Aromatic amine organic compounds, mixtures, compositions and organic electronic devices

Abstract

The present invention discloses an aromatic amine organic compound, mixture, composition, and organic electronic device having a structure represented by general formula (I). The aromatic amine organic compound of the present invention can be used as a novel hole transport material. Application of the aromatic amine organic compound in organic functional layer materials and organic electronic devices can effectively improve the stability and lifespan of the devices.

Description

Technical Field

[0001] The present application relates to the technical field of organic electroluminescence, and in particular to an aromatic amine organic compound, a mixture, a composition and an organic electronic device. Background Art

[0002] Organic optoelectronic materials offer diverse synthesis, relatively low manufacturing costs, and excellent optical and electrical properties. Organic light-emitting diodes (OLEDs) have broad potential for development in optoelectronic devices (such as flat-panel displays and lighting) due to their advantages, including wide viewing angles, fast response times, low operating voltages, and thin panels.

[0003] Organic electroluminescence refers to the phenomenon of converting electrical energy into light energy using organic substances. Organic electroluminescent elements that utilize organic electroluminescence typically have a structure with a positive electrode, a negative electrode, and an organic functional layer between them. To improve the efficiency and lifespan of organic electroluminescent elements, the organic functional layer has a multilayer structure, with each layer containing different organic substances. Specifically, it may include a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, etc. 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, and electrons are injected from the negative electrode into the organic functional layer. When the injected holes and electrons meet, excitons are formed, and when the excitons transition back to the ground state, light is emitted. Such organic electroluminescent elements have characteristics such as self-luminescence, high brightness, high efficiency, low driving voltage, wide viewing angle, and high contrast.

[0004] In addition to the light-emitting layer, organic light-emitting diode devices also require organic functional layers involved in hole transport, such as the hole transport layer and the light-assisted layer, to achieve balanced transport of holes and electrons, thereby improving device efficiency and lifespan. In order to achieve efficient organic electroluminescent devices, in addition to high-performance light-emitting layer materials, the development of corresponding hole transport materials is also crucial.

[0005] Therefore, the present application urgently needs to provide a new hole transport material to improve the efficiency and lifespan of organic electroluminescent devices, especially the efficiency and lifespan of red organic light emitting diode devices. Summary of the Invention

[0006] The purpose of this application is to provide aromatic amine organic compounds and their applications, aiming to provide a new type of hole transport material to improve the stability and life of the device.

[0007] The technical solutions of the present invention are as follows:

[0008] An aromatic amine organic compound represented by general formula (I):

[0009]

[0010] in:

[0011] L1 is selected from a substituted or unsubstituted aromatic group having 6 to 40 ring atoms or a substituted or unsubstituted heteroaromatic group having 6 to 40 ring atoms;

[0012] A is selected from 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;

[0013] Ar1 and Ar2 are independently selected from a substituted or unsubstituted aromatic group having 6 to 40 ring atoms, or a substituted or unsubstituted heteroaromatic group or non-aromatic ring system having 5 to 40 ring atoms.

[0014] The present invention also provides a mixture, which includes the above-mentioned aromatic amine organic compound and at least one organic functional material, wherein the organic functional material is selected from at least one of hole injection materials, hole transport materials, electron transport materials, electron injection materials, electron blocking materials, hole blocking materials, luminescent materials, host materials and organic dyes.

[0015] The present invention also provides a composition comprising the above aromatic amine organic compound, or the above mixture, and at least one organic solvent.

[0016] The present invention also provides an organic electronic device comprising a first electrode, a second electrode, and one or more organic functional layers located between the first electrode and the second electrode, wherein the organic functional layer material comprises the above-mentioned aromatic amine organic compound, or the above-mentioned mixture, or is prepared from the above-mentioned composition.

[0017] Beneficial effect: The above organic compound adopts the structure of carbazole derivative-triarylamine and introduces group. The group has a non-completely conjugated five-membered ring structure, and the carbazole group is a conjugated group. Through the intermolecular interaction between the non-conjugated group and the conjugated group, the hole transport properties of the carbazole derivative are beneficially exerted, thereby facilitating the improvement of the exciton utilization rate and device stability of the OLED device using the compound of the present invention as a hole transport material, thereby achieving the purpose of improving the luminous efficiency and life of the device. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the following briefly introduces the drawings required for use in the description of the embodiments. Obviously, the drawings described below are only some embodiments of the present application. For those skilled in the art, other drawings can be obtained based on these drawings without creative work.

[0019] Figure 1 Schematic diagram of the structure of the organic light emitting diode device provided in the embodiment of the present application.

[0020] The numbers in the figure are:

[0021] 1. Substrate; 2. First electrode; 3. Hole injection layer; 4. First hole transport layer; 5. Second hole transport layer; 6. Light-emitting layer; 7. Electron transport layer; 8. Electron injection layer; 9. Second electrode; 10. Organic light-emitting diode device. DETAILED DESCRIPTION

[0022] The following will be combined with the drawings in the embodiments of this application to clearly and completely describe the technical solutions in the embodiments of this application. Obviously, the embodiments described are only part of the embodiments of this application, not all of the embodiments. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without making creative efforts are within the scope of protection of this application.

[0023] It should be noted that the order of description of the following embodiments is not intended to limit the preferred order of the embodiments. In addition, in the description of this application, the term "including" means "including but not limited to". The terms first, second, third, etc. are used only as labels and do not impose numerical requirements or establish an order. The various embodiments of the present application may be presented in the form of a range; it should be understood that the description in the form of a range is merely for convenience and brevity and should not be understood as a hard limitation on the scope of this application; therefore, it should be considered that the range description has specifically disclosed all possible sub-ranges and single numerical values ​​within the range. For example, the range description from 1 to 6 should be considered to have 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 numbered range, such as 1, 2, 3, 4, 5 and 6, regardless of the range. In addition, whenever a numerical range is indicated in this article, it is meant to include any quoted number (integer) within the indicated range.

[0024] In the present application, "substituted" means that a hydrogen atom in a substituted group is replaced by a substituent.

[0025] In this application, when the same substituent appears multiple times, it can be independently selected from different groups. If the general formula contains multiple R1, then R1 can be independently selected from different groups. For example 6 R on the benzene ring 1 They may be the same as or different from each other.

[0026] In this application, "substituted or unsubstituted" means that the defined group may be substituted or unsubstituted. When the defined group is substituted, it should be understood that it is optionally substituted with groups acceptable in the art, including but not limited to: D (deuterium), C1-30 Alkyl, heterocyclic group containing 3-20 ring atoms, aryl group containing 6-20 ring atoms, heteroaryl group containing 5-20 ring atoms, silanyl, carbonyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, haloformyl, formyl, -NRR', cyano, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, trifluoromethyl, nitro or halogen, and the above groups can also be further substituted by substituents acceptable in the art. It is understood that R and R' in -NRR' are each independently substituted by groups acceptable in the art, including but not limited to: H, D, C 1-6 C 1-6 Any of alkyl, cycloalkyl containing 3-8 ring atoms, heterocyclyl containing 3-8 ring atoms, aryl containing 6-20 ring atoms or heteroaryl containing 5-10 ring atoms is substituted by one or more of the following groups: C 1-6 Alkyl, cycloalkyl containing 3 to 8 ring atoms, heterocyclyl containing 3 to 8 ring atoms, halogen, hydroxy, nitro or amino.

[0027] In this application, the "number of ring atoms" represents the number of atoms among the atoms constituting the ring itself of a structural compound (e.g., a monocyclic compound, a condensed ring compound, a cross-linked compound, a carbocyclic compound, a heterocyclic compound) formed by atoms bonded together to form a ring. When the ring is substituted with a substituent, the atoms contained in the substituent are not included in the ring atoms. The "number of ring atoms" described below is also the same unless otherwise specified. For example, the number of ring atoms of a benzene ring is 6, the number of ring atoms of a naphthalene ring is 10, and the number of ring atoms of a thienyl group is 5.

[0028] In this application, "alkyl" may refer to a straight chain, branched chain 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, for example, "C 1-9"Alkyl" refers to an alkyl group containing 1 to 9 carbon atoms, which can be independently C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl or C9 alkyl at each occurrence. Non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3,3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-butyl, 2-ethylbutyl, 3,3-dimethylbutyl, 2-pentyl ... 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, 2,2-dimethylheptyl, 2-ethylheptyl, 2-butylheptyl, n-octyl, tert-octyl, 2-ethyloctyl, 2-butyloctyl, 2-hexyloctyl, 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, etc.

[0029] In this application, an aromatic group refers to a hydrocarbon group containing at least one aromatic ring. A heteroaromatic group refers to an aromatic hydrocarbon group containing at least one heteroatom. The heteroatom is preferably selected from Si, N, P, O, S and / or Ge, and is particularly preferably selected from Si, N, P, O and / or S. A fused ring aromatic group refers to an aromatic group having two or more rings, wherein two carbon atoms are shared by two adjacent rings, i.e., a fused ring. A fused heterocyclic aromatic group refers to a fused heterocyclic aromatic hydrocarbon group containing at least one heteroatom. For the purposes of this application, aromatic groups or heteroaromatic groups include not only aromatic ring systems, but also non-aromatic ring systems. Therefore, systems such as pyridine, thiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, pyrazine, pyridazine, pyrimidine, triazine, and carbene are also considered aromatic groups or heterocyclic aromatic groups for the purposes of this invention. For the purposes of this application, fused aromatic or fused heteroaromatic ring systems include not only systems containing aromatic or heteroaromatic groups, but also systems in which multiple aromatic or heteroaromatic groups are interrupted by short non-aromatic units (<10% non-H atoms, preferably less than 5% non-H atoms, such as C, N, or O atoms). Thus, 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.

[0030] In a preferred embodiment, the aromatic group is selected from the group consisting of 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 triazine, pyridine, pyrimidine, imidazole, furan, thiophene, benzofuran, benzothiophene, indole, carbazole, pyrrolimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrole, furofuran, thienothiophene, benzisoxazole, benzisothiazole, benzimidazole, quinoline, isoquinoline, o-naphthylidene, quinoxaline, phenanthridine, primary idine, quinazoline, quinazolinone, dibenzofuran, dibenzothiophene, carbazole, and derivatives thereof.

[0031] In this application, “*” represents a linking site or a fusion site.

[0032] In this application, when the linking site is not specified in the group, it means that any linking site in the group can be used as the linking site;

[0033] In this application, when the fusion site is not specified in the group, it means that any fusion site in the group can be used as the fusion site, and preferably two or more sites in the ortho position in the group are fusion sites;

[0034] A non-aromatic ring refers to a ring system containing at least one non-aromatic ring. In the present application, preferably, the non-aromatic ring system only contains rings formed by carbon-carbon single bonds.

[0035] In the present application, the single bond to which the substituent is connected runs through the corresponding ring, indicating that the substituent can be connected to any position of the ring, for example In the formula, R is connected to any substitutable position of the benzene ring. express It can form a ring with any position on the benzene ring, preferably adjacent C atoms on the benzene ring.

[0036] In the present invention, adjacent groups can form a ring with each other, which means that adjacent groups combine to form a substituted or unsubstituted aliphatic ring system, a substituted or unsubstituted aromatic ring system, a substituted or unsubstituted aliphatic heterocyclic ring system or a substituted or unsubstituted heteroaromatic ring system; the above ring systems can be monocyclic or polycyclic.

[0037] The present invention provides an aromatic amine organic compound as shown in the general formula (I):

[0038]

[0039] in:

[0040] L1 is 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;

[0041] A is selected from a substituted or unsubstituted aromatic group having 6 to 20 ring atoms or a substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms;

[0042] Ar1 and Ar2 are independently selected from a substituted or unsubstituted aromatic group having 6 to 40 ring atoms, or a substituted or unsubstituted heteroaromatic group or non-aromatic ring system having 5 to 40 ring atoms.

[0043] In one embodiment, the substituents of the present invention are preferably selected from alkyl groups having 1-30 carbon atoms, aromatic groups containing 6-20 ring atoms, or heteroaromatic groups containing 5-20 ring atoms; further, the substituents are selected from alkyl groups having 1-8 carbon atoms, aromatic groups containing 6-10 ring atoms, or heteroaromatic groups containing 6-13 ring atoms.

[0044] In some embodiments, the aromatic amine organic compound is selected from one of the following structures:

[0045]

[0046] In some embodiments, in the aromatic amine organic compound, A is independently selected from any one of formulas (B-1) to (B-6):

[0047]

[0048] in:

[0049] X1 is selected from N or CR1;

[0050] Y1 is selected from O, S, S═O, SO2, NR2, PR2, CR2R3 or SiR2R3;

[0051] R1, R2, R3, at each occurrence, are independently selected from: -H, or -D, or a straight-chain alkyl group having 1 to 20 C atoms, or a straight-chain alkoxy group having 1 to 20 C atoms, or a straight-chain thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl group having 3 to 20 C atoms, or a branched or cyclic alkoxy group having 3 to 20 C atoms, or a branched or cyclic thioalkoxy group having 3 to 20 C atoms, or a silyl group, or a keto group having 1 to 20 C atoms, or an alkoxycarbonyl group having 2 to 20 C atoms, or a 7 to 20 C carbonyl group. an aryloxycarbonyl group having 20 C atoms, or a cyano group, or a carbamoyl group, or a haloformyl group, or a formyl group, or an isocyano group, or an isocyanate group, or a thiocyanate group, or an isothiocyanate group, or a hydroxyl group, or a nitro group, or -CF3, or -Cl, or -Br, or -F, or a crosslinkable group, or a substituted or unsubstituted aromatic group having 6 to 60 ring atoms, or a substituted or unsubstituted heteroaromatic group having 6 to 60 ring atoms, or a substituted or unsubstituted aryloxy group having 6 to 60 ring atoms, or a heteroaryloxy group having 6 to 60 ring atoms, or a combination of these groups;

[0052] Adjacent R1, R2 and R3 are connected to each other to form a ring or not;

[0053] Ar3 is selected from 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.

[0054] It can be understood that in the present invention, when X1 is a linking site, X1 is C.

[0055] Preferably, each occurrence of R1, R2, and R3 is independently selected from -H, or -D, or a linear alkyl group having 1 to 10 C atoms, or a branched or cyclic alkyl group having 3 to 10 C atoms, or a phenyl group, or a naphthyl group.

[0056] In one embodiment, Ar3 is selected from a substituted or unsubstituted aromatic group having 6 to 13 ring atoms, or a substituted or unsubstituted heteroaromatic group having 6 to 13 ring atoms.

[0057] Further, Ar3 is selected from

[0058] In one embodiment, A is selected from the following groups:

[0059]

[0060] Wherein: * indicates the connection site.

[0061] Preferably, X1 is selected from CH.

[0062] In some embodiments, the aromatic amine organic compound is selected from any one of the structures of formula (II-1) to (II-4):

[0063]

[0064] In some embodiments, L1 is selected from a substituted or unsubstituted aromatic group having 6 to 18 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 18 ring atoms.

[0065] Furthermore, L1 is selected from the following groups:

[0066]

[0067] in:

[0068] X is selected from N or CR5;

[0069] Y is selected from O, S, S=O, SO2, NR6, PR6, CR6R7 or SiR6R7;

[0070] R5, R6, R7, at each occurrence, are independently selected from: -H, or -D, or a linear alkyl group having 1 to 20 C atoms, or a linear alkoxy group having 1 to 20 C atoms, or a linear thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl group having 3 to 20 C atoms, or a branched or cyclic alkoxy group having 3 to 20 C atoms, or a branched or cyclic thioalkoxy group having 3 to 20 C atoms, or a silyl group, or a keto group having 1 to 20 C atoms, or an alkoxycarbonyl group having 2 to 20 C atoms, or a 7 or a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, or a substituted or unsubstituted aryloxy group having 5 to 60 ring atoms, or a substituted or unsubstituted aryloxy group having 5 to 60 ring atoms, or a heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups.

[0071] When X is a linking site, X is selected from C.

[0072] Further, L1 is selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted 9,9-fluorenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted carbazolyl, or substituted or unsubstituted 9-carbazolyl; further, the substituent is selected from -D, or a linear alkyl group having 1 to 10 C atoms, or a branched or cyclic alkyl group having 3 to 10 C atoms, or a phenyl group, or a naphthyl group.

[0073] Furthermore, L1 is selected from the following groups:

[0074]

[0075] Wherein: * indicates the connection site.

[0076] In some embodiments, Ar1 and Ar2 are independently selected from 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.

[0077] In some embodiments, Ar1 and Ar2 are each independently selected from any one of (C-1) to (C-6):

[0078]

[0079] in:

[0080] X2 is selected from N or CR8;

[0081] Y2 is selected from O, S, S=O, SO2, NR9, PR9, CR9R 10 or SiR9R 10 ;

[0082] R8, R9, R 10Each occurrence is independently selected from: -H, or -D, or a straight-chain alkyl group having 1 to 20 C atoms, or a straight-chain alkoxy group having 1 to 20 C atoms, or a straight-chain thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl group having 3 to 20 C atoms, or a branched or cyclic alkoxy group having 3 to 20 C atoms, or a branched or cyclic thioalkoxy group having 3 to 20 C atoms, or a silyl group, or a keto group having 1 to 20 C atoms, or an alkoxycarbonyl group having 2 to 20 C atoms, or a 7 to 20 C atom C atom, or a cyano group, or a carbamoyl group, or a haloformyl group, or a formyl group, or an isocyano group, or an isocyanate group, or a thiocyanate group, or an isothiocyanate group, or a hydroxyl group, or a nitro group, or -CF3, or -Cl, or -Br, or -F, or a crosslinkable group, or a substituted or unsubstituted aromatic group having 6 to 60 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, a substituted or unsubstituted aryloxy group having 5 to 60 ring atoms, a heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups.

[0083] Ar4 is independently selected from substituted or unsubstituted aromatic or heteroaromatic groups having 6 to 20 ring atoms;

[0084] Preferably, Ar4 is selected from

[0085] In some embodiments, Ar1 and Ar2 are each independently selected from the following structures:

[0086]

[0087] In some embodiments, Ar1 is selected from substituted or unsubstituted phenyl or Furthermore, the substituent is selected from -D, or a linear alkyl group having 1 to 10 C atoms, or a branched or cyclic alkyl group having 3 to 10 C atoms, or a phenyl group, or a biphenyl group or a naphthyl group.

[0088] In some embodiments, Ar1 and Ar2 are each independently selected from the following groups:

[0089]

[0090] Wherein: * indicates the connection site.

[0091] In some embodiments, the structure formed by Ar1 and Ar2 and the N connected to them is Selected from the following groups:

[0092]

[0093] Wherein: n1 is selected from any integer from 0 to 4; n2 is selected from any integer from 0 to 7; and n3 is selected from any integer from 0 to 5.

[0094] Preferably, R5 and R8 are independently selected from: -H, or -D, or a linear alkyl group having 1 to 10 C atoms, or a branched or cyclic alkyl group having 3 to 10 C atoms, or a phenyl group, or a biphenyl group, or a naphthyl group.

[0095] further, Selected from the following groups:

[0096]

[0097] In some embodiments, the general formula of the aromatic amine organic compound is selected from any one of formulas (III-1) to (III-4):

[0098] Wherein: n1 is selected from any integer from 0 to 4; n2 is selected from any integer from 0 to 7; and n3 is selected from any integer from 0 to 5.

[0099] Preferably, R5 and R8 in formula (III-1)-(III-4) are independently selected from: -H, or -D, or a straight-chain alkyl group having 1 to 10 C atoms, or a branched or cyclic alkyl group having 3 to 10 C atoms, or a phenyl group, or a biphenyl group, or a naphthyl group.

[0100] Furthermore, the aromatic amine organic compound is selected from the following structures:

[0101]

[0102] Wherein: R5, R8, Y, Y1, Y2, n1, n2, n3 have the same meanings as above.

[0103] In some embodiments, the aromatic amine organic compound preferably has, but is not limited to, the following structures, which may be arbitrarily substituted:

[0104]

[0105]

[0106]

[0107]

[0108]

[0109]

[0110] The aromatic amine organic compound described herein can be used as a functional material in the functional layers of electronic devices. 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 emitting layer (EML).

[0111] In one embodiment, the aromatic amine organic compound according to the present invention is used in a hole transport layer.

[0112] The present invention further relates to a mixture comprising at least one of the aromatic amine organic compounds described above and at least one other organic functional material. The at least one other organic functional material can be 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), an emitter, a host material, and an organic dye. For example, various organic functional materials are described in detail in WO2010135519A1, US20090134784A1, and WO2011110277A1, the entire contents of which are hereby incorporated herein by reference.

[0113] In one embodiment, the another organic functional material is selected from electron transport materials and is used as a co-host in electronic devices.

[0114] The present 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 at least one organic solvent is selected from aromatic or heteroaromatic compounds, esters, aromatic ketones or aromatic ethers, aliphatic ketones or aliphatic ethers, alicyclic or olefinic compounds, or borate or phosphate compounds, or a mixture of two or more solvents.

[0115] In a preferred embodiment, according to a composition of the present invention, the at least one organic solvent is selected from aromatic or heteroaromatic based solvents.

[0116] Alternatively, examples of aromatic or heteroaromatic solvents suitable for the present invention include, but are not limited to: p-diisopropylbenzene, pentylbenzene, tetralin, 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, dimethyl Naphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, 1-methylnaphthalene, 1,2,4-trichlorobenzene, 4,4-difluorodiphenylmethane, 1,2-dimethoxy-4-(1-propenyl)benzene, diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, α,α-dichlorodiphenylmethane, 4-(3-phenylpropyl)pyridine, benzyl benzoate, 1,1-bis(3,4-dimethylphenyl)ethane, 2-isopropylnaphthalene, quinoline, isoquinoline, methyl 2-furoate, ethyl 2-furoate, etc.

[0117] Alternatively, examples of aromatic ketone-based solvents suitable for the present invention include, but are not limited to: 1-tetralone, 2-tetralone, 2-(phenylepoxy)tetralone, 6-(methoxy)tetralone, acetophenone, propiophenone, benzophenone, and their derivatives, such as 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylpropiophenone, 3-methylpropiophenone, 2-methylpropiophenone, etc.

[0118] Alternatively, examples of aromatic ether-based solvents suitable for the present invention include, 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-ethyl acetate, 1,3-dipropoxybenzene, 1,2,4-trimethoxybenzene, 4-(1-propenyl)-1,2-dimethoxybenzene, 1,3-dimethoxybenzene, glycidyl phenyl ether, dibenzyl ether, 4-tert-butylanisole, trans-p-propenylanisole, 1,2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran, and ethyl-2-naphthyl ether.

[0119] In some preferred embodiments, according to the composition of the present invention, the at least one solvent can be selected from: aliphatic ketones, for example, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 2,5-hexanedione, 2,6,8-trimethyl-4-nonanone, fenchone, phorone, isophorone, di-n-amyl ketone, etc.; or aliphatic ethers, for example, 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, etc.

[0120] In other preferred embodiments, according to the composition of the present invention, the at least one solvent can be selected from ester-based solvents: alkyl octanoate, alkyl sebacate, alkyl stearate, alkyl benzoate, alkyl phenylacetate, alkyl cinnamate, alkyl oxalate, alkyl maleate, alkyl lactone, alkyl oleate, etc. Octyl octanoate, diethyl sebacate, diallyl phthalate, and isononyl isononanoate are particularly preferred.

[0121] The solvent can be used alone or as a mixture of two or more organic solvents.

[0122] In certain preferred embodiments, a composition according to the present invention comprises at least one organic compound or mixture as described above and at least one organic solvent, and may further comprise another organic solvent. The other organic solvent is selected from (but not limited to) methanol, ethanol, 2-methoxyethanol, dichloromethane, 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, tetralin, decalin, indene and / or mixtures thereof.

[0123] In some preferred embodiments, the solvents particularly suitable for the present invention are solvents having a Hansen solubility parameter within the following ranges:

[0124] δd (dispersion force) is in the range of 17.0 to 23.2 MPa1 / 2, especially in the range of 18.5 to 21.0 MPa1 / 2;

[0125] δp (polar force) is in the range of 0.2 to 12.5 MPa1 / 2, especially in the range of 2.0 to 6.0 MPa1 / 2;

[0126] δh (hydrogen bond strength) is in the range of 0.9 to 14.2 MPa1 / 2, and particularly in the range of 2.0 to 6.0 MPa1 / 2.

[0127] In the composition of the present invention, the organic solvent should be selected based on its boiling point. In the present invention, the boiling point of the organic solvent is ≥150°C; preferably ≥180°C; more preferably ≥200°C; even more preferably ≥250°C; and most preferably ≥275°C or ≥300°C. Boiling points within these ranges are beneficial for preventing nozzle clogging in inkjet printheads. The organic solvent can be evaporated from the solvent system to form a film containing the functional material.

[0128] In a preferred embodiment, the composition according to the invention is a solution.

[0129] In another preferred embodiment, the composition according to the invention is a suspension.

[0130] The composition in the embodiment of the present invention may include 0.01wt% to 10wt% of the aromatic amine organic compound or mixture according to the present invention, preferably 0.1wt% to 15wt%, more preferably 0.2wt% to 5wt%, and most preferably 0.25wt% to 3wt%.

[0131] The present invention also relates to the use of the composition as a coating or printing ink in the preparation of organic electronic devices, and particularly preferably a preparation method by printing or coating.

[0132] Suitable printing or coating techniques include, but are not limited to, inkjet printing, nozzle printing, letterpress printing, screen printing, dip coating, spin coating, doctor blade coating, roller printing, twist roll printing, lithographic printing, flexographic printing, rotary printing, spray coating, brush or pad printing, and slot extrusion coating. Gravure printing, nozzle printing, and inkjet printing are preferred. The solution or suspension may further include one or more components, such as surfactants, lubricants, wetting agents, dispersants, hydrophobic agents, and adhesives, to adjust viscosity, film-forming properties, and enhance adhesion. Relevant printing techniques and their associated requirements for the relevant solutions, such as solvent, concentration, and viscosity, are discussed in detail.

[0133] The present invention also provides a use of the aromatic amine organic compound, mixture, or composition described above in an organic electronic device. The organic electronic device may 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 (OLED), an organic laser, an organic spintronic device, an organic sensor, and an organic plasmon emitting diode (OPED). OLEDs are particularly preferred. In an embodiment of the present invention, the organic compound is preferably used in a hole transport layer of an OLED device.

[0134] The present 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 and second electrodes, wherein the organic functional layers comprise the aromatic amine organic compound, mixture, or composition described above. Furthermore, the organic electronic device comprises a cathode, an anode, and one or more organic functional layers positioned between the cathode and the anode.

[0135] 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, organic lasers, organic spintronic devices, organic sensors and organic plasmon emitting diodes (Organic Plasmon Emitting Diodes), etc., and organic electroluminescent devices such as OLEDs, OLEECs and organic light emitting field effect transistors are particularly preferred.

[0136] The organic functional layer according to the present invention can be selected from a hole injection layer (HIL), a hole transport layer (HTL), an emissive layer (EML), an electron blocking layer (EBL), an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer (HBL). Materials suitable for use in these functional layers are described in detail above and in WO2010135519A1, US20090134784A1, and WO2011110277A1, the entire contents of which are hereby incorporated by reference.

[0137] In one embodiment, the organic functional layer comprises at least one hole transport layer or electron blocking layer, and the hole transport layer or electron blocking layer comprises the aromatic amine organic compound as described above. The specific definition of the aromatic amine organic compound is as described above.

[0138] In some more preferred embodiments, the organic functional layer comprises at least two hole transport layers, wherein the hole transport layer close to the light-emitting layer (the second hole transport layer) comprises the aromatic amine organic compound as described above.

[0139] In one embodiment, the organic electronic device according to the present invention is a red light-emitting organic electronic device.

[0140] In one embodiment, the organic electronic device according to the present invention comprises a first electrode, a second electrode, and one or more organic functional layers located between the first electrode and the second electrode, wherein the functional layers comprise at least two functional layers: one of which is a hole transport layer or an electron blocking layer, and the functional layer comprises the aromatic amine organic compound described above; and the other functional layer is a light-emitting layer, the material of the light-emitting layer comprises a metal complex, and the structure thereof is shown in general formula (IV):

[0141]

[0142] in:

[0143] q is selected from 1 or 2;

[0144] Ar7, when present multiple times, is independently selected from a substituted or unsubstituted heteroaromatic group having 5 to 40 ring atoms;

[0145] Ar8, when present multiple times, is 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;

[0146] R 11 -R 12 Each occurrence is independently selected from: -H, or -D (deuterium), or a straight-chain alkyl group having 1 to 20 C atoms, or a branched or cyclic alkyl group having 3 to 20 C atoms, or a substituted or unsubstituted aromatic group having 6 to 60 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, or a combination of these groups.

[0147] In one embodiment, Ar7, when present multiple times, is independently selected from quinoline or isoquinoline and their derivatives.

[0148] In one embodiment, multiple occurrences of Ar8 are independently selected from phenyl and its derivatives.

[0149] Preferably, the metal complex is selected from any one of the general formulas (V-1) to (V-3):

[0150]

[0151] in:

[0152] a is selected from any integer between 0 and 6, b is selected from any integer between 0 and 4;

[0153] R 13 -R 14Each occurrence is independently selected from: -D (deuterium), or a straight-chain alkyl group having 1 to 20 C atoms, or a branched or cyclic alkyl group having 3 to 20 C atoms, or a substituted or unsubstituted aromatic group having 6 to 60 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, or a combination of these groups.

[0154] In one embodiment, at least one R 13 or R 14 It is selected from a linear alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms.

[0155] In one embodiment, at least one R 14 is selected from a linear alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms. 13 It is selected from a linear alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms.

[0156] In some embodiments, the metal complex (such as a metal iridium complex) is preferably selected from but not limited to the following structures, which may be arbitrarily substituted:

[0157]

[0158]

[0159] In some embodiments, the light emitting device has a light emission wavelength between 600 and 700 nm, preferably between 600 and 650 nm, and more preferably between 600 and 630 nm.

[0160] In addition, the present application also relates to an application of the above-mentioned electroluminescent device in various electronic devices, including, but not limited to, display devices, lighting devices, light sources, sensors, etc. Specific embodiments

[0162] The following will be combined with the drawings in the embodiments of this application to clearly and completely describe the technical solutions in the embodiments of this application. Obviously, the embodiments described are only part of the embodiments of this application, not all of the embodiments. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without making creative efforts are within the scope of protection of this application.

[0163] Example 1 Synthesis of Compound 1

[0164] This embodiment provides an aromatic amine organic compound (Compound 1), the preparation method of which is as follows:

[0165]

[0166] Synthesis of Intermediate 1-2: 1-1 (60 mmol), pinacol diboronate (60 mmol), Pd(dppf)Cl2 (0.2 mmol), and sodium acetate (70 mmol) were added to 180 mL of 1,4-dioxane and stirred at 100°C under nitrogen for 8 h. After cooling, the solvent was removed by rotary evaporation. The residue was dissolved in dichloromethane and washed with water. The organic phase was collected and the solvent was removed by rotary evaporation. The resulting crude product was recrystallized to obtain Intermediate 1-2 in a 75% yield.

[0167] Synthesis of Intermediate 1-4: Intermediate 1-2 (42 mmol) and Intermediate 1-3 (42 mmol) were dissolved in a mixture of 1,4-dioxane and water (200 / 20 ml), and Pd(PPh3)4 (0.5 mmol) and potassium carbonate (75 mmol) were added. Stirring was carried out at 100°C under a nitrogen atmosphere for 6 h. After cooling, the solvent was mostly removed by rotary evaporation. The product was then extracted with dichloromethane and washed with water. The organic phase was collected and the solvent was removed by rotary evaporation. The crude product was purified by column chromatography to obtain Intermediate 1-4 in a 90% yield.

[0168] Synthesis of Compound 1: Intermediate 1-4 (30 mmol), Intermediate 1-5 (30 mmol), Pd(dba)2 (0.3 mmol), tri-tert-butylphosphine (0.6 mmol), and sodium tert-butoxide (40 mmol) were dissolved in toluene and stirred at 100°C under nitrogen for 12 h. After cooling, the mixture was washed with water and separated. The organic phase was collected and the solvent removed by rotary evaporation. The crude product was purified by column chromatography and recrystallization to obtain Compound 1 in an 80% yield. MS (ASAP): 714.

[0169] Example 2 Synthesis of Compound 2

[0170] This embodiment provides an aromatic amine organic compound (Compound 2), the preparation method of which is as follows:

[0171]

[0172] Synthesis of Intermediate 2-3: Intermediate 2-1 (50 mmol), Intermediate 2-2 (50 mmol), Pd(dba)2 (0.5 mmol), tri-tert-butylphosphine (1.0 mmol), and sodium tert-butoxide (70 mmol) were dissolved in toluene and stirred at 75°C under nitrogen for 5 h. After cooling, the mixture was washed with water and separated. The organic phase was collected and the solvent was removed by rotary evaporation. The crude product was purified by column chromatography and recrystallization to obtain Intermediate 2-3 in a yield of 75%.

[0173] Synthesis of Intermediate 2-4: Intermediate 2-3 (35 mmol), 1,4-dibromobenzene (35 mmol), Pd(dba)2 (0.3 mmol), tri-tert-butylphosphine (0.6 mmol), and sodium tert-butoxide (50 mmol) were dissolved in toluene and stirred at 75°C under nitrogen for 5 h. After cooling, the mixture was washed with water and separated. The organic phase was collected and the solvent was removed by rotary evaporation. The crude product was purified by column chromatography and recrystallization to obtain Intermediate 2-4 in a yield of 75%.

[0174] Synthesis of Compound 2: Intermediate 2-4 (25 mmol), intermediate 1-4 (25 mmol), Pd(dba)2 (0.3 mmol), tri-tert-butylphosphine (0.6 mmol), and sodium tert-butoxide (40 mmol) were dissolved in toluene and stirred at 100°C under nitrogen for 12 h. After cooling, the mixture was washed with water and separated. The organic phase was collected and the solvent removed by rotary evaporation. The resulting crude product was purified by column chromatography and recrystallization to obtain an aromatic amine organic compound (i.e., Compound 2) in a yield of 79%. MS (ASAP): 754.

[0175] Example 3 Synthesis of Compound 3

[0176] This embodiment provides an aromatic amine organic compound (Compound 3), the preparation method of which is as follows:

[0177]

[0178] Synthesis of intermediate 3-2: Refer to the synthesis of intermediate 2-3 in Example 2, except that 2-2 is replaced by 3-1, with a yield of 75%.

[0179] Synthesis of intermediate 3-3: Refer to the synthesis of intermediate 2-4 in Example 2, except that 2-3 is replaced by 3-2, with a yield of 73%.

[0180] Synthesis of Compound 3: Refer to the synthesis of Compound 1 in Example 1, except that 1-5 is replaced by 3-3, yield 80%. MS (ASAP): 744.

[0181] Example 4 Synthesis of Compound 4

[0182] This embodiment provides an aromatic amine organic compound (Compound 4), the preparation method of which is as follows:

[0183]

[0184] Synthesis of intermediate 4-3: Refer to the synthesis of intermediate 2-3 in Example 2, except that 2-1 is replaced by 4-1, and 2-2 is replaced by 4-2. The yield is 70%.

[0185] Synthesis of intermediate 4-4: Refer to the synthesis of intermediate 2-4 in Example 2, except that 2-3 is replaced by 4-3, with a yield of 71%.

[0186] Synthesis of Compound 4: Refer to the synthesis of Compound 1 in Example 1, except that 1-5 is replaced by 4-4, yield 76%. MS (ASAP): 754.

[0187] Example 5 Synthesis of Compound 5

[0188] This embodiment provides an aromatic amine organic compound (Compound 5), the preparation method of which is as follows:

[0189]

[0190] Synthesis of intermediate 5-2: Refer to the synthesis of intermediate 2-3 in Example 2, except that 2-2 is replaced by 5-1, with a yield of 75%.

[0191] Synthesis of intermediate 5-3: Refer to the synthesis of intermediate 2-4 in Example 2, except that 2-3 is replaced by 5-2, with a yield of 74%.

[0192] Synthesis of Compound 5: Refer to the synthesis of Compound 1 in Example 1, except that 1-5 is replaced by 5-3, yield 85%. MS (ASAP): 738.

[0193] Example 6 Synthesis of Compound 6

[0194] This embodiment provides an aromatic amine organic compound (Compound 6), the preparation method of which is as follows:

[0195]

[0196] Synthesis of intermediate 6-2: Refer to the synthesis of intermediate 2-3 in Example 2, except that 2-2 is replaced by 6-1, with a yield of 75%.

[0197] Synthesis of intermediate 6-3: Refer to the synthesis of intermediate 2-4 in Example 2, except that 2-3 is replaced by 6-2, with a yield of 76%.

[0198] Synthesis of Compound 6: Refer to the synthesis of Compound 1 in Example 1, except that 1-5 is replaced by 6-3, yield 82%. MS (ASAP): 846.

[0199] Example 7 Synthesis of Compound 7

[0200] This embodiment provides an aromatic amine organic compound (Compound 7), the preparation method of which is as follows:

[0201]

[0202] Synthesis of intermediate 7-2: Refer to the synthesis of intermediate 2-3 in Example 2, except that 2-2 is replaced by 7-1, with a yield of 76%.

[0203] Synthesis of intermediate 7-4: Refer to the synthesis of intermediate 2-4 in Example 2, except that 2-3 is replaced by 7-2, and 1,4-dibromobenzene is replaced by 7-3, with a yield of 80%.

[0204] Synthesis of Compound 7: Intermediate 7-4 (25 mmol), Intermediate 1-4 (25 mmol), Pd(dba)2 (0.3 mmol), tri-tert-butylphosphine (0.6 mmol), and sodium tert-butoxide (40 mmol) were dissolved in toluene and stirred at 100°C under nitrogen for 12 h. After cooling, the mixture was washed with water and separated. The organic phase was collected and the solvent removed by rotary evaporation. The crude product was purified by column chromatography and recrystallization to obtain Compound 7 in a 70% yield. MS (ASAP): 734.

[0205] Example 8 Synthesis of Compound 8

[0206] This embodiment provides an aromatic amine organic compound (Compound 8), the preparation method of which is as follows:

[0207]

[0208] Synthesis of intermediate 8-3: Refer to the synthesis of intermediate 2-3 in Example 2, except that 2-1 is replaced by 8-1, and 2-2 is replaced by 8-2. The yield is 72%.

[0209] Synthesis of intermediate 8-3: Refer to the synthesis of intermediate 2-4 in Example 2, except that 2-3 is replaced by 8-3, with a yield of 75%.

[0210] Synthesis of Compound 8: Refer to the synthesis of Compound 1 in Example 1, except that 1-5 is replaced by 8-4, yield 82%. MS (ASAP): 794.

[0211] Example 9 Synthesis of Compound 9

[0212] This embodiment provides an aromatic amine organic compound (Compound 9), the preparation method of which is as follows:

[0213]

[0214] In this example, the synthesis of an aromatic amine organic compound (Compound 9) was carried out by referring to the synthesis of Compound 1 in Example 1, except that 1-5 was replaced by 9-1, with a yield of 84%. MS (ASAP): 638.

[0215] Example 10 Synthesis of Compound 10

[0216] This embodiment provides an aromatic amine organic compound (Compound 10), the preparation method of which is as follows:

[0217]

[0218] Synthesis of intermediate 10-2: Refer to the synthesis of intermediate 1-4 in Example 1, except that 1-3 is replaced by 10-1, with a yield of 85%.

[0219] Synthesis of Compound 10: Refer to the synthesis of Compound 1 in Example 1, except that 1-5 is replaced by 10-3, and 1-4 is replaced by 10-2, with a yield of 86%. MS (ASAP): 688.

[0220] Example 11 Synthesis of Compound 11

[0221] This embodiment provides an aromatic amine organic compound (Compound 11), the preparation method of which is as follows:

[0222]

[0223] Synthesis of intermediate 11-2: Refer to the synthesis of intermediate 1-4 in Example 1, except that 1-3 is replaced by 11-1, with a yield of 86%.

[0224] Synthesis of intermediate 11-4: Refer to the synthesis of intermediate 2-3 in Example 2, except that 2-2 is replaced by 11-3, with a yield of 75%.

[0225] Synthesis of intermediate 11-5: Refer to the synthesis of intermediate 2-4 in Example 2, except that 2-3 is replaced by 11-4, with a yield of 72%.

[0226] Synthesis of Compound 11: Refer to the synthesis of Compound 1 in Example 1, except that 1-4 is replaced by 11-2, and 1-5 is replaced by 11-5, with a yield of 85%. MS (ASAP): 744.

[0227] Example 12 Synthesis of Compound 12

[0228] This embodiment provides an aromatic amine organic compound (Compound 12), the preparation method of which is as follows:

[0229]

[0230] Synthesis of intermediate 12-2: Refer to the synthesis of intermediate 1-4 in Example 1, except that 1-3 is replaced by 12-1, with a yield of 84%.

[0231] Synthesis of intermediate 12-5: Refer to the synthesis of intermediate 2-3 in Example 2, except that 2-2 is replaced by 12-4, and 2-1 is replaced by 12-3, with a yield of 76%.

[0232] Synthesis of intermediate 12-6: Refer to the synthesis of intermediate 2-4 in Example 2, except that 2-3 is replaced by 12-5, with a yield of 74%.

[0233] Synthesis of Compound 12: Refer to the synthesis of Compound 1 in Example 1, except that 1-4 is replaced by 12-2, and 1-5 is replaced by 11-6, with a yield of 82%. MS (ASAP): 728.

[0234] Example 13 Synthesis of Compound 13

[0235] This embodiment provides an aromatic amine organic compound (Compound 13), the preparation method of which is as follows:

[0236]

[0237] Synthesis of intermediate 13-2: Refer to the synthesis of intermediate 1-4 in Example 1, except that 1-3 is replaced by 13-1, with a yield of 83%.

[0238] Synthesis of compound 13: Refer to the synthesis of compound 1 in Example 1, except that 1-4 is replaced by 13-2, and 1-5 is replaced by 13-3. MS (ASAP): 680.

[0239] Example 14 Synthesis of Compound 14

[0240] This embodiment provides an aromatic amine organic compound (Compound 14), the preparation method of which is as follows:

[0241]

[0242] Synthesis of intermediate 14-2: Refer to the synthesis of intermediate 1-4 in Example 1, except that 1-3 is replaced by 14-1, with a yield of 85%.

[0243] Synthesis of Compound 14: Refer to the synthesis of Compound 1 in Example 1, except that 1-4 is replaced by 14-2, and 1-5 is replaced by 10-3, with a yield of 80%. MS (ASAP): 744.

[0244] Example 15 Synthesis of Compound 15

[0245] This embodiment provides an aromatic amine organic compound (Compound 15), the preparation method of which is as follows:

[0246]

[0247] Synthesis of intermediate 15-2: Refer to the synthesis of intermediate 1-4 in Example 1, except that 1-3 is replaced by 15-1, with a yield of 75%.

[0248] Synthesis of Compound 15: Refer to the synthesis of Compound 1 in Example 1, except that 1-4 is replaced by 15-2, and 1-5 is replaced by 15-3, with a yield of 70%. MS (ASAP): 712.

[0249] Example 16 Synthesis of Compound 16

[0250] This embodiment provides an aromatic amine organic compound (Compound 16), the preparation method of which is as follows:

[0251]

[0252] Synthesis of compound 16: Refer to the synthesis of compound 1, except that 1-5 is replaced by 16-1, yield 72%. MS (ASAP): 714.

[0253] Example 17 Synthesis of Compound 17

[0254] This embodiment provides an aromatic amine organic compound (Compound 17), the preparation method of which is as follows:

[0255]

[0256] Synthesis of Intermediate 17-3: 17-1 (35 mmol), 17-2 (35 mmol), Pd(dba)2 (0.3 mmol), tri-tert-butylphosphine (0.6 mmol), and sodium tert-butoxide (50 mmol) were dissolved in toluene and stirred at 75°C under nitrogen for 5 h. After cooling, the mixture was washed with water and separated. The organic phase was collected and the solvent was removed by rotary evaporation. The crude product was purified by column chromatography and recrystallization to obtain Intermediate 17-3 in a yield of 76%.

[0257] The synthesis of compound 17 was carried out by referring to the synthesis of compound 1, except that 1-5 was replaced by 17-3, with a yield of 76%. MS (ASAP): 728.

[0258] Example 18 Synthesis of Compound 18

[0259] This embodiment provides an aromatic amine organic compound (Compound 18), the preparation method of which is as follows:

[0260]

[0261] Synthesis of intermediate 18-3: Refer to the synthesis of intermediate 17-3, except that 17-1 is replaced by 18-1, and 17-2 is replaced by 18-2, with a yield of 74%.

[0262] Synthesis of compound 18: Refer to the synthesis of compound 1, except that 1-5 is replaced by 18-3, yield 80%. MS (ASAP): 718.

[0263] Example 19 Synthesis of Compound 19

[0264] This embodiment provides an aromatic amine organic compound (Compound 19), the preparation method of which is as follows:

[0265]

[0266] Synthesis of intermediate 19-2: Refer to the synthesis of intermediate 1-4, except that 1-3 is replaced by 19-1, with a yield of 85%.

[0267] Synthesis of compound 19: Refer to the synthesis of compound 1, except that 1-4 is replaced by 19-2, yield 75%. MS (ASAP): 714.

[0268] Example 20 Synthesis of Compound 20

[0269] This embodiment provides an aromatic amine organic compound (Compound 20), the preparation method of which is as follows:

[0270]

[0271] Synthesis of intermediate 20-2: Refer to the synthesis of intermediate 1-4, except that 1-3 is replaced by 20-1, with a yield of 84%.

[0272] Synthesis of compound 20: Refer to the synthesis of compound 1, except that 1-4 is replaced by 20-2, yield 78%. MS (ASAP): 714.

[0273] Device Example 1

[0274] This embodiment provides an organic light emitting diode device (OLED device), see Figure 1The organic light-emitting diode device 10 includes a substrate 1, a first electrode 2 (such as an anode), a hole injection layer 3, a first hole transport layer 4, a second hole transport layer 5, a light-emitting layer 6, an electron transport layer 7, an electron injection layer 8 and a second electrode 9 (such as a cathode) stacked in sequence, wherein the light-emitting layer 6 contains the metal complex of the present application, and the hole transport layer 5 contains the aromatic amine organic compound of the present application.

[0275] Specifically, the OLED device structure is ITO (electrode) / hole injection layer (10nm) / first hole transport layer (60nm) / second hole transport layer (60nm) / host material RH1-red light guest RD2 / ETM:Liq / LiF / Al, where the mass ratio of host material RH1 to RD2 is 95:5.

[0276] The preparation process of the organic light emitting diode device is as follows:

[0277] a. Cleaning of conductive glass substrate: When used for the first time, it can be cleaned with a variety of solvents, such as chloroform, ketone, isopropyl alcohol, and then treated with UV ozone plasma;

[0278] b. The hole injection layer was made of HT1 / HATCN (97 / 3, w / w) on the ITO layer in a high vacuum (1×10 -6 mbar) by medium heat evaporation;

[0279] c. On the hole injection layer, HT1 with a thickness of 60 nm was evaporated as the first hole transport layer;

[0280] d. On the first hole transport layer, evaporating a 60 nm thick layer of compound 1 of the present application as a second hole transport layer;

[0281] e. Vacuum-deposit a 40 nm thick light-emitting layer on the second hole transport layer; the light-emitting layer includes RH1 as a host material and RD2 as a guest material;

[0282] f. On the light-emitting layer, a 25 nm thick ETM / Liq (1:1 mass ratio) mixture was evaporated as an electron transport layer; on the electron transport layer, a 0.5 nm thick LiF was used as an electron injection layer; and a 150 nm thick Al was used as the cathode;

[0283] g. Packaging: The device is encapsulated with UV curable resin in a nitrogen glove box.

[0284] In this embodiment, the structural formulas of some materials used in the OLED device are as follows:

[0285]

[0286] Device Examples 2 to 24

[0287] Device Examples 2 to 24 respectively provide an organic light-emitting diode device. The structure of the organic light-emitting diode device is the same as that of the organic light-emitting diode device of Device Example 1, except that the red light guest and the second hole transport layer materials in Device Examples 2 to 24 are different; wherein the red light guest in each device embodiment is selected from RD1 or RD2, and the second hole transport layer in each device embodiment is selected from any one of Compounds 1 to 20 in Examples 1 to 20. For details, please see Table 1.

[0288] The preparation method of the organic light emitting diode device is the same as that of device embodiment 1.

[0289] The structure of RD1 in the red light guest material is:

[0290] Comparative Example 1 to Comparative Example 3

[0291] Comparative Examples 1 to 3 provide an organic light-emitting diode device. The structure of each organic light-emitting diode device is the same as that of the organic light-emitting diode device in Device Example 1, except that the materials of the red light-emitting guest and the second hole transport layer in Comparative Examples 1 to 3 are different, as shown in Table 1. The preparation method of the organic light-emitting diode device is similar to that of Device Example 1.

[0292] The structural formula of the comparative example 1 in the second hole transport layer material is:

[0293] Test Example 1:

[0294] In this test example, the organic light emitting diode devices obtained in device examples 1 to 24 and comparative examples 1 to 3 were respectively tested for current-voltage (JV) characteristics, characterized by characterization equipment, and important parameters such as lifetime and external quantum efficiency were recorded.

[0295] As shown in Table 1

[0296] Table 1: Comparison of organic light-emitting diode device structure and performance

[0297]

[0298] Table 1 compares the lifetime (LT95) and external quantum efficiency of various OLED devices. LT95 is the time it takes for the brightness to drop to 95% of the initial brightness @ 1000 nits at a constant current. The LT95 and external quantum efficiency values ​​in Table 1 are calculated relative to Comparative Device Example 1 (corresponding materials: RD2 and Comparative Example 1), assuming the lifetime of Comparative Device Example 1 is 1 and the external quantum efficiency is 100.

[0299] As shown in Table 1, the external quantum efficiency and lifetime of the devices of Device Examples 1 to 24 are significantly higher than those of Comparative Device Example 1 (corresponding to RD2 and Comparative Example 1), Comparative Device Example 2 (corresponding to RD1 and Comparative Example 1), and Comparative Device Example 3 (corresponding to RD2, without the second hole transport layer). This can illustrate at least three points, as follows:

[0300] 1) The presence of the second hole transport layer helps improve device performance. This may be because the presence of the second hole transport layer improves the injection efficiency of holes into the light-emitting layer, while blocking the diffusion of electrons from the light-emitting layer to the hole transport layer, acting as an electron blocking layer, thereby improving the utilization efficiency of excitons;

[0301] 2) The performance of the OLED device of the present invention is better than that of the comparative device in Example 1, which shows that when the substituent group on the carbazole is selected When (1,2-dihydroacenaphthene) is used, the hole transport performance is better. The reason is that the 1,2-dihydroacenaphthene group has a non-completely conjugated five-membered ring structure, and the carbazole group is a conjugated group. The intermolecular interaction between the non-conjugated group and the conjugated group can improve the hole transport performance of the material.

[0302] 3) The performance of device embodiments 1 to 22 of the material of the present invention is better than that of device embodiments 23 to 24, which shows that ortho-position substitution is better than other sites. The reason is that: ortho-position connection results in greater steric hindrance between the two groups, which limits the rotation of the substituents and makes the molecules more rigid, thereby improving the stacking of the molecules and increasing the efficiency, stability and life of the device.

[0303] The above is a detailed introduction to an aromatic amine organic compound, mixture, composition and organic electronic device provided in the embodiments of the present application. Specific examples are used herein to illustrate the principles and implementation methods of the present application. The description of the above embodiments is only used to help understand the method of the present application and its core idea. At the same time, for those skilled in the art, based on the ideas of the present application, there may be changes in the specific implementation methods and application scopes. In summary, the content of this specification should not be understood as limiting the present application.

Claims

1. An aromatic amine organic compound, characterized in that: It has the structure shown in general formula (Ⅰ): in: The A is independently selected from any one of formulas (B-1) to (B-3) and (B-5): in: X1 is selected from CR1; Y1 is selected from O or S; The L1 is selected from the following groups: in: X is selected from CR5; Y is selected from O; R5 is independently selected from: -H, or -D, or a linear alkyl group having 1 to 10 C atoms, or a branched or cyclic alkyl group having 3 to 10 C atoms, or a phenyl group, or a biphenyl group, or a naphthyl group; Ar1 and Ar2 are each independently selected from any one of (C-1) to (C-3): in: X2 is selected from CR8; Y2 is selected from S or CR9R 10 ; The Ar3 is selected from the following groups: wherein X3 is selected from CH; R1 is independently selected from -H, or -D, or a linear alkyl group having 1 to 10 C atoms, or a branched or cyclic alkyl group having 3 to 10 C atoms, or a phenyl group, or a naphthyl group; Ar4 is selected from X4 is selected from N or CR8; R8, R9, R 10 Each occurrence is independently selected from: -H, or -D, or linear alkyl having 1 to 20 C atoms, or branched or cyclic alkyl having 3 to 20 C atoms.

2. The aromatic amine organic compound according to claim 1, characterized in that The aromatic amine organic compound is selected from one of the following structures:

3. The aromatic amine organic compound according to claim 2, characterized in that The A is selected from the following groups: Wherein: * indicates the connection site.

4. The aromatic amine organic compound according to claim 2, characterized in that The aromatic amine organic compound is selected from any one of the structures of formula (II-1) to (II-4):

5. The aromatic amine organic compound according to claim 1, characterized in that The L1 is selected from the following groups: Wherein: * indicates the connection site.

6. The aromatic amine organic compound according to claim 1, characterized in that The aromatic amine organic compound is selected from the following structures: n1 is selected from 1 or 2; n3 is selected from 1 or 2.

7. A mixture, characterized in that The method comprises at least one aromatic amine organic compound according to any one of claims 1 to 6, and at least one organic functional material; the organic functional material is selected from at least one of hole injection materials, hole transport materials, electron transport materials, electron injection materials, electron blocking materials, hole blocking materials, luminescent materials, host materials and organic dyes.

8. A composition, characterized in that The method comprises at least one aromatic amine organic compound according to any one of claims 1 to 6 or the mixture according to claim 7, and at least one organic solvent.

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