly heating to 90 ℃ for reaction for 4 hours, adding ethyl acetate for dilution after the raw materials are completely reacted, filtering the silica gel, and then leaching the silica gel by using 200mL of ethyl acetate. The organic phases were combined and distilled under reduced pressure to remove excess solvent, and the crude product was recrystallized from petroleum ether. About 5.2g of compound 4-1 was obtained in yield: 83.8%. Ms 311.36

Synthesis of Compound 50:

accurately weighing compound 4-1 (4.7 g,15 mmol), compound A (6.4 g,15 mmol) of tris (dibenzylideneacetone) dipalladium (0.43 g,0.75 mmol), sodium tert-butoxide (4.3 g,45 mmol) were sequentially added to a 250mL three-necked flask, anhydrous toluene was added about 100mL, and after three times of nitrogen-charging, 3mL of toluene solution of tri-tert-butylphosphine was slowly added dropwise to the reaction system. Then the temperature is raised to 90 ℃ for reaction for 4 hours. After the raw materials are completely reacted, adding water for dilution, separating liquid, extracting three times by using ethyl acetate, combining organic phase anhydrous sodium sulfate for drying, and then decompressing and distilling to remove redundant solvent. The crude product is heated and dissolved by toluene, filtered by heat and then cooled and separated out by adding petroleum ether. About 6.3g of compound 50 was obtained in 63.9% yield. Ms 657.8.

Example 5: synthesis of Compound 79

Synthesis of Compound 5-1:

accurately weighing the compound 1-iodo-3-bromonaphthalene (33.3 g,100 mmol), 2-methylthiophenylboronic acid (16.8 g,100 mmol), and tetraphenylphosphine palladium (3.46 g,3 mmol), adding potassium carbonate (27.6 g,200 mmol) into a 1000mL three-necked flask in sequence, adding 500mL dioxane, pumping 100mL water and nitrogen three times, and heating to 90 ℃ for reaction for 6 hours. After the raw materials are completely reacted, adding water for dilution, extracting for three times by ethyl acetate, combining organic phases, drying by anhydrous sodium sulfate, removing redundant solvent by reduced pressure distillation, and carrying out silica gel sample column chromatography, wherein the eluent is PE:EA=10:1 (volume ratio), so that the yield of the compound 5-1 is about 22.4 g: 68%. Ms 330.26 Synthesis of Compound 5-2:

Accurately weighing compound 5-1 (22.4 g,68 mmol) and adding into a 500mL three-necked flask, adding about 50mL of dichloromethane, and slowly dropwise adding H into the reaction system ₂ O ₂ (30%) about 30mL, stirred at room temperature overnight, left to stand after the reaction was completed to separate the liquid, the aqueous phase was extracted three times with methylene chloride, then the organic phase was washed with aqueous sodium sulfite solution, dried over anhydrous sodium sulfate, and the excess solvent was distilled off under reduced pressure. The crude product was obtained, and then about 150mL of trifluoromethanesulfonic acid was added to the reaction system, followed by heating to 60℃for reaction for 4 hours. After the raw materials are completely reacted, water is added for dilution, and suction filtration is carried out to obtain about 18.3g of compound 5-2, and the yield is: 85.9%. Ms 314.21. Synthesis of Compound 5-3:

accurately weighing 5-2 (15.7 g,50 mmol) of compound, 2-aminobiphenyl (8.5 g,50 mmol) of tris (dibenzylideneacetone) dipalladium (0.86 g,1.5 mmol), sequentially adding sodium tert-butoxide (9.6 g,100 mmol) into a 200mL three-neck flask, adding about 500mL of anhydrous toluene, pumping nitrogen three times, and slowly dropwise adding 6mL of toluene solution of tri-tert-butylphosphine into the reaction system. Then slowly heating to 90 ℃ for reaction for 4 hours, adding ethyl acetate for dilution after the raw materials are completely reacted, filtering the silica gel, and then leaching the silica gel by using 200mL of ethyl acetate. The organic phases were combined and distilled under reduced pressure to remove excess solvent, and the crude product was recrystallized from petroleum ether. About 15.8g of compound 5-3 was obtained in yield: 78.7%. Ms 402.53

Synthesis of compound 79:

accurately weighing 5-3 (4 g,10 mmol) of compound C (4.1 g,10 mmol), dipalladium tris (dibenzylideneacetone) (0.29 g,0.5 mmol), sodium tert-butoxide (1.9 g,20 mmol) was sequentially added into a 250mL three-neck flask, anhydrous toluene was added about 100mL, and after three times of nitrogen filling, 6mL of toluene solution of tri-tert-butylphosphine was slowly added dropwise to the reaction system. Then slowly heating to 90 ℃ for reaction for 4 hours, adding ethyl acetate for dilution after the raw materials are completely reacted, filtering the silica gel, and then leaching the silica gel by using 200mL of ethyl acetate. The organic phases were combined and distilled under reduced pressure to remove excess solvent, and the crude product was recrystallized from petroleum ether. About 5.7g of compound 79 was obtained in the yield: 77.8%. Ms 732.91

Example 6: synthesis of Compound 82

Synthesis of Compound 6-1:

3-chloro-2-naphthol (17.9 g,100 mmol) was accurately weighed and put into a 500mL three-necked flask, about 100mL of anhydrous DMF was added, the temperature was lowered to about-10 ℃ by an ice salt bath after three times of nitrogen filling, a DMF solution of NBS (17.8 g,100 mmol) was slowly added dropwise to the reaction system, and then the reaction was carried out at room temperature for four hours by natural temperature rise. After the raw materials are completely reacted, the redundant solvent is removed by reduced pressure distillation, and the silica gel is subjected to column chromatography, wherein the eluting agent is PE (polyethylene) and EA=5:1 (volume ratio). About 21.2g of compound 6-1 was obtained in yield: 82.3%.

Ms:258.51

Synthesis of Compound 6-2:

accurately weighing 6-1 (20.6 g,80 mmol), 2-fluorobenzeneboronic acid (11.2 g,80 mmol), pd-132 (2.84 g,4 mmol), and potassium carbonate (22.1 g,160 mmol) were sequentially added into a 1000mL three-necked flask, about 400mL of toluene and 100mL of water were added, and after pumping in nitrogen three times, the temperature was raised to 80 ℃ for reaction for 4 hours. After the raw materials are completely reacted, cooling to room temperature, adding water for dilution, extracting with ethyl acetate for three times, combining organic phases, drying with anhydrous sodium sulfate, removing redundant solvent by reduced pressure distillation, and performing silica gel sample column chromatography, wherein the eluting agent is PE (polyethylene) with EA=5:1 (volume ratio). About 18.5g of Compound 6-2 was obtained in yield: 84.8%. Ms 273.70

Synthesis of Compound 6-3:

compound 6-2 (18.5 g,67.8 mmol) was accurately weighed, cesium carbonate (44.2 g,135.6 mmol) was added sequentially to a 500mL three-necked flask, anhydrous DMF was added about 260mL, nitrogen was purged three times, and the temperature was raised to 40℃for reaction for 8 hours. Cooling to room temperature after the raw materials are completely reacted, adding water for dilution, and carrying out suction filtration to obtain about 13g of compound 6-3, wherein the yield is as follows: 75.9%. Synthesis of Ms 253.70 Compound 6-4:

accurately weighing 6-3 (5.1 g,20 mmol), 2-amino-dibenzothiophene (4.0 g,20 mmol), dipalladium tris (dibenzylideneacetone) (0.58 g,1 mmol), sodium tert-butoxide (5.76 g,60 mmol) were sequentially added to a 250mL three-neck flask, anhydrous toluene was added in an amount of about 100mL, and after three times of nitrogen gas was introduced, 4.1mL of a toluene solution of tri-tert-butylphosphine was slowly added dropwise to the reaction system. Then slowly heating to 90 ℃ for reaction for 4 hours, adding ethyl acetate for dilution after the raw materials are completely reacted, filtering the silica gel, and then leaching the silica gel by using 200mL of ethyl acetate. The organic phases were combined and distilled under reduced pressure to remove excess solvent, and the crude product was recrystallized from petroleum ether. About 6.8g of compound 6-4 was obtained in yield: 81.8%. Ms 416.51

Synthesis of compound 82:

accurately weighing compound 6-4 (6.2 g,15 mmol), compound A (6.4 g,15 mmol) of tris (dibenzylideneacetone) dipalladium (0.43 g,0.75 mmol), sodium tert-butoxide (4.3 g,45 mmol) was sequentially added to a 250mL three-necked flask, anhydrous toluene was added about 100mL, and after three times of nitrogen-charging, 3mL of toluene solution of tri-tert-butylphosphine was slowly added dropwise to the reaction system. Then the temperature is raised to 90 ℃ for reaction for 4 hours. After the raw materials are completely reacted, adding water for dilution, separating liquid, extracting three times by using ethyl acetate, combining organic phase anhydrous sodium sulfate for drying, and then decompressing and distilling to remove redundant solvent. The crude product is heated and dissolved by toluene, filtered by heat and then cooled and separated out by adding petroleum ether. About 5.9g of compound 82 was obtained in a yield of 51.6%. Ms 762.96.

Example 7: synthesis of Compound 86

Synthesis of Compound 7-1:

accurately weighing 6-3 (5.1 g,20 mmol), 2-aminopyridine (1.9 g,20 mmol), dipalladium tris (dibenzylideneacetone) (0.58 g,1 mmol), sodium tert-butoxide (5.76 g,60 mmol) were sequentially added to a 250mL three-necked flask, anhydrous toluene was added about 100mL, and after three nitrogen-charging steps, 4.1mL of a toluene solution of tri-tert-butylphosphine was slowly added dropwise to the reaction system. Then slowly heating to 90 ℃ for reaction for 4 hours, adding ethyl acetate for dilution after the raw materials are completely reacted, filtering the silica gel, and then leaching the silica gel by using 200mL of ethyl acetate. The organic phases were combined and distilled under reduced pressure to remove excess solvent, and the crude product was recrystallized from petroleum ether. About 5.3g of compound 7-1 was obtained in yield: 85.4%. Ms 311.36

Synthesis of Compound 86:

accurately weighing compound 7-1 (4.65 g,15 mmol), compound A (6.4 g,15 mmol) of tris (dibenzylideneacetone) dipalladium (0.43 g,0.75 mmol), sodium tert-butoxide (4.3 g,45 mmol) were sequentially added to a 250mL three-necked flask, anhydrous toluene was added about 100mL, and after three times of nitrogen-charging, 3mL of toluene solution of tri-tert-butylphosphine was slowly added dropwise to the reaction system. Then the temperature is raised to 90 ℃ for reaction for 4 hours. After the raw materials are completely reacted, adding water for dilution, separating liquid, extracting three times by using ethyl acetate, combining organic phase anhydrous sodium sulfate for drying, and then decompressing and distilling to remove redundant solvent. The crude product is heated and dissolved by toluene, filtered by heat and then cooled and separated out by adding petroleum ether. About 6.7g of compound 86 was obtained, and the yield was 51.6%. Ms 657.80.

Example 8: synthesis of Compound 2

Synthesis of Compound 8-1:

accurately weighing 1-3 (5.9 g,20 mmol) of compound, aniline (1.9 g,20 mmol), dipalladium tris (dibenzylideneacetone) (0.58 g,1 mmol), sodium tert-butoxide (5.76 g,60 mmol) were sequentially added into a 250mL three-necked flask, anhydrous toluene was added about 100mL, and after three times of nitrogen gas filling, 4.1mL of toluene solution of tri-tert-butylphosphine was slowly added dropwise to the reaction system. Then slowly heating to 90 ℃ for reaction for 4 hours, adding ethyl acetate for dilution after the raw materials are completely reacted, filtering the silica gel, and then leaching the silica gel by using 200mL of ethyl acetate. The organic phases were combined and distilled under reduced pressure to remove excess solvent, and the crude product was recrystallized from petroleum ether. About 5.3g of compound 8-1 was obtained in yield: 85.7%. Ms 310.37

Synthesis of Compound 2:

accurately weighing compound 8-1 (4.64 g,15 mmol), compound A (6.4 g,15 mmol) of tris (dibenzylideneacetone) dipalladium (0.43 g,0.75 mmol), sodium tert-butoxide (4.3 g,45 mmol) were sequentially added to a 250mL three-necked flask, anhydrous toluene was added about 100mL, and after three times of nitrogen-charging, 3mL of toluene solution of tri-tert-butylphosphine was slowly added dropwise to the reaction system. Then the temperature is raised to 90 ℃ for reaction for 4 hours. After the raw materials are completely reacted, adding water for dilution, separating liquid, extracting three times by using ethyl acetate, combining organic phase anhydrous sodium sulfate for drying, and then decompressing and distilling to remove redundant solvent. The crude product is heated and dissolved by toluene, filtered by heat and then cooled and separated out by adding petroleum ether. About 6.1g of compound 2 was obtained in 62% yield. Ms 656.82

Example 9: synthesis of Compound 3

Synthesis of Compound 9-1:

accurately weighing 1-3 (5.9 g,20 mmol), 2-aminobiphenyl (3.4 g,20 mmol), dipalladium tris (dibenzylideneacetone) (0.58 g,1 mmol), sodium tert-butoxide (5.76 g,60 mmol) were sequentially added into a 250mL three-necked flask, anhydrous toluene was added about 100mL, and after three times of nitrogen filling, 4.1mL of a toluene solution of tri-tert-butylphosphine was slowly added dropwise to the reaction system. Then slowly heating to 90 ℃ for reaction for 4 hours, adding ethyl acetate for dilution after the raw materials are completely reacted, filtering the silica gel, and then leaching the silica gel by using 200mL of ethyl acetate. The organic phases were combined and distilled under reduced pressure to remove excess solvent, and the crude product was recrystallized from petroleum ether. About 6.1g of compound 9-1 was obtained in yield: 79.1%. Ms 386.47

Synthesis of Compound 3:

accurately weighing compound 9-1 (5.78 g,15 mmol), compound A (6.2 g,15 mmol) of tris (dibenzylideneacetone) dipalladium (0.43 g,0.75 mmol), sodium tert-butoxide (4.3 g,45 mmol) were sequentially added to a 250mL three-necked flask, anhydrous toluene was added about 100mL, and after three nitrogen charges were pumped in, 3mL of a toluene solution of tri-tert-butylphosphine was slowly added dropwise to the reaction system. Then the temperature is raised to 90 ℃ for reaction for 4 hours. After the raw materials are completely reacted, adding water for dilution, separating liquid, extracting three times by using ethyl acetate, combining organic phase anhydrous sodium sulfate for drying, and then decompressing and distilling to remove redundant solvent. The crude product is heated and dissolved by toluene, filtered by heat and then cooled and separated out by adding petroleum ether. About 6.6g of compound 3 was obtained in a yield of 61.5%. Ms 716.85

Preparing a device:

the process of preparing an OLED device including the above-described compounds is described in detail below by way of specific examples. The device 1 was prepared as follows:

(1) An ITO (indium tin oxide) conductive glass substrate was washed with various solvents (e.g., one or more of deionized water, chloroform, acetone, or isopropyl alcohol) for 15 minutes, and then subjected to ultraviolet ozone plasma treatment.

(2) And (3) transferring the ITO conductive glass substrate into vacuum vapor deposition equipment, and evaporating a hole injection layer material HATCN in a vacuum evaporation mode, wherein the thickness is 5nm.

(3) On the hole injection layer, the hole transport material compound 14 was vapor-deposited by vacuum vapor deposition to a thickness of 80nm, thereby forming a hole transport layer.

(4) On the hole transport layer, the compound HT1 was evaporated to a thickness of 20nm, forming an electron blocking layer.

(5) Evaporating a light-emitting layer on the electron blocking layer, wherein GH1 is selected as a main material, GD1 is selected as a doping material, the mass ratio of GD1 to GH1 is 1:9, and the thickness is 30nm.

(6) On the light-emitting layer, ET1 and LiQ were vapor deposited in a mass ratio of 5:5, forming an electron transport layer with a thickness of 30nm.

(7) On the electron transport layer, liQ was vacuum evaporated to a thickness of 2nm to form an electron injection layer.

(8) And vacuum evaporating a cathode Al layer with the thickness of 80nm on the electron injection layer to form a cathode.

(9) The device was encapsulated with an ultraviolet curable resin in a nitrogen glove box.

The device is prepared by adopting a vacuum evaporation mode, and the evaporation environment is 1-10 ^-5 Pa, evaporation rate of the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the electron transport layer and the electron injection layer isThe evaporation rate of the cathode layer is->

Device example 2: the compound 23 for hole transport layer material of the organic electroluminescent device was substituted for the compound 14 in device example 1, with the other conditions unchanged.

Device example 3: the compound 42 for hole transport layer material of the organic electroluminescent device was substituted for the compound 14 in device example 1, with the other conditions unchanged.

Device example 4: the compound 50 for hole transport layer material of organic electroluminescent device was substituted for the compound 14 in device example 1, with the other conditions unchanged.

Device example 5: the hole transport layer material of the organic electroluminescent device was replaced with the compound 79 in the device example 1, except that the other conditions were not changed.

Device example 6: the hole transport layer material compound 82 of the organic electroluminescent device was used instead of the compound 14 of device example 1, with the other conditions unchanged.

Device example 7: the compound 86 for hole transport layer material of the organic electroluminescent device was substituted for the compound 14 in device example 1, with the other conditions unchanged.

Device example 8: the hole transport layer material of the organic electroluminescent device was replaced with compound 2, instead of compound 14 in device example 1, with the other conditions unchanged.

Device example 9: the hole transport layer material of the organic electroluminescent device was replaced with compound 3, instead of compound 14 in device example 1, with the other conditions unchanged.

Comparative example 1: the hole transport layer material of the organic electroluminescent device was replaced with Ref-1, the compound 14 in device example 1, and the other conditions were unchanged.

The structure of the compound involved in the device is as follows:

synthesis of Ref-1 is referred to CN104781247B.

The current-voltage (J-V) characteristics of the organic light emitting diodes of device examples 1-9 and comparative example 1 were tested using a characterization apparatus while recording important parameters such as lifetime and external quantum efficiency. The luminous efficiency is the relative value obtained at a current density of 10mA/cm2, and LT95@1000nits is the time during which the luminance decreases from the initial luminance 1000nits to 95% of the initial luminance at a constant current. All external quantum efficiencies and lifetimes are relative values with respect to the organic light emitting diode of comparative example 1. Characterization results are shown in table 1, and it can be seen that the efficiency and lifetime of the examples according to the present invention are improved to a significant extent with respect to comparative example 1, and in particular, the luminous efficiency and lifetime of the example 6 based device are highest among the same type of devices.

TABLE 1

Numbering device	Hole transport layer material	Luminous efficiency	Life span
				Device example 1	Compound 14	1.16	1.13
Device example 2	Compound 23	1.11	1.05
				Device example 3	Compound 42	1.14	1.11
Device example 4	Compound 50	1.04	1.08
				Device example 5	Compound 79	1.09	1.08
Device example 6	Compound 82	1.15	1.1
				Device example 7	Compound 86	1.06	1.02
Device example 8	Compound 2	1.12	1.07
				Device example 9	Compound 3	1.08	1.06
Comparative example 1	Compound Ref1	1	1

It can be seen from table 1 that the compound of the present invention can effectively improve the efficiency and lifetime of the organic electroluminescent device as a hole transport layer, compared to comparative example 1.

The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims

1. An arylamine compound, characterized by being represented by the general formula (I):

wherein;

the aromatic amine compound shown in the formula (I) is selected from the general formula (II-1) or the general formula (II-2):

w is selected from O or S;

z is selected from O or S;

R ₁ 、R ₂ 、R ₃ independently selected from-H, -D, or a straight chain alkyl group having 1 to 6C atoms, orBranched alkyl groups having 3 to 6C atoms;

m, n, t are independently selected from 0 or 1;

When Ar is ₁ Selected from the group consisting ofX is independently selected from CR at each occurrence ₆ Or N; r is R ₆ Independently for each occurrence, -H, -D, or a straight chain alkyl group having 1 to 6 carbon atoms, or a branched alkyl group having 3 to 6 carbon atoms, or phenyl, or biphenyl, or pyridinyl, or a combination of these groups;

when Ar is ₁ Independently selected fromX is independently selected from CR at each occurrence ₆ Or N; r is R ₆ Each occurrence is independently selected from-H, -D, or a straight chain alkyl group having 1 to 6 carbon atoms, or a branched alkyl group having 3 to 6 carbon atoms, or a combination of these groups;

y is independently selected from CR for each occurrence ₇ R ₈ O or S;

R ₇ 、R ₈ each occurrence is independently selected from-H, -D, or a straight chain alkyl group having 1 to 6 carbon atoms, or a branched alkyl group having 3 to 6 carbon atoms, or a combination of these groups.

2. The arylamine compound according to claim 1, wherein Ar ₁ Independently selected from the following groups:

wherein: * Expression of the ligation site.

3. An arylamine compound according to claim 1 or 2, characterized by a structure selected from the group consisting of:

4. an arylamine compound selected from the group consisting of:

5. a hole transport material selected from the arylamine compounds according to any one of claims 1-4.

6. A mixture comprising at least one aromatic amine compound according to any one of claims 1 to 4 and at least one further organic functional material, wherein the at least one further organic functional material is selected from the group consisting of a hole injecting material, a hole transporting material, an electron injecting material, an electron blocking material, a hole blocking material, a luminescent guest material, a luminescent host material or an organic dye.

7. A composition comprising an aromatic amine compound according to any one of claims 1 to 4 or a mixture according to claim 6, and at least one organic solvent.

8. An organic electronic device comprising at least one functional layer, wherein said functional layer comprises an arylamine compound according to any one of claims 1-4 or a mixture according to claim 6, or said functional layer is prepared from a composition according to claim 7.