CN114426492B - Aromatic amine organic compound, mixture, composition and organic electronic device - Google Patents

Aromatic amine organic compound, mixture, composition and organic electronic device Download PDF

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CN114426492B
CN114426492B CN202110550688.0A CN202110550688A CN114426492B CN 114426492 B CN114426492 B CN 114426492B CN 202110550688 A CN202110550688 A CN 202110550688A CN 114426492 B CN114426492 B CN 114426492B
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CN114426492A (en
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李涛
宋晶尧
刘爱香
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Guangzhou Chinaray Optoelectronic Materials Ltd
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    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
    • C07C211/61—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton with at least one of the condensed ring systems formed by three or more rings
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/76—Dibenzothiophenes
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/625—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing at least one aromatic ring having 7 or more carbon atoms, e.g. azulene
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    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/92—Systems containing at least three condensed rings with a condensed ring system consisting of at least two mutually uncondensed aromatic ring systems, linked by an annular structure formed by carbon chains on non-adjacent positions of the aromatic system, e.g. cyclophanes

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Abstract

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

Description

Aromatic amine organic compound, mixture, composition and organic electronic device
The present application claims priority from chinese patent office, application number 202011175887X, chinese patent application entitled "an aromatic amine compound and its use" filed on 29 th 10 th 2020, the entire contents of which are incorporated herein by reference.
Technical Field
The invention relates to the technical field of organic electroluminescent materials, in particular to an arylamine organic compound, a mixture, a composition and an organic electronic device.
Background
The organic electroluminescent display device is a self-luminous display device, which generates excitons by transfer and recombination of carriers between functional layers, and emits light by means of organic compounds or metal complexes having high quantum efficiency. The organic electroluminescent element generally has a structure in which a positive electrode and a negative electrode and an organic functional layer is included therebetween. In order to improve the efficiency and lifetime of the organic electroluminescent device, the organic functional layers have a multi-layered structure, each layer containing a different organic material. Specifically, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like may be included. In such an organic electroluminescent element, when a voltage is applied between two electrodes, holes are injected from a positive electrode into an organic functional layer, electrons are injected from a negative electrode into the organic functional layer, and when the injected holes meet the electrons, excitons are formed, and light is emitted when the excitons transition back to a ground state. The organic electroluminescent element has the characteristics of self-luminescence, high brightness, high efficiency, low driving voltage, wide viewing angle, high contrast ratio and the like.
In recent years, the luminous efficiency of organic electroluminescent diodes (OLEDs) has been greatly improved, but the internal quantum efficiency thereof has been approaching the theoretical limit. The difference in mobility of holes and electrons causes that the recombination region is not completely uniformly dispersed in the light emitting layer, reducing the light emitting efficiency of the device. By further improving the material structure and the device structure, the hole mobility can be improved, the difference between the hole mobility and the electron mobility can be reduced, and the deflection of a composite region can be avoided, so that the luminous efficiency of the device and the service life of the device can be improved.
Disclosure of Invention
Based on this, the present invention aims to provide an arylamine organic compound, a mixture, a composition and an organic electronic device, which improve the efficiency and the lifetime of the device.
The technical proposal is as follows:
an arylamine organic compound has a structure formed by combining a chemical formula (1) and a chemical formula (2):
Wherein:
* Represents a condensed site of chemical formula (1) and chemical formula (2);
n1 and n2 are independently selected from 0 or 1, and n1+n2 is 1 or more;
l 1 and L 2 are each independently selected from a single bond, or a substituted or unsubstituted aryl group having 6 to 40 ring atoms, or a substituted or unsubstituted heteroaryl group having 6 to 40 ring atoms;
Ar 1-Ar4 is independently selected from a substituted or unsubstituted aryl group having 6 to 40 ring atoms, or a substituted or unsubstituted heteroaryl group having 5 to 40 ring atoms;
Ring a is a non-aromatic ring system having 5 to 20 ring atoms.
The invention also provides a mixture, which comprises the aromatic amine organic compound and at least one organic functional material, wherein the organic functional material is at least one of a hole injection material, a hole transport material, an electron injection material, an electron blocking material, a hole blocking material, a luminescent material, a main body material and an organic dye.
The invention also provides a composition comprising the aromatic amine organic compound or the mixture of the aromatic amine organic compound and at least one organic solvent.
The invention also provides an organic electronic device, which comprises a first electrode, a second electrode and one or more organic functional layers positioned between the first electrode and the second electrode, wherein the organic functional layers comprise the aromatic amine organic compound, or the mixture of the aromatic amine organic compound and the mixture or are prepared from the composition.
Compared with the prior art, the invention has the following beneficial effects:
the arylamine organic compound provided by the invention has excellent hole transmission property and stability, can be used as a hole transmission material or an electron blocking layer material for an organic light-emitting electronic device, especially for a green light organic light-emitting electronic device, and can obviously improve the luminous efficiency and the service life of the device.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
In the present invention, "substituted" means that a hydrogen atom in a substituted group is substituted by a substituent.
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 1, R 1 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 to be optionally substituted with groups acceptable in the art, including but not limited to: c 1-30 alkyl, heterocyclyl containing 3 to 20 ring atoms, aryl containing 5 to 20 ring atoms, heteroaryl containing 5 to 20 ring atoms, silyl, carbonyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, haloformyl, formyl, -NRR', cyano, isocyano, thiocyanate, isothiocyanate, hydroxy, trifluoromethyl, nitro or halogen, and which may be further substituted with art acceptable substituents; it is understood that R and R 'in-NRR' are each independently substituted with a group acceptable in the art, including but not limited to H, C 1-6 alkyl, cycloalkyl containing 3 to 8 ring atoms, heterocyclyl containing 3 to 8 ring atoms, aryl containing 5 to 20 ring atoms, or heteroaryl containing 5 to 10 ring atoms; the C 1-6 alkyl, cycloalkyl containing 3 to 8 ring atoms, heterocyclyl containing 3 to 8 ring atoms, aryl containing 5 to 20 ring atoms, or heteroaryl containing 5 to 10 ring atoms is optionally further substituted with one or more of the following groups: c 1-6 alkyl, cycloalkyl having 3 to 8 ring atoms, heterocyclyl having 3 to 8 ring atoms, halogen, hydroxy, nitro or amino.
In the present invention, the "number of ring atoms" 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.
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. The phrase containing the term, for example, "C 1-9 alkyl" refers to an alkyl group containing 1 to 9 carbon atoms, which at each occurrence may be, independently of one another, 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 alkyl. 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-dimethyloctyl, cyclooctyl, n-nonyl, n-decyl, adamantyl, 2-ethyldecyl, 2-butyldecyl, 2-hexyldecyl, 2-octyldecyl, n-undecyl, n-dodecyl, 2-ethyldodecyl, 2-butyldodecyl, 2-hexyldodecyl, 2-octyldodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, 2-ethylhexadecyl, 2-butylhexadecyl, 2-hexylhexadecyl, 2-octylhexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, 2-ethyleicosyl, 2-butyleicosyl, 2-hexyleicosyl, 2-octyleicosyl, n-heneicosyl, n-docosyl, n-tricosyl, n-tetracosyl, n-pentacosyl, n-hexacosyl, n-heptacosyl, n-octacosyl, n-nonacosyl, n-triacontyl, adamantane, and the like.
"Aryl, or aromatic group" refers to a hydrocarbon group containing at least one aromatic ring. "heteroaryl" or "heteroaromatic" refers to an aromatic hydrocarbon group containing at least one heteroatom. The heteroatoms are preferably selected from Si, N, P, O, S and/or Ge, particularly preferably from Si, N, P, O and/or S. Fused ring aromatic group means that the ring of the aromatic group may have two or more rings in which two carbon atoms are shared by two adjacent rings, i.e., fused rings. Fused heterocyclic aromatic groups refer to fused ring aromatic hydrocarbon groups containing at least one heteroatom. For the purposes of the present invention, aromatic or heteroaromatic groups include not only aromatic ring systems but also non-aromatic ring systems. Thus, systems such as pyridine, thiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, pyrazine, pyridazine, pyrimidine, triazine, carbene, and the like are also considered aromatic or heterocyclic aromatic groups for the purposes of this invention. For the purposes of the present invention, fused-ring aromatic or fused-heterocyclic aromatic ring systems include not only aromatic or heteroaromatic systems, but also systems in which a plurality of aromatic or heterocyclic aromatic groups may also be interrupted by short non-aromatic units (< 10% of non-H atoms, preferably less than 5% of non-H atoms, such as C, N or O atoms). Thus, for example, systems such as 9,9' -spirobifluorene, 9-diaryl fluorene, triarylamine, diaryl ether, and the like are also considered fused ring aromatic ring systems for the purposes of this invention.
In a preferred embodiment, the aromatic group is selected from: benzene, naphthalene, anthracene, fluoranthene, phenanthrene, benzophenanthrene, perylene, naphthacene, pyrene, benzopyrene, acenaphthene, fluorene, and derivatives thereof; the heteroaromatic group is selected from the group consisting of triazines, pyridines, pyrimidines, imidazoles, furans, thiophenes, benzofurans, benzothiophenes, indoles, carbazoles, pyrroloimidazoles, pyrrolopyrroles, thienopyrroles, thienothiothiophenes, furopyrroles, furofurans, thienofurans, benzisoxazoles, benzisothiazoles, benzimidazoles, quinolines, isoquinolines, phthalazines, quinoxalines, phenanthridines, primary pyridines, quinazolines, quinazolinones, dibenzothiophenes, dibenzofurans, carbazoles, and derivatives thereof.
Non-aromatic ring means a ring system containing at least one non-aromatic ring, and in the present invention, it is preferable that the non-aromatic ring system contains only a ring formed by a single carbon-carbon bond, such as an adamantyl group or a cyclohexyl group.
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.
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 1 groups on the benzene ring may be the same or different from each other.
In the present invention, "ring-forming" means forming an aliphatic ring, an aromatic ring, a heteroaromatic ring, an aliphatic heterocyclic ring, or a combination thereof.
In the present invention, "×" indicates a ligation site.
The technical scheme of the invention is as follows:
an arylamine organic compound has a structure formed by combining a chemical formula (1) and a chemical formula (2):
Wherein:
* Represents a condensed site of chemical formula (1) and chemical formula (2);
n1 and n2 are independently selected from 0 or 1, and n1+n2 is 1 or more;
l 1 and L 2 are each independently selected from a single bond, or a substituted or unsubstituted aryl group having 6 to 40 ring atoms, or a substituted or unsubstituted heteroaryl group having 6 to 40 ring atoms;
ar 1-Ar4 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;
Ring a is a non-aromatic ring system having 5 to 20 ring atoms.
In one embodiment, n1 is selected from 1; in one embodiment, n2 is selected from 1. In one embodiment, n1 and n2 are each selected from 1.
Further, the arylamine organic compound of the present invention has a structure represented by any one of formulas (3-1) to (3-5):
still further, the arylamine organic compounds of the present invention are selected from structures described in any one of formulas (4-1) - (4-4):
further, the arylamine organic compound of the present invention has a structure represented by formula (4-5) or (4-6):
In one embodiment, ar 1-Ar4 described herein is independently selected from substituted or unsubstituted aromatic groups having 6 to 30 ring atoms, or substituted or unsubstituted heteroaromatic groups having 5 to 30 ring atoms.
Further, ar 1-Ar4 is independently selected from any one of the groups shown in (B-1) to (B-7):
Wherein:
x is independently selected from N or CR 1 for each occurrence;
Y is selected from O, S, S = O, SO 2、NR2、PR2、CR3R4 or SiR 3R4;
Ar 5 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;
R 1-R4 is independently selected at each occurrence from the group consisting of-H, -D, straight chain alkyl having 1 to 20C atoms, straight chain alkoxy having 1 to 20C atoms, straight chain thioalkoxy having 1 to 20C atoms, branched or cyclic alkyl having 3 to 20C atoms, branched or cyclic alkoxy having 3 to 20C atoms, branched or cyclic thioalkoxy having 3 to 20C atoms, silyl, keto having 1 to 20C atoms, alkoxycarbonyl having 2 to 20C atoms, aryloxycarbonyl having 7 to 20C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, CF 3, cl, br, F, a crosslinkable group, a substituted or unsubstituted aryl having 5 to 30 ring atoms, a substituted or unsubstituted heteroaryl having 5 to 30 ring atoms, an aryloxy having 5 to 30 ring atoms, a heteroaryl having 5 to 30 ring atoms, and combinations thereof;
R 3 and R 4 are cyclic or acyclic with each other.
In a preferred embodiment Ar 5 is selected from (B-1) or (B-2) orX and Y are as defined above.
In one embodiment, each occurrence of X in (B-1) - (B-7) is selected from CR 1; further, R 1 is independently selected at each occurrence from the group consisting of-H, -D, -F, a straight chain alkyl group having 1 to 10C atoms, a branched or cyclic alkyl group having 3 to 10C atoms, a substituted or unsubstituted aromatic group having 5 to 10 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 10 ring atoms, or a combination of such groups;
Further, ar 1-Ar4 in the arylamine organic compound is independently selected from (B-1) - (B-3). And X is selected from CR 1. More preferably, ar 1-Ar4 is independently selected from any of the groups shown in (C-1) - (C-5):
Wherein: * Represents a ligation site; m1, m2, m3, m4 and m5 are each independently selected from 0,1, 2,3 or 4.
Particularly preferably, ar 1-Ar4 is independently selected from the group consisting of (C-1) and (C-2):
In one embodiment, m1 is selected from 1,2, 3, or 4; further, m1 is selected from 1.
In one embodiment, m2 is selected from 0.
In one embodiment, Y in (C-2) is selected from O, S or CR 3R4; further, Y is selected from CR 3R4.
In one embodiment, R 1 in (C-1) - (C-5) is independently selected at each occurrence from the group consisting of-H, -D, -F, straight chain alkyl having 1 to 10C atoms, branched or cyclic alkyl having 3 to 10C atoms, phenyl, or naphthyl.
In one embodiment, each occurrence of R 3 and R 4 is independently selected from the group consisting of-H, -D, a straight chain alkyl group having 1 to 10C atoms, a branched or cyclic alkyl group having 3 to 10C atoms, a substituted or unsubstituted aryl group having 5 to 20 ring atoms, a substituted or unsubstituted heteroaryl group having 5 to 20 ring atoms, or a combination of these groups;
Further, R 3 and R 4 are each independently selected from the group consisting of-H, -D, straight chain alkyl groups having 1 to 8C atoms, branched or cyclic alkyl groups having 3 to 8C atoms, and aryl or heteroaryl groups having 6 ring atoms.
In one embodiment, R 3 and R 4 are not cyclic, and further, R 3 and R 4 are each independently selected from the group consisting of-H, -D, methyl, ethyl, and phenyl.
In one embodiment, R 3 and R 4 form a ring system having 5 to 20 ring atoms; further, (C-2) may be selected from any one of the following groups:
In one embodiment, R 1 in (C-1) and (C-2) is independently selected at each occurrence from the group consisting of-D, -F, straight chain alkyl having 1 to 10C atoms, branched or cyclic alkyl having 3 to 10C atoms, substituted or unsubstituted aryl having 5 to 20 ring atoms, substituted or unsubstituted heteroaryl having 5 to 20 ring atoms, or a combination of these groups.
Preferably, R 1 in (C-1) or (C-2), each occurrence, is independently selected from the group consisting of-D, -F, straight chain alkyl groups having 1 to 8C atoms, branched or cyclic alkyl groups having 3 to 8C atoms, substituted or unsubstituted aromatic groups having 5 to 20 ring atoms.
Further, R 1 in (C-1) or (C-2), for each occurrence, is selected from the group consisting of-D, -F, phenyl, cyclohexyl, methyl, or adamantyl.
In one embodiment, at least one of Ar 1-Ar2 is selected from (C-2). In one embodiment, at least one of Ar 3-Ar4 is selected from (C-2).
Further, the aromatic amine-based organic compound has a structure represented by any one of formulas (5-1) to (5-8):
In one embodiment, L 1 and L 2 are each independently selected from a single bond, or a substituted or unsubstituted aromatic group having 6 to 20 ring atoms, or a substituted or unsubstituted heteroaromatic group having 6 to 20 ring atoms; further, L 1 and L 2 are each independently selected from a single bond, or an aromatic group having a number of ring atoms of 6 to 13.
Further, L 1 and L 2 are each independently selected from a single bond, or any one of the following groups:
Wherein:
x is independently selected from N or CR 1 for each occurrence;
Each occurrence of Y is independently selected from O, S, S = O, SO 2、NR2、PR2、CR3R4 or SiR 3R4;
R 1-R4 is independently selected at each occurrence from the group consisting of-H, -D, straight chain alkyl having 1 to 20C atoms, straight chain alkoxy having 1 to 20C atoms, straight chain thioalkoxy having 1 to 20C atoms, branched or cyclic alkyl having 3 to 20C atoms, branched or cyclic alkoxy having 3 to 20C atoms, branched or cyclic thioalkoxy having 3 to 20C atoms, silyl, keto having 1 to 20C atoms, alkoxycarbonyl having 2 to 20C atoms, aryloxycarbonyl having 7 to 20C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, CF 3, cl, br, F, a crosslinkable group, a substituted or unsubstituted aryl having 5 to 30 ring atoms, a substituted or unsubstituted heteroaryl having 5 to 30 ring atoms, an aryloxy having 5 to 30 ring atoms, a heteroaryl having 5 to 30 ring atoms, and combinations thereof;
R 3 and R 4 are cyclic or acyclic with each other.
In one embodiment, each occurrence of X in L 1 and L 2 is independently selected from CR 1; further, R 1 in L 1 and L 2, each occurrence, is independently selected from the group consisting of-H, -D, straight chain alkyl groups having 1 to 10C atoms, branched or cyclic alkyl groups having 3 to 10C atoms, substituted or unsubstituted aromatic groups having 5 to 30 ring atoms, substituted or unsubstituted heteroaromatic groups having 5 to 30 ring atoms, or combinations of these groups; further, R 1 in L 1 and L 2 are each independently selected from H at each occurrence.
In one embodiment, L 1 and L 2 are each independently selected from a single bond, or a group structurally having a benzene ring, pyridine, pyrimidine, triazine, naphthalene ring, quinoline, isoquinoline, dibenzofuran, dibenzothiophene, carbazole, fluorene, or phenanthrene.
In a preferred embodiment, L 1 and L 2 are each independently selected from the group consisting of a single bond,
In a preferred embodiment, L 1 and L 2 are both selected from single bonds.
In the formula (I-1) and the formula (I-2)/>Each independently selected from any one of the following groups:
in one embodiment, the non-aromatic ring system is selected from the group consisting of R-substituted or unsubstituted cyclohexyl, R-substituted or unsubstituted adamantyl, R-substituted or unsubstituted cyclopentyl, R-substituted or unsubstituted Substituted or unsubstituted by ROr R is substituted or unsubstituted/>The R is selected from-D, straight chain alkyl having 1 to 10C atoms, branched alkyl having 3 to 10C atoms.
In one embodiment, ring a of the present invention is selected from any one of the following groups:
wherein: the H atom on the ring may be further substituted.
Further, the method comprises the steps of,Selected from/>The following list of arylamine organic compound structures according to the present invention, but not limited thereto:
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The arylamine organic compound can be used as a functional material in a functional layer of an electronic device. 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).
In one embodiment, the aromatic amine-based organic compound according to the present invention is used in a hole transport layer or an electron blocking layer, and further, the aromatic amine-based organic compound according to the present invention is used in an electron blocking layer of a green light organic electronic device.
The invention further relates to a mixture comprising at least one aromatic amine-type organic compound as described above, and a 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, WO2010135519A1, US20090134784A1 and WO 2011110277A1, the entire contents of which 3 patent documents are hereby incorporated by reference.
In an embodiment, the further organic functional material is selected from hole injection materials.
The invention also relates to a composition comprising at least one aromatic amine organic compound or mixture as described above, and at least one organic solvent; the organic solvent is selected from aromatic or heteroaromatic, ester, aromatic ketone or aromatic ether, aliphatic ketone or aliphatic ether, alicyclic or olefin compound, or boric acid ester or phosphate ester compound, or mixture of two or more solvents.
In one of the preferred embodiments, a composition according to the invention, the 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 arylamine organic compound 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, solvents particularly suitable 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 23.2MPa 1/2, especially in the range of 18.5 to 21.0MPa 1/2;
δp (polar force) is in the range of 0.2 to 12.5MPa 1/2, especially in the range of 2.0 to 6.0MPa 1/2;
δh (hydrogen bonding force) is in the range of 0.9 to 14.2MPa 1/2, especially 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 composition according to embodiments of the present invention may comprise 0.01wt% to 10wt% of the aromatic amine-based organic compound or mixture according to the present invention, preferably 0.1wt% to 15wt%, more preferably 0.2wt% to 5wt%, most preferably 0.25wt% to 3wt%.
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 organic 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 organic compound is preferably used for a hole transport layer or an electron blocking layer of an OLED device.
The invention further relates to an organic electronic device comprising a first electrode, a second electrode, one or more organic functional layers between the first electrode and the second electrode, said organic functional layers comprising or being prepared from an arylamine 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). Materials suitable for use in these functional layers are described in detail above and in WO2010135519A1, US20090134784A1 and WO2011110277A1, 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 or electron blocking layer, and the hole transporting layer or electron blocking layer comprises the arylamine organic compound as described above. The definition of specific arylamine organic compounds is as described above.
The invention also relates to the use of the electroluminescent device according to the invention in various electronic devices, including but not limited to display devices, lighting devices, light sources, sensors, etc.
The 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.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
1. Synthesis of Compounds
Example 1: synthesis of Compound G11
Z1 (11.58 g,30 mmol) was dissolved in anhydrous tetrahydrofuran, cooled to-78℃and butyllithium (1.6M, 18.7 mL) was slowly added. After about 0.5 hours, a solution of adamantanone (5.4 g,30 mmoL) in anhydrous tetrahydrofuran was added dropwise to the flask, and the reaction was continued at this temperature for half an hour, then allowed to warm to room temperature, and continued for 8 hours. The solvent was removed under reduced pressure, hydrochloric acid and acetic acid were added, and the mixture was refluxed for about 2 hours. Cooled to room temperature, deionized water was added, and extraction was performed with ethyl acetate. After concentration, the mixture was separated by a silica gel column, and the solvent was removed to obtain a total of 10g of Z2, and the yield was 76%.
Z2 (8.8 g,20 mmol) was dissolved in anhydrous tetrahydrofuran, cooled to-78℃and butyllithium (1.6M, 8.7 mL) was slowly added. After about 0.5 hours, a solution of 4-bromofluorenone (5.18 g,20 mmoL) in anhydrous tetrahydrofuran was added dropwise to the reaction flask, the reaction was continued at this temperature for half an hour, and then, the temperature was raised to room temperature, and the reaction was continued for 8 hours. The solvent was removed under reduced pressure, hydrochloric acid and acetic acid were added, and the mixture was refluxed for about 2 hours. Cooled to room temperature, deionized water was added, and extraction was performed with ethyl acetate. After concentration, the mixture was separated by a silica gel column, and the solvent was removed to obtain 9.75g of Z3 in a yield of 81%.
Compounds Z3 (9 g,15 mmol) and Z3-1 (4.55 g,15 mmol) were dissolved in anhydrous toluene, sodium t-butoxide (1.73 g,18 mmol) and dibenzylideneacetone dipalladium (0.41 g,0.45 mmol) were added, nitrogen was replaced three times, and then tri-t-butylphosphine (0.45 mmol) was added, and the temperature was gradually raised to 80℃and the reaction was stirred for 12 hours, followed by removal of the heat source. After the system is cooled, deionized water is added, an organic layer is separated, and extracted with ethyl acetate for three times, concentrated under reduced pressure, and the product G11 with the yield of 65G is obtained through a silica gel column; MS 825[ M + ].
Example 2: synthesis of Compound G16
Compound Z3 (6.02 g,10 mmol) and Z4-1 (3.77 g,10 mmol) were dissolved in anhydrous toluene, sodium tert-butoxide (1.15 g,12 mmol) and dibenzylideneacetone dipalladium (0.27 g,0.3 mmol) were added, nitrogen was replaced three times, and then tri-tert-butylphosphine (0.3 mmol) was added, and the temperature was gradually raised to 80℃and the reaction was stirred for 12 hours, followed by removal of the heat source. After the system was cooled, deionized water was added, the organic layer was separated, extracted three times with ethyl acetate, concentrated under reduced pressure, and passed through a silica gel column to give 6.83G of product G16 in 76% yield; MS 899[ M + ].
Example 3: synthesis of Compound G23
Z1 (11.58 g,30 mmol) was dissolved in anhydrous tetrahydrofuran, cooled to-78℃and butyllithium (1.6M, 18.7 mL) was slowly added. After about 0.5 hours, a solution of cyclohexanone (2.94 g,30 mmoL) in anhydrous tetrahydrofuran was added dropwise to the flask, and the reaction was continued at this temperature for half an hour, then warmed to room temperature, and continued for 8 hours. The solvent was removed under reduced pressure, hydrochloric acid and acetic acid were added, and the mixture was refluxed for about 2 hours. Cooled to room temperature, deionized water was added, and extraction was performed with ethyl acetate. After concentration, the mixture was separated by a silica gel column, and the solvent was removed to obtain 8.5g of Z4 in 73% yield.
Z4 (7.76 g,20 mmol) was dissolved in anhydrous tetrahydrofuran, cooled to-78℃and butyllithium (1.6M, 12.5 mL) was slowly added. After about 0.5 hours, a solution of 4-bromofluorenone (5.18 g,20 mmoL) in anhydrous tetrahydrofuran was added dropwise to the reaction flask, the reaction was continued at this temperature for half an hour, and then, the temperature was raised to room temperature, and the reaction was continued for 8 hours. The solvent was removed under reduced pressure, hydrochloric acid and acetic acid were added, and the mixture was refluxed for about 2 hours. Cooled to room temperature, deionized water was added, and extraction was performed with ethyl acetate. After concentration, the mixture was separated by a silica gel column, and the solvent was removed to obtain 9.02g of Z5 in 82% yield.
Compounds Z5 (8.25 g,15 mmol) and Z6 (4.35 g,15 mmol) were dissolved in anhydrous toluene, sodium t-butoxide (1.73 g,18 mmol) and dibenzylideneacetone dipalladium (0.41 g,0.45 mmol) were added, nitrogen was replaced three times, and then tri-t-butylphosphine (0.45 mmol) was added, and the temperature was gradually raised to 80℃and the reaction was stirred for 12 hours, followed by removal of the heat source. After the system was cooled, deionized water was added, the organic layer was separated, extracted three times with ethyl acetate, concentrated under reduced pressure, and passed through a silica gel column to give 8.89G of product G23, yield 78%; MS 760[ M + ].
Example 4: synthesis of Compound G37
Compound Z5 (5.1 g,10 mmol) and Z7 (2.85 g,10 mmol) were dissolved in anhydrous toluene, sodium t-butoxide (1.15 g,12 mmol) and dibenzylideneacetone dipalladium (0.27 g,0.3 mmol) were added, nitrogen was replaced three times, and then tri-t-butylphosphine (0.3 mmol) was added, and the temperature was gradually raised to 80℃and the reaction was stirred for 12 hours, followed by removal of the heat source. After the system was cooled, deionized water was added, the organic layer was separated, extracted three times with ethyl acetate, concentrated under reduced pressure, and passed through a silica gel column to give 6.28G of product G37 in 85% yield; MS:739[ M + ].
Example 5: synthesis of Compound G27
Compounds Z5 (5.5 g,10 mmol) and Z8 (3.61 g,10 mmol) were dissolved in anhydrous toluene, sodium t-butoxide (1.15 g,12 mmol) and dibenzylideneacetone dipalladium (0.27 g,0.3 mmol) were added, nitrogen was replaced three times, and then tri-t-butylphosphine (0.3 mmol) was added, and the temperature was gradually raised to 80℃and the reaction was stirred for 12 hours, followed by removal of the heat source. After the system was cooled, deionized water was added, the organic layer was separated, extracted three times with ethyl acetate, concentrated under reduced pressure, and passed through a silica gel column to give 5.9G of product G27 in 71% yield; MS:831[ M + ].
Example 6: synthesis of Compound G59
Z2 (8.8 g,20 mmol) was dissolved in anhydrous tetrahydrofuran, cooled to-78℃and butyllithium (1.6M, 12.5 mL) was slowly added. After about 0.5 hours, a solution of 3-bromofluorenone (5.18 g,20 mmoL) in anhydrous tetrahydrofuran was added dropwise to the reaction flask, the reaction was continued at this temperature for half an hour, and then, the temperature was raised to room temperature, and the reaction was continued for 8 hours. The solvent was removed under reduced pressure, hydrochloric acid and acetic acid were added, and the mixture was refluxed for about 2 hours. Cooled to room temperature, deionized water was added, and extraction was performed with ethyl acetate. After concentration, the mixture was separated by a silica gel column, and the solvent was removed to obtain 9.51g of Z9 in 79% yield.
Compounds Z9 (6.02 g,10 mmol) and Z10 (2.75 g,10 mmol) were dissolved in anhydrous toluene, sodium t-butoxide (1.15 g,12 mmol) and dibenzylideneacetone dipalladium (0.27 g,0.3 mmol) were added, nitrogen was replaced three times, and then tri-t-butylphosphine (0.3 mmol) was added, and the temperature was gradually raised to 80℃and the reaction was stirred for 12 hours, followed by removal of the heat source. After the system was cooled, deionized water was added, the organic layer was separated, extracted three times with ethyl acetate, concentrated under reduced pressure, and passed through a silica gel column to give 6.53G of product G59 in 82% yield; MS:797[ M + ].
Example 7: synthesis of Compound G61
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Z2 (8.8 g,20 mmol) was dissolved in anhydrous tetrahydrofuran, cooled to-78℃and butyllithium (1.6M, 12.5 mL) was slowly added. After about 0.5 hours, a solution of 2-bromofluorenone (5.18 g,20 mmoL) in anhydrous tetrahydrofuran was added dropwise to the reaction flask, the reaction was continued at this temperature for half an hour, and then, the temperature was raised to room temperature, and the reaction was continued for 8 hours. The solvent was removed under reduced pressure, hydrochloric acid and acetic acid were added, and the mixture was refluxed for about 2 hours. Cooled to room temperature, deionized water was added, and extraction was performed with ethyl acetate. After concentration, the mixture was separated by a silica gel column, and the solvent was removed to obtain 8.79g of Z11 in 73% yield.
Compounds Z11 (6.02 g,10 mmol) and Z12 (2.85 g,10 mmol) were dissolved in anhydrous toluene, sodium t-butoxide (1.15 g,12 mmol) and dibenzylideneacetone dipalladium (0.27 g,0.3 mmol) were added, nitrogen was replaced three times, and then tri-t-butylphosphine (0.3 mmol) was added, and the temperature was gradually raised to 80℃and the reaction was stirred for 12 hours, followed by removal of the heat source. After the system was cooled, deionized water was added, the organic layer was separated, extracted three times with ethyl acetate, concentrated under reduced pressure, and passed through a silica gel column to give 6.94G of product G61 in 86% yield; MS 807[ M + ].
Example 8: synthesis of Compound G116
Z14 (5.56 g,30 mmol), methyl o-bromobenzoate (6.45 g,30 mmol), potassium carbonate (12.42 g,90 mmol), tetrakis (triphenylphosphine) palladium (1.04 g,0.9 mmol) were weighed into a 250mL two-necked flask, 120mL of a mixed solvent of toluene and methanol was added, nitrogen was purged three times, and the temperature was raised to 90℃and stirred overnight. After the reaction solution is cooled to room temperature, water is added, ethyl acetate is used for extraction, sodium sulfate is used for drying, the organic solvent is removed by reduced pressure distillation, and the silica gel is subjected to column chromatography separation. The intermediate is placed in a methanesulfonic acid solution, heated to 130 ℃, continuously reacted for 2 hours, cooled to room temperature, added with NaOH for neutralization, suction filtered and separated by silica gel sample column chromatography to obtain a target product Z15 of 4.13g, and the yield is 41%.
Z16 (3.72 g,12 mmol) was dissolved in anhydrous tetrahydrofuran, cooled to-78℃and butyllithium (1.6M, 7.5 mL) was slowly added. After about 0.5 hours, a solution of Z15 (4.03 g,12 mmoL) in anhydrous tetrahydrofuran was added dropwise to the flask, the reaction was continued at this temperature for half an hour, and then it was warmed to room temperature and continued for 8 hours. The solvent was removed under reduced pressure, hydrochloric acid and acetic acid were added, and the mixture was refluxed for about 2 hours. Cooled to room temperature, deionized water was added, and extraction was performed with ethyl acetate. After concentration, the mixture was separated by a silica gel column, and the solvent was removed to obtain 5.15g of Z17 in 78% yield.
Compound Z17 (4.4 g,8 mmol) and Z17-1 (3.26 g,8 mmol) were dissolved in anhydrous toluene, sodium tert-butoxide (0.92 g,9.6 mmol) and dibenzylideneacetone dipalladium (0.22 g,0.24 mmol) were added, nitrogen was replaced three times, and then tri-tert-butylphosphine (0.24 mmol) was added, and the temperature was gradually raised to 80℃and the reaction was stirred for 12 hours, followed by removal of the heat source. After the system was cooled, deionized water was added, the organic layer was separated, extracted three times with ethyl acetate, concentrated under reduced pressure, and passed through a silica gel column to give 5.61G of product G116 in 80% yield; MS 877[ M + ].
Example 9: synthesis of Compound G173
Z18 (9.9 g,30 mmol), Z19 (10.77 g,30 mmol), potassium carbonate (12.42 g,90 mmol) and tetrakis (triphenylphosphine) palladium (1.04 g,0.9 mmol) were weighed into a 250mL two-necked flask, 160mL of a mixed solvent of toluene and methanol was added, nitrogen was purged three times, and the temperature was raised to 90℃and stirred overnight. After the reaction solution is cooled to room temperature, water is added, ethyl acetate is used for extraction, sodium sulfate is used for drying, the organic solvent is removed through reduced pressure distillation, and the target product Z20 is obtained through silica gel sample mixing column chromatography separation, wherein the total yield is 5.9g, and the yield is 38%.
Z20 (5.18 g,10 mmol) was dissolved in anhydrous tetrahydrofuran, cooled to-78℃and butyllithium (1.6M, 6.3 mL) was slowly added. After about 0.5 hours, a solution of fluorenone (1.8 g,10 mmoL) in anhydrous tetrahydrofuran was added dropwise to the reaction flask, the reaction was continued at this temperature for half an hour, and then, the reaction was allowed to warm to room temperature and continued for 8 hours. The solvent was removed under reduced pressure, hydrochloric acid and acetic acid were added, and the mixture was refluxed for about 2 hours. Cooled to room temperature, deionized water was added, and extraction was performed with ethyl acetate. After concentration, the mixture was separated by a silica gel column, and the solvent was removed to obtain a total of 4.7g of Z21, and the yield was 78%.
Compound Z21 (4.5 g,7.5 mmol) and Z22 (1.84 g,7.5 mmol) were dissolved in anhydrous toluene, sodium tert-butoxide (0.86 g,9 mmol) and dibenzylideneacetone dipalladium (0.2 g,0.22 mmol) were added, nitrogen was replaced three times, and then tri-tert-butylphosphine (0.22 mmol) was added, and the temperature was gradually raised to 80℃and the reaction was stirred for 12 hours, followed by removal of the heat source. After the system was cooled, deionized water was added, the organic layer was separated, extracted three times with ethyl acetate, concentrated under reduced pressure, and passed through a silica gel column to give 4.95G of product G173, 86% yield; MS:767[ M + ].
Example 10: synthesis of Compound G186
Compound Z23 (9.44 g,20 mmol) and Z24 (4.38 g,20 mmol) were dissolved in anhydrous toluene, sodium t-butoxide (2.3 g,24 mmol) and dibenzylideneacetone dipalladium (0.55 g,0.6 mmol) were added, nitrogen was replaced three times, and then tri-t-butylphosphine (0.6 mmol) was added, and the temperature was gradually raised to 80℃and the reaction was stirred for 12 hours, followed by removal of the heat source. After the system was cooled, deionized water was added, the organic layer was separated, extracted three times with ethyl acetate, concentrated under reduced pressure, and passed through a silica gel column to give 8.06g of product Z25 in 66% yield.
A250 mL two-necked flask was charged with Z25 (7.33 g,12 mmol), o-bromophenylboric acid (2.4 g,12 mmol), potassium carbonate (5 g,36 mmol), tetrakis (triphenylphosphine) palladium (0.42 g,0.36 mmol), 150mL of a mixed solvent of toluene and methanol, and nitrogen was purged three times, and the temperature was raised to 90℃and stirred overnight. After the reaction solution was cooled to room temperature, water was added thereto, and the mixture was extracted with ethyl acetate, dried over sodium sulfate, the organic solvent was removed by distillation under reduced pressure, and 4.78g of the product Z26 was isolated by column chromatography on a silica gel column, in 58% yield.
Z26 (4.12 g,6 mmol) was dissolved in anhydrous tetrahydrofuran, cooled to-78℃and butyllithium (1.6M, 3.7 mL) was slowly added. After about 0.5 hours, a solution of adamantanone (0.9 g,6 mmoL) in anhydrous tetrahydrofuran was added dropwise to the flask, and the reaction was continued at this temperature for half an hour, then warmed to room temperature, and continued for 8 hours. The solvent was removed under reduced pressure, hydrochloric acid and acetic acid were added, and the mixture was refluxed for about 2 hours. Cooled to room temperature, deionized water was added, and extraction was performed with ethyl acetate. After concentration, the mixture was separated by a silica gel column, and the solvent was removed to obtain 3.65G of G186 in 82% yield. MS 741[ M + ].
Example 11: synthesis of Compound G113
Compound Z17 (4.4 g,8 mmol) and Z27 (2.6 g,8 mmol) were dissolved in anhydrous toluene, sodium t-butoxide (0.92 g,9.6 mmol) and dibenzylideneacetone dipalladium (0.22 g,0.24 mmol) were added, nitrogen was replaced three times, and then tri-t-butylphosphine (0.24 mmol) was added, and the temperature was gradually raised to 80℃and the reaction was stirred for 12 hours, followed by removal of the heat source. After the system was cooled, deionized water was added, the organic layer was separated, extracted three times with ethyl acetate, concentrated under reduced pressure, and passed through a silica gel column to give 5.47G of product G113 in 86% yield; MS:795[ M + ].
Example 12: synthesis of Compound G216
Z3 (12.04 g,20 mmol), p-chlorobenzeneboronic acid (3.12 g,20 mmol), potassium carbonate (8.28 g,60 mmol) and tetrakis (triphenylphosphine) palladium (0.69 g,0.6 mmol) were weighed into a 250mL two-necked flask, a mixed solvent of toluene and methanol was added, nitrogen was introduced three times, and the temperature was raised to 90℃and stirred overnight. After the reaction solution is cooled to room temperature, water is added, ethyl acetate is used for extraction, sodium sulfate is used for drying, the organic solvent is removed through reduced pressure distillation, and 9.63g of target product Z28 is obtained through silica gel sample column chromatography separation, and the yield is 76%.
Compound Z28 (6.34 g,10 mmol) and Z29 (2.19 g,10 mmol) were dissolved in anhydrous toluene, sodium tert-butoxide (1.15 g,12 mmol) and dibenzylideneacetone dipalladium (0.27 g,0.3 mmol) were added, nitrogen was replaced three times, and then tri-tert-butylphosphine (0.3 mmol) was added, and the temperature was gradually raised to 80℃and the reaction was stirred for 12 hours, followed by removal of the heat source. After the system was cooled, deionized water was added, the organic layer was separated, extracted three times with ethyl acetate, concentrated under reduced pressure, and passed through a silica gel column to give 6.04G of product G216 in 74% yield; MS 817[ M + ].
Example 13: synthesis of Compound G229
Z18 (9.9 g,30 mmol), Z30 (9.45 g,30 mmol), potassium carbonate (12.42 g,90 mmol) and tetrakis (triphenylphosphine) palladium (1.04 g,0.9 mmol) were weighed into a 250mL two-necked flask, a mixed solvent of toluene and methanol was added, nitrogen was introduced three times, and the temperature was raised to 90℃and stirred overnight. After the reaction solution is cooled to room temperature, water is added, ethyl acetate is used for extraction, sodium sulfate is used for drying, the organic solvent is removed through reduced pressure distillation, and 8.24g of target product Z31 is obtained through silica gel sample-mixing column chromatography separation, and the yield is 58%.
Z31 (7.11 g,15 mmol) was dissolved in anhydrous tetrahydrofuran, cooled to-78℃and butyllithium (1.6M, 9.3 mL) was slowly added. After about 0.5 hours, a solution of fluorenone (2.7 g,15 mmoL) in anhydrous tetrahydrofuran was added dropwise to the reaction flask, the reaction was continued at this temperature for half an hour, and then, the reaction was allowed to warm to room temperature and continued for 8 hours. The solvent was removed under reduced pressure, hydrochloric acid and acetic acid were added, and the mixture was refluxed for about 2 hours. Cooled to room temperature, deionized water was added, and extraction was performed with ethyl acetate. After concentration, the mixture was separated by a silica gel column, and the solvent was removed to obtain 4.52g of Z32 in a yield of 54%.
Compound Z32 (4.18 g,7.5 mmol) and Z32-1 (3.04 g,7.5 mmol) were dissolved in anhydrous toluene, sodium tert-butoxide (0.86 g,9 mmol) and dibenzylideneacetone dipalladium (0.2 g,0.22 mmol) were added, nitrogen was replaced three times, and then tri-tert-butylphosphine (0.22 mmol) was added, and the temperature was gradually raised to 80℃and the reaction was stirred for 12 hours, followed by removal of the heat source. After the system was cooled, deionized water was added, the organic layer was separated, extracted three times with ethyl acetate, concentrated under reduced pressure, and passed through a silica gel column to give 5.7G of product G229 in 86% yield; MS:883[ M + ].
Example 14: synthesis of Compound G223
Z11 (9.03 g,15 mmol), m-chlorobenzeneboronic acid (2.34 g,15 mmol), potassium carbonate (6.21 g,45 mmol) and tetrakis (triphenylphosphine) palladium (0.52 g,0.45 mmol) were weighed into a 250mL two-necked flask, a mixed solvent of toluene and methanol was added, nitrogen was introduced three times, and the temperature was raised to 90℃and stirred overnight. After the reaction solution is cooled to room temperature, water is added, ethyl acetate is used for extraction, sodium sulfate is used for drying, the organic solvent is removed through reduced pressure distillation, and the target product Z33 is obtained through silica gel sample mixing column chromatography separation, wherein the total yield is 6.56g, and the yield is 69%.
Compound Z33 (6.34 g,10 mmol) and Z34 (1.79 g,10 mmol) were dissolved in anhydrous toluene, sodium t-butoxide (1.15 g,12 mmol) and dibenzylideneacetone dipalladium (0.27 g,0.3 mmol) were added, nitrogen was replaced three times, and then tri-t-butylphosphine (0.3 mmol) was added, and the temperature was gradually raised to 80℃and the reaction was stirred for 12 hours, followed by removal of the heat source. After the system was cooled, deionized water was added, the organic layer was separated, extracted three times with ethyl acetate, concentrated under reduced pressure, and passed through a silica gel column to give 6.6G of product G223 in 85% yield; MS 777[ M + ].
Example 15: synthesis of Compound G245
Z35 (8.34 g,30 mmol), Z19 (10.77 g,30 mmol), potassium carbonate (12.42 g,90 mmol) and tetrakis (triphenylphosphine) palladium (1.04 g,0.9 mmol) were weighed into a 250mL two-necked flask, a mixed solvent of toluene and methanol was added, nitrogen was introduced three times, and the temperature was raised to 90℃and stirred overnight. After the reaction solution is cooled to room temperature, water is added, ethyl acetate is used for extraction, sodium sulfate is used for drying, the organic solvent is removed through reduced pressure distillation, and the target product Z36 is obtained through silica gel sample mixing column chromatography separation, wherein the total yield is 5.73g, and the yield is 41%.
Z36 (5.59 g,12 mmol) was dissolved in anhydrous tetrahydrofuran, cooled to-78℃and butyllithium (1.6M, 7.5 mL) was slowly added. After about 0.5 hours, a solution of 4-bromofluorenone (3.1 g,12 mmoL) in anhydrous tetrahydrofuran was added dropwise to the reaction flask, the reaction was continued at this temperature for half an hour, and then, the temperature was raised to room temperature, and the reaction was continued for 8 hours. The solvent was removed under reduced pressure, hydrochloric acid and acetic acid were added, and the mixture was refluxed for about 2 hours. Cooled to room temperature, deionized water was added, and extraction was performed with ethyl acetate. After concentration, the mixture was separated by a silica gel column, and the solvent was removed to obtain 5.43g of Z37 in a yield of 72%.
Compound Z37 (5.02 g,8 mmol) and Z29 (3.5 g,16 mmol) were dissolved in anhydrous toluene, sodium t-butoxide (0.92 g,9.6 mmol) and dibenzylideneacetone dipalladium (0.22 g,0.24 mmol) were added, nitrogen was replaced three times, and then tri-t-butylphosphine (0.24 mmol) was added, and the temperature was gradually raised to 80℃and the reaction was stirred for 12 hours, followed by removal of the heat source. After the system was cooled, deionized water was added, the organic layer was separated, extracted three times with ethyl acetate, concentrated under reduced pressure, and passed through a silica gel column to give 4.5G of product G245, yield 62%; MS 906[ M + ].
Example 16: synthesis of Compound G248
Z1 (11.58 g,30 mmol) was dissolved in anhydrous tetrahydrofuran, cooled to-78℃and butyllithium (1.6M, 18.7 mL) was slowly added. After about 0.5 hours, a solution of cyclopentanone (2.52 g,30 mmoL) in anhydrous tetrahydrofuran was added dropwise to the flask, the reaction was continued at this temperature for half an hour, and then it was warmed to room temperature and continued for 8 hours. The solvent was removed under reduced pressure, hydrochloric acid and acetic acid were added, and the mixture was refluxed for about 2 hours. Cooled to room temperature, deionized water was added, and extraction was performed with ethyl acetate. After concentration, the mixture was separated by a silica gel column, and the solvent was removed to obtain 8.41g of Z38 in total, and the yield was 75%.
Z38 (7.48 g,20 mmol) was dissolved in anhydrous tetrahydrofuran, cooled to-78℃and butyllithium (1.6M, 8.7 mL) was slowly added. After about 0.5 hours, a solution of 4-bromofluorenone (5.18 g,20 mmoL) in anhydrous tetrahydrofuran was added dropwise to the reaction flask, the reaction was continued at this temperature for half an hour, and then, the temperature was raised to room temperature, and the reaction was continued for 8 hours. The solvent was removed under reduced pressure, hydrochloric acid and acetic acid were added, and the mixture was refluxed for about 2 hours. Cooled to room temperature, deionized water was added, and extraction was performed with ethyl acetate. After concentration, the mixture was separated by a silica gel column, and the solvent was removed to obtain a total of 7.72g of Z39, and the yield was 72%.
Compounds Z39 (6.43 g,12 mmol) and Z12 (3.42 g,12 mmol) were dissolved in anhydrous toluene, sodium tert-butoxide (1.34 g,14 mmol) and dibenzylideneacetone dipalladium (0.33 g,0.36 mmol) were added, nitrogen was replaced three times, and then tri-tert-butylphosphine (0.36 mmol) was added, and the temperature was gradually raised to 80℃and the reaction was stirred for 12 hours, followed by removal of the heat source. After the system was cooled, deionized water was added, the organic layer was separated, extracted three times with ethyl acetate, concentrated under reduced pressure, and passed through a silica gel column to give 5.33G of product G248 in 60% yield; MS 741[ M + ].
Example 17: synthesis of Compound G249
Z1 (11.58 g,30 mmol) was dissolved in anhydrous tetrahydrofuran, cooled to-78℃and butyllithium (1.6M, 18.7 mL) was slowly added. After about 0.5 hours, a solution of bicyclo [2.2.2] octan-2-one (3.72 g,30 mmoL) in anhydrous tetrahydrofuran was added dropwise to the flask, and the reaction was continued at this temperature for half an hour, then warmed to room temperature, and continued for 8 hours. The solvent was removed under reduced pressure, hydrochloric acid and acetic acid were added, and the mixture was refluxed for about 2 hours. Cooled to room temperature, deionized water was added, and extraction was performed with ethyl acetate. After concentration, the mixture was separated by a silica gel column, and the solvent was removed to obtain 8.82g of Z40 in 71% yield.
Z40 (8.28 g,20 mmol) was dissolved in anhydrous tetrahydrofuran, cooled to-78℃and butyllithium (1.6M, 8.7 mL) was slowly added. After about 0.5 hours, a solution of 4-bromofluorenone (5.18 g,20 mmoL) in anhydrous tetrahydrofuran was added dropwise to the reaction flask, the reaction was continued at this temperature for half an hour, and then, the temperature was raised to room temperature, and the reaction was continued for 8 hours. The solvent was removed under reduced pressure, hydrochloric acid and acetic acid were added, and the mixture was refluxed for about 2 hours. Cooled to room temperature, deionized water was added, and extraction was performed with ethyl acetate. After concentration, the mixture was separated by a silica gel column, and the solvent was removed to obtain a total of 7.6g of Z41, and the yield was 66%.
Compound Z41 (5.76 g,10 mmol) and Z22 (2.45 g,10 mmol) were dissolved in anhydrous toluene, sodium t-butoxide (1.15 g,12 mmol) and dibenzylideneacetone dipalladium (0.27 g,0.3 mmol) were added, nitrogen was replaced three times, and then tri-t-butylphosphine (0.3 mmol) was added, and the temperature was gradually raised to 80℃and the reaction was stirred for 12 hours, followed by removal of the heat source. After the system was cooled, deionized water was added, the organic layer was separated, extracted three times with ethyl acetate, concentrated under reduced pressure, and passed through a silica gel column to give 4.6G of product G249 in 62% yield; MS 741[ M + ].
2. Preparation and characterization of OLED devices
The following describes in detail the preparation process of the OLED device using the above-described method by means of specific examples.
The structure of the compound involved in the device is as follows:
device example 1 the preparation steps are as follows:
The ITO conductive glass anode layer was cleaned, then ultrasonically cleaned with deionized water, acetone, isopropanol for 15 minutes, and then treated in a plasma cleaner for 5 minutes to increase the work function of the electrode. Evaporating cavity injection layer material HATCN with thickness of 5nm by vacuum evaporation on ITO anode layer On the hole injection layer, a hole transport material H1 was deposited by vacuum deposition to a thickness of 80nm. The electron blocking layer G11 was 20nm thick over the hole transport layer. And (3) evaporating a light-emitting layer on the electron blocking layer, wherein GH1 is used as a main material, GD1 is used as a doping material, the mass ratio of GD1 to GH1 is 1:9, and the thickness is 30nm. On the light-emitting layer, electron transport materials ET1 and LiQ were vapor-deposited by vacuum vapor deposition in a ratio of 5:5, thickness is 30nm. And on the electron transport layer, an electron injection layer LiQ is evaporated in vacuum, and the thickness is 2nm. And vacuum evaporating a cathode Al layer with the thickness of 80nm on the electron injection layer.
Device examples 2 to 18 and device comparative examples 1 to 2 were prepared in substantially the same manner as device example 1, except that:
Device example 2: the electron blocking layer of the organic electroluminescent device becomes G16.
Device example 3: the electron blocking layer of the organic electroluminescent device becomes G23.
Device example 4: the electron blocking layer of the organic electroluminescent device becomes G37.
Device example 5: the electron blocking layer of the organic electroluminescent device becomes G27.
Device example 6: the electron blocking layer of the organic electroluminescent device becomes G59.
Device example 7: the electron blocking layer of the organic electroluminescent device becomes G61.
Device example 8: the electron blocking layer of the organic electroluminescent device becomes G116.
Device example 9: the electron blocking layer of the organic electroluminescent device becomes G173.
Device example 10: the electron blocking layer of the organic electroluminescent device becomes G186.
Device example 11: the electron blocking layer of the organic electroluminescent device becomes G113.
Device example 12: the electron blocking layer of the organic electroluminescent device becomes G216.
Device example 13: the electron blocking layer of the organic electroluminescent device becomes G229.
Device example 14: the electron blocking layer of the organic electroluminescent device becomes G223.
Device example 15: the electron blocking layer of the organic electroluminescent device becomes G245.
Device example 16: the electron blocking layer of the organic electroluminescent device becomes G248.
Device example 17: the electron blocking layer of the organic electroluminescent device becomes G249.
Device comparative example 1: the electron blocking layer of the organic electroluminescent device becomes C1.
Device comparative example 2: the electron blocking layer of the organic electroluminescent device becomes C2.
The luminous efficiency was obtained at a current density of 10mA/cm 2, the LT95 was obtained at a current density of 40mA/cm 2, and the test results are shown in Table 1.
TABLE 1 characterization results of devices
It can be seen that the use of the aromatic amine compound of the present invention as an electron blocking material in device examples 1 to 17 can effectively improve the luminous efficiency and the lifetime of an organic electroluminescent device as compared with device comparative examples 1 to 2. This is mainly because the non-aromatic rings in examples 17 are large in volume, and the interactions between the molecular groups can be effectively reduced. In addition, the degree of freedom of the cycloalkyl is small, the vibration in the molecule is small, the stability of the molecule is high, and the stability of carrier transmission is improved.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
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 (9)

1. An arylamine organic compound is characterized in that the structure is formed by combining a chemical formula (1) and a chemical formula (2):
Wherein:
* Represents a condensed site of chemical formula (1) and chemical formula (2);
n1 and n2 are independently selected from 0 or 1, and n1+n2 is 1 or more;
l 1 and L 2 are each independently selected from the group consisting of a single bond,
Ar 1-Ar4 is independently selected from any one of the groups shown in (B-1) to (B-7):
Wherein:
X is independently selected from CR 1 for each occurrence;
y is selected from O, S, or CR 3R4;
Ar 5 is selected from phenyl;
R 1 is independently selected from the group consisting of-H, -D, -F, -Cl, -I, straight-chain alkyl having 1 to 8C atoms, branched or cyclic alkyl having 3 to 8C atoms, aromatic groups having 5 to 20 ring atoms for each occurrence;
R 3-R4 is independently selected at each occurrence from-H, -D, a straight chain alkyl group having 1 to 10C atoms, a branched or cyclic alkyl group having 3 to 10C atoms, a substituted or unsubstituted aryl group having 5 to 20 ring atoms, or a substituted or unsubstituted heteroaryl group having 5 to 20 ring atoms; r 3 and R 4 are mutually cyclic or acyclic;
Ring a is selected from any one of the following groups:
2. The aromatic amine-based organic compound according to claim 1, which has a structure represented by any one of formulas (3-1) to (3-5):
3. The aromatic amine-based organic compound according to claim 1, wherein Ar 1-Ar4 is independently selected from any one of the groups (C-1) to (C-5):
Wherein: * Represents a ligation site; m1, m2, m3, m4 and m5 are each independently selected from 0,1, 2,3 or 4.
4. An arylamine organic compound according to claim 3, wherein at least one of said Ar 1-Ar2 is selected from (C-2), and/or at least one of said Ar 3-Ar4 is selected from (C-2).
5. The aromatic amine-type organic compound according to any one of claim 1 to 4,Selected from the group consisting of
6. A mixture comprising an arylamine-based organic compound according to any one of claims 1 to 5, and at least one organic functional material that is a hole injection material, a hole transport material, an electron injection material, an electron blocking material, a hole blocking material, a light emitting material, a host material, or an organic dye.
7. A composition comprising an arylamine organic compound according to any one of claims 1-5 or a mixture according to claim 6, and at least one organic solvent.
8. An organic electronic device comprising a first electrode, a second electrode, one or more organic functional layers between the first electrode and the second electrode, wherein the organic functional layers comprise an arylamine organic compound according to any one of claims 1-5, or a mixture according to claim 6, or are prepared from a composition according to claim 7.
9. The organic electronic device according to claim 8, wherein the organic functional layer comprises at least one hole transporting layer or electron blocking layer comprising the arylamine organic compound according to any one of claims 1-5, or the mixture according to claim 6, or the composition according to claim 7.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104024373A (en) * 2011-12-30 2014-09-03 第一毛织株式会社 Compound For Organic Optoelectric Device, Organic Light-Emitting Diode Including Same, And Display Device Including Organic Light-Emitting Diode
WO2019120099A1 (en) * 2017-12-21 2019-06-27 广州华睿光电材料有限公司 Organic mixture and use thereof in organic electronic device
CN110964021A (en) * 2018-09-30 2020-04-07 江苏三月光电科技有限公司 Compound with fluorene as core, preparation method and application thereof
CN111454161A (en) * 2020-03-23 2020-07-28 陕西莱特光电材料股份有限公司 Spiro compound, application thereof, organic electroluminescent device using spiro compound and electronic device using spiro compound

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104024373A (en) * 2011-12-30 2014-09-03 第一毛织株式会社 Compound For Organic Optoelectric Device, Organic Light-Emitting Diode Including Same, And Display Device Including Organic Light-Emitting Diode
WO2019120099A1 (en) * 2017-12-21 2019-06-27 广州华睿光电材料有限公司 Organic mixture and use thereof in organic electronic device
CN110964021A (en) * 2018-09-30 2020-04-07 江苏三月光电科技有限公司 Compound with fluorene as core, preparation method and application thereof
CN111454161A (en) * 2020-03-23 2020-07-28 陕西莱特光电材料股份有限公司 Spiro compound, application thereof, organic electroluminescent device using spiro compound and electronic device using spiro compound

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