CN112876382B - Organic compounds, mixtures, compositions and uses thereof - Google Patents

Organic compounds, mixtures, compositions and uses thereof Download PDF

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CN112876382B
CN112876382B CN202011095656.8A CN202011095656A CN112876382B CN 112876382 B CN112876382 B CN 112876382B CN 202011095656 A CN202011095656 A CN 202011095656A CN 112876382 B CN112876382 B CN 112876382B
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organic
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atoms
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CN112876382A (en
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谭甲辉
宋鑫龙
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Guangzhou Chinaray Optoelectronic Materials Ltd
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Abstract

The present application relates to organic compounds, mixtures, compositions and their use, in particular in organic light emitting diodes. The organic compound according to the present application, as shown in the general formula (1), has excellent hole transport property and stability, and can be used as a hole injection layer material in an organic electroluminescent element, and also can be used as a dopantThe impurity agent is doped in the hole injection layer or the hole transport layer, so that the low-voltage driving can be used, the electroluminescent efficiency can be improved, and the service life of the device can be prolonged.

Description

Organic compounds, mixtures, compositions and uses thereof
The present application claims priority from chinese patent office, application No. 201911202496.X, chinese patent application entitled "a pyrene quinone organic compound and its use", filed on 11/29/2019, the entire contents of which are incorporated herein by reference.
Technical Field
The application relates to the technical field of organic electroluminescence, in particular to an organic compound, a mixture, a composition and application thereof.
Background
Organic Light Emitting Diodes (OLEDs) have great potential for applications in optoelectronic devices such as flat panel displays and lighting due to their variety, low manufacturing cost, and good optical and electrical properties.
The organic light emitting diode consists of a positive electrode, a negative electrode and an organic layer in between. In order to improve the efficiency and lifetime of the organic light emitting diode, the organic layer generally has a multi-layer structure, and each layer contains different organic substances. 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. The basic principle of the organic light emitting diode is that: when a voltage is applied between the two electrodes, the positive electrode injects holes into the organic layer, the negative electrode injects electrons into the organic layer, and when the injected holes meet the electrons, excitons are formed, and light is emitted when the excitons transition back to the ground state. The organic light emitting diode has the advantages of self-luminescence, high brightness, high efficiency, low driving voltage, wide viewing angle, high contrast, high responsiveness and the like. In order to increase the recombination efficiency of injected holes and electrons, further improvements in the structure, materials, and the like of the organic light emitting diode are required.
At present, merck company uses aromatic diamine derivative or aromatic condensed ring diamine derivative as hole transport material of organic light emitting diode to raise hole injection efficiency, but at this time, the use voltage needs to be raised to make the organic light emitting diode fully emit light, which results in the problems of reduced service life and increased power consumption of the organic light emitting diode.
Recently, organic light emitting diodes have been doped with hole acceptors to solve such problems, such as Tetracyanoquinodimethane (TCNQ) or 2,3,5, 6-tetrafluoro-tetracyano-1, 4-benzoquinone dimethane (F4 TCNQ) (Chemical Science 2018,9 (19), 4468-4476; appl. Phys. Lett.,2018,112 (8), 083303/1-083303/2;Chemistry of Materials 2018,30 (3), 998-1010), however, these compounds have many drawbacks when used to dope organic layers, such as: the organic light emitting diode is unstable in operation in a manufacturing process of the organic light emitting diode, is not stable enough in driving the organic light emitting diode, has a reduced life, or is diffused in the device to contaminate the device in manufacturing the organic light emitting diode by vacuum evaporation.
Therefore, there is a need for further improvements in the electron acceptor doped in the hole transport layer, i.e., the P-dopant type dopant, particularly, the dopant that can achieve low voltage and long lifetime of the organic light emitting diode.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention provides an organic compound, a mixture, a composition and applications thereof, which aims to provide a novel class of organic photoelectric functional materials to improve the efficiency and the lifetime of devices.
The technical scheme of the invention is as follows:
an organic compound represented by the general formula (1):
wherein:
x is independently selected from CR at each occurrence 1 Or N;
y is independently selected from CR at each occurrence 2 R 3 、NR 2 、SiR 2 R 3 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 substituted or unsubstituted non-aromatic ring system group having 3 to 30 ring atoms;
R 1 independently at each occurrence, selected from H, D, or a linear alkyl group having 1 to 20C atoms, or a linear alkoxy group having 1 to 20C atoms, or a linear thioalkoxy group having 1 to 20C atoms, or a branched or cyclic alkyl group having 3 to 20C atoms, or a branched or cyclic alkoxy group having 3 to 20C atoms, or a branched or cyclic thioalkoxy group having 3 to 20C atoms, or a silyl group, or a ketone group having 1 to 20C atoms, or an alkoxycarbonyl group having 2 to 20C atoms, or an aryloxycarbonyl group having 7 to 20C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate or isothiocyanate groups, hydroxyl, nitro, CF 3 Cl, br, F, I, a crosslinkable group, or a substituted or unsubstituted aromatic group having 5 to 60 ring atoms or a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 60 ring atoms, or a combination of these systems;
R 2 -R 3 Independently at each occurrence selected from nitro, nitroso, CF 3 Cl, br, F, I, cyano, alkoxy, or keto having 1 to 20C atoms, or alkoxycarbonyl having 2 to 20C atoms, or aryloxycarbonyl having 7 to 20C atoms, carbamoyl, haloformyl, formyl, isocyano, thiocyanate or isothiocyanate, hydroxy, or a substituted or unsubstituted aromatic group having 5 to 60 ring atomsA heteroaromatic group, or an aryloxy or heteroaryloxy group having 5 to 60 ring atoms, or a combination of these systems.
The invention further relates to a mixture comprising one of the above-mentioned organic compounds and at least one organic functional material selected from hole-injecting materials, hole-transporting materials, electron-injecting materials, electron-blocking materials, hole-blocking materials, luminophores, host materials or organic dyes.
The invention further relates to a composition comprising an organic compound or mixture as described above, and at least one organic solvent.
The invention further relates to an organic electronic device comprising at least one functional layer comprising the above-mentioned organic compound or mixture or prepared from the above-mentioned composition.
Compared with the prior art, the invention has the following beneficial effects:
the organic compound has a pyrene quinone structure, has excellent hole transport property and stability, can be used as a hole injection layer material in an organic electroluminescent element, and can be used as a doping agent doped in the hole injection layer or the hole transport layer, so that the organic compound can be driven by low voltage, the electroluminescent efficiency can be improved, and the service life of the device can be prolonged.
Drawings
Fig. 1 is a structural diagram of a light emitting device of the present invention, in which 101 is a substrate, 102 is an anode, 103 is a Hole Injection Layer (HIL), 104 is a Hole Transport Layer (HTL), 105 is a light emitting layer, 106 is an Electron Injection Layer (EIL) or an Electron Transport Layer (ETL), and 107 is a cathode.
Detailed Description
In order that the invention may be understood, a more complete description of the invention will be rendered by reference to the appended drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth 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 compounds of the invention, when any variable (e.g., R 1 、R 2 Etc.) occur more than once in any component, the definition of each occurrence is independent of the definition of each other occurrence. Also, combinations of substituents and variables are permissible provided that such combinations stabilize the compounds.
In the present invention, the Host material, the Matrix material, the Host material, and the Matrix material have the same meaning and are interchangeable.
In the present invention, the composition, printing ink, and ink have the same meaning and are interchangeable.
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. Containing a plurality of R as shown in the general formula 1 R is then 1 May 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 (C) 1-30 Alkyl, heterocyclyl having 3 to 20 ring atoms, aryl having 5 to 20 ring atoms, heteroaryl having 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 substituents acceptable in the art; it can be understood thatR 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 having 3 to 8 ring atoms, heterocyclyl having 3 to 8 ring atoms, aryl having 5 to 20 ring atoms or heteroaryl having 5 to 10 ring atoms; the C is 1-6 Alkyl, cycloalkyl having 3 to 8 ring atoms, heterocyclyl having 3 to 8 ring atoms, aryl having 5 to 20 ring atoms, or heteroaryl having 5 to 10 ring atoms is optionally further substituted with one or more of the following groups: c (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. Phrases containing this term, e.g., "C 1-9 Alkyl "means an alkyl group containing 1 to 9 carbon atoms, and each occurrence may be, independently of the other, C 1 Alkyl, C 2 Alkyl, C 3 Alkyl, C 4 Alkyl, C 5 Alkyl, C 6 Alkyl, C 7 Alkyl, C 8 Alkyl or C 9 An alkyl group. Non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl, 4-methylcyclohexyl, 4-tert-butylcyclohexyl, n-heptyl, 1-methylheptyl, 2-dimethylheptyl, 2-ethylheptyl, 2-butylheptyl, n-octyl, tert-octyl, 2-ethyloctyl, 2-butyloctyl, 2-hexyloctyl, 3, 7-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-eicosyl, n-heneicocosyl, n-di-eicosyl, n-triceicosyl, n-hexyleicosyl, n-eicosyl, n-triceicosyl, n-eicosyl, n-heptacosyl, n-nonacosyl, n-eicosyl, n-tetraeicosyl, and the like.
An aromatic group refers to a hydrocarbon group containing at least one aromatic ring. Heteroaromatic groups refer to aromatic hydrocarbon groups 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.
In the embodiment of the invention, the energy level structure, triplet state energy level E of the organic material T HOMO, LUMO play a key role. The determination of these energy levels is described below.
HOMO and LUMO energy levels can be measured by photoelectric effects such as XPS (X-ray photoelectron spectroscopy) and UPS (ultraviolet electron spectroscopy) or by cyclic voltammetry (hereinafter referred to as CV). Recently, quantum chemical methods, such as density functional theory (hereinafter abbreviated as DFT), have also become effective methods for calculating molecular orbital energy levels.
Triplet energy level E of organic material T1 Can be measured by low temperature Time resolved luminescence spectroscopy, or by quantum analog calculations (e.g. by Time-dependent DFT), such as by commercial software Gaussian 03W (Gaussian inc.), specific analog methods can be seen in WO2011141110 or as described in the examples below.
Note that HOMO, LUMO, E T1 Depending on the measurement or calculation method used, even for the same method, different evaluation methods, e.g. starting points and peak points on the CV curve, may give different HOMsO/LUMO value. Thus, a reasonable and meaningful comparison should be made with the same measurement method and the same evaluation method. In the description of the embodiments of the present invention, HOMO, LUMO, E T1 The values of (2) are based on a simulation of the Time-dependent DFT, but do not affect the application of other measurement or calculation methods.
In the invention, (HOMO-1) is defined as the second highest occupied orbital level, (HOMO-2) is the third highest occupied orbital level, and so on. (lumo+1) is defined as the second lowest unoccupied orbital level, (lumo+2) is the third lowest occupied orbital level, and so on.
An organic compound represented by the general formula (I):
wherein:
X is independently selected from CR at each occurrence 1 Or N;
y is independently selected from CR at each occurrence 2 R 3 、NR 2 、SiR 2 R 3 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 substituted or unsubstituted non-aromatic ring system group having 3 to 30 ring atoms;
R 1 independently at each occurrence, selected from H, D, or a linear alkyl group having 1 to 20C atoms, or a linear alkoxy group having 1 to 20C atoms, or a linear thioalkoxy group having 1 to 20C atoms, or a branched or cyclic alkyl group having 3 to 20C atoms, or a branched or cyclic alkoxy group having 3 to 20C atoms, or a branched or cyclic thioalkoxy group having 3 to 20C atoms, or a silyl group, or a ketone group having 1 to 20C atoms, or an alkoxycarbonyl group having 2 to 20C atoms, or an aryloxycarbonyl group having 7 to 20C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate or isothiocyanate groups, hydroxyl, nitro, CF 3 Cl, br, F, I, crosslinkable groups, or having 5 toA substituted or unsubstituted aromatic group of 60 ring atoms or a substituted or unsubstituted heteroaromatic group of 5 to 60 ring atoms, or an aryloxy or heteroaryloxy group of 5 to 60 ring atoms, or a combination of these systems;
R 2 -R 3 Independently at each occurrence selected from nitro, nitroso, CF 3 Cl, br, F, I, cyano, alkoxy, or a ketone group having 1 to 20C atoms, or an alkoxycarbonyl group having 2 to 20C atoms, or an aryloxycarbonyl group having 7 to 20C atoms, carbamoyl, haloformyl, formyl, isocyano, isocyanato, thiocyanate or isothiocyanate groups, hydroxy, or a substituted or unsubstituted aromatic group having 5 to 60 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 60 ring atoms, or a combination of these systems.
In one embodiment, Y is selected from CR 2 R 3 、NR 2 Or a substituted or unsubstituted aromatic group containing 6 to 60C atoms or a heteroaromatic group containing 5 to 60 ring atoms, or a non-aromatic ring system group containing 3 to 30 ring atoms.
In one embodiment, at least one Y is selected from CR 2 R 3 The method comprises the steps of carrying out a first treatment on the surface of the In one embodiment, at least two Y's are selected from CR 2 R 3 The method comprises the steps of carrying out a first treatment on the surface of the In one embodiment, at least three Y's are selected from CR 2 R 3 The method comprises the steps of carrying out a first treatment on the surface of the In one embodiment, Y is selected from CR 2 R 3 。
In one embodiment, at least one Y is selected from NR 2 The method comprises the steps of carrying out a first treatment on the surface of the In one embodiment, at least two Y's are selected from NR 2 The method comprises the steps of carrying out a first treatment on the surface of the In one embodiment, at least three Y's are selected from NR 2 The method comprises the steps of carrying out a first treatment on the surface of the In one embodiment, Y is each selected from NR 2 。
In one embodiment, at least two Y's are selected from the same group.
In one embodiment, Y is selected from the same groups at each occurrence.
In one embodiment, R 2 -R 3 Independently at each occurrence selected from nitro, nitroso, CF 3 Cl, br, F, I, cyanoA group, or an alkoxycarbonyl group having 2 to 20C atoms, or a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 30 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 30 ring atoms, or a combination of these systems.
In one embodiment, R 2 -R 3 Independently at each occurrence selected from nitro, nitroso, CF 3 Cl, br, F, I, cyano, or by nitro, nitroso, CF 3 Cl, br, F, I or cyano-substituted aromatic or heteroaromatic groups having 5 to 60 ring atoms.
In one embodiment, R 2 -R 3 At least one of them is selected from nitro, nitroso, CF 3 Cl, br, F, I, cyano-substituted aromatic or heteroaromatic groups having 5 to 60 ring atoms.
In one embodiment, R 2 -R 3 Wherein each is selected from nitro, nitroso, CF 3 Cl, br, F, I, cyano-substituted aromatic or heteroaromatic groups having 5 to 60 ring atoms.
In one embodiment, Y is selected from CR 2 R 3 The method comprises the steps of carrying out a first treatment on the surface of the Preferably, Y is selected from the following groups:
in one embodiment, Y is selected from NR 2 The method comprises the steps of carrying out a first treatment on the surface of the Preferably, Y is selected from:
in one embodiment, Y is selected from a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 20 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 20 ring atoms; preferably, Y is selected from the following groups:
in one embodiment, X is selected from CR 1 ；
In one embodiment, R 1 Selected from H, D, cyano, isocyano, nitro, CF 3 Cl, br, F, I, or a substituted or unsubstituted aromatic group having 5 to 60 ring atoms or a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, or a combination of these systems;
in one embodiment, R 1 Selected from H.
In one embodiment, at least one R 1 Selected from cyano, isocyano, nitro, CF 3 Cl, br, F, I, or a substituted or unsubstituted aromatic group having 5 to 60 ring atoms or a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, or a combination of these systems.
In one embodiment, at least one R 1 Selected from substituted or unsubstituted aromatic or heteroaromatic groups having 5 to 30 ring atoms; preferably, at least one R 1 Selected from nitro, nitroso and CF 3 Cl, br, F, I or cyano-substituted aromatic or heteroaromatic groups; more preferably, at least one R 1 Selected from substituted or unsubstituted benzene; more preferably, at least one R 1 Selected from nitro, nitroso and CF 3 Cl, br, F, I or cyano-substituted benzene.
Preferably, at least two R 1 Selected from substituted or unsubstituted aromatic or heteroaromatic groups having 5 to 30 ring atoms; preferably, at least two R 1 Selected from nitro, nitroso and CF 3 Cl, br, F, I or cyano-substituted aromatic or heteroaromatic groups; more preferably, at least two R 1 Selected from substituted or unsubstituted benzene; more preferably, at least two R 1 Selected from nitro, nitroso and CF 3 Cl, br, F, I or cyano-substituted benzene.
In one embodiment, formula (1) is selected from any one of formulas (2-1) - (2-3):
wherein:
R 4 independently at each occurrence, selected from H, D, or a linear alkyl group having 1 to 20C atoms, or a linear alkoxy group having 1 to 20C atoms, or a linear thioalkoxy group having 1 to 20C atoms, or a branched or cyclic alkyl group having 3 to 20C atoms, or a branched or cyclic alkoxy group having 3 to 20C atoms, or a branched or cyclic thioalkoxy group having 3 to 20C atoms, or a silyl group, or a ketone group having 1 to 20C atoms, or an alkoxycarbonyl group having 2 to 20C atoms, or an aryloxycarbonyl group having 7 to 20C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate or isothiocyanate groups, hydroxyl, nitro, CF 3 Cl, br, F, I, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 60 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 60 ring atoms, or a combination of these systems.
Preferably, R 4 Independently at each occurrence selected from H, nitro, nitroso, CF 3 Cl, br, F, I, cyano, or by nitro, nitroso, CF 3 Cl, br, F, I, cyano-substituted aromatic or heteroaromatic groups having 5 to 60 ring atoms; more preferably, R 4 Independently at each occurrence, selected from nitro, nitroso, CF 3 F, I or cyano.
In some of these embodiments, R 1 Independently at each occurrence selected from H, nitro, nitroso, CF 3 Cl, br, F, I, cyano, or by nitro, nitroso, CF 3 Cl, br, F, I or cyano-substituted aromatic or heteroaromatic groups having 5 to 60 ring atoms.
In one embodiment, formula (1) is selected from formula (2-1);
in one embodiment, R in formula (2-1) 1 Are all selected from H;
in one embodiment, at least one R in formula (2-1) 1 Selected from nitro, nitroso, CF 3 ，Cl，Br, F, I, cyano, or by nitro, nitroso, CF 3 Cl, br, F, I or cyano-substituted aromatic or heteroaromatic groups having 5 to 60 ring atoms.
In one embodiment, R in formula (2-1) 1 Are all selected from nitro, nitroso, CF 3 Cl, br, F, I, cyano, or by nitro, nitroso, CF 3 Cl, br, F, I or cyano-substituted aromatic or heteroaromatic groups having 5 to 60 ring atoms.
In one embodiment, formula (1) is selected from formula (2-2);
in one embodiment, R in formula (2-2) 1 Are all selected from H;
in one embodiment, at least one R in formula (2-2) 1 Selected from nitro, nitroso, CF 3 Cl, br, F, I, cyano, or by nitro, nitroso, CF 3 Cl, br, F, I or cyano-substituted aromatic or heteroaromatic groups having 5 to 60 ring atoms.
In one embodiment, R in formula (2-2) 1 Are all selected from nitro, nitroso, CF 3 Cl, br, F, I, cyano, or by nitro, nitroso, CF 3 Cl, br, F, I or cyano-substituted aromatic or heteroaromatic groups having 5 to 60 ring atoms.
In one embodiment, formula (1) is selected from formulas (2-3);
in one embodiment, R in formula (2-3) 1 Are all selected from H;
in one embodiment, at least one R in formula (2-3) 1 Selected from nitro, nitroso, CF 3 Cl, br, F, I, cyano, or by nitro, nitroso, CF 3 Cl, br, F, I or cyano-substituted aromatic or heteroaromatic groups having 5 to 60 ring atoms.
In one embodiment, R in formula (2-3) 1 Are all selected from nitro, nitroso, CF 3 Cl, br, F, I, cyano, or by nitro, nitroso, CF 3 Cl, br, F, I or cyano-substituted aromatic or heteroaromatic groups having 5 to 60 ring atoms.
In one embodiment, at least one R in formula (2-3) 4 Selected from nitro, nitroso, CF 3 Cl, br, F, I, cyano, or by nitro, nitroso, CF 3 Cl, br, F, I or cyano-substituted aromatic or heteroaromatic groups having 5 to 60 ring atoms.
In one embodiment, R in formula (2-3) 4 Are all selected from nitro, nitroso, CF 3 Cl, br, F, I, cyano, or by nitro, nitroso, CF 3 Cl, br, F, I or cyano-substituted aromatic or heteroaromatic groups having 5 to 60 ring atoms.
In one embodiment, Y in formulas (2-1) - (2-3) is selected from CR 2 R 3 Or NR (NR) 2 。R 2 And R is 3 The definitions are as described above.
In one embodiment, the organic compound according to the present invention is selected from the following structures, but is not limited thereto:
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The invention also relates to the organic compound as an organic ferromagnetic material, wherein the ferromagnetic organic compound is an organic material with ferromagnetism, namely an organic ferromagnetic material, the traditional ferromagnetic material is an inorganic material such as an alloy, an oxide and the like containing iron group or rare earth group metal elements, the ferromagnetic material is derived from atomic magnetic moment and consists of two parts of electron orbit magnetic moment and electron spin magnetic moment, the inorganic magnetic material has the defects of high density, difficult processing and forming and the like, and in the quinone organic compound, the free radical anion salt or the dianion salt has low LUMO energy level, stable ground state and stable unsatisfied electron layer, can provide a stable magnetic moment source, and therefore, the ferromagnetic material shows magnetism, and can be applied to the ferromagnetic material (concretely, the ferromagnetic material can be referred to as Angew.chem.int.ed.Ed.Engl.1994, 33.385-415).
The organic compound according to the invention can be used as a functional material in a functional layer of an electronic device. Organic functional layers include, but are not limited to, hole Injection Layers (HIL), hole Transport Layers (HTL), electron Transport Layers (ETL), electron Injection Layers (EIL), electron Blocking Layers (EBL), hole Blocking Layers (HBL), light emitting layers (EML).
In a particularly preferred embodiment, the organic compound according to the invention is used in a Hole Injection Layer (HIL) or a Hole Transport Layer (HTL).
In a very preferred embodiment, the organic compound according to the invention is used as p-type doping material in a Hole Injection Layer (HIL) or a Hole Transport Layer (HTL).
In certain embodiments, the organic compounds according to the invention, T 1 Not less than 0.3eV, preferably not less than 0.6eV, and most preferably not less than 0.8eV. T (T) 1 Representing the triplet energy level of the compound.
Functional materials require good thermal stability. Generally, the organic compounds according to the present invention have a glass transition temperature Tg of 100 ℃, in a preferred embodiment Tg of 120 ℃, in a more preferred embodiment Tg of 140 ℃, in a more preferred embodiment Tg of 160 ℃, and in a most preferred embodiment Tg of 180 ℃.
An appropriate LUMO level is necessary as a p-type dopant material. In certain embodiments, the organic compounds according to the invention have a LUMO of 5.30eV or less, more preferably 5.50eV or less, most preferably 5.60eV or less. LUMO represents the lowest unoccupied orbital level of a compound.
In certain preferred embodiments, the organic compound according to the invention has a HOMO- (HOMO-1))of0.2 eV or more, preferably 0.25eV or more, more preferably 0.3eV or more, more preferably 0.35eV or more, even more preferably 0.4eV or more, and most preferably 0.45eV or more. HOMO represents the highest occupied orbital level of a compound.
The present invention also provides a polymer comprising at least one repeating unit comprising the structure of an organic compound as any one of the above.
When the repeating unit is as in any of the structures of the organic compounds described above, the site of attachment of the organic compound to other structures in the repeating unit may be any attachable position in the organic compound.
The polymer has the functional characteristics of any one of the organic compounds.
The invention also provides a mixture, which is characterized by comprising at least one organic compound or polymer and at least one organic functional material, wherein the at least one 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), 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 WO2011110277A1, the entire contents of which 3 patent documents are hereby incorporated by reference.
In some preferred embodiments, the mixture wherein the organic functional material is selected from the group consisting of a Hole Injection Material (HIM), a Hole Transport Material (HTM), and a Host material (Host).
In certain preferred embodiments, the mixture wherein the LUMO of the organic compound is equal to or lower than the homo+0.2eV of the other organic functional material.
In certain preferred embodiments, the mixture wherein the organic compound has a LUMO equal to or lower than the homo+0.1ev of the other organic functional material.
In certain particularly preferred embodiments, the mixture wherein the organic compound has a LUMO equal to or lower than the HOMO of another organic functional material.
In one embodiment, the mixture comprises at least one Hole Injection Material (HIM) or hole transport material and one dopant selected from the above organic compounds, the molar ratio of dopant to host being from 1:1 to 1:100000.
Wherein a detailed description of HIM/HTM/EBM, and Host (Host material/matrix material) is given in patent WO2018095395A1.
It is another object of the invention to provide a material solution for printed OLEDs.
In certain embodiments, the organic compounds according to the invention have a molecular weight of 800g/mol or more, preferably 900g/mol or more, very preferably 1000g/mol or more, more preferably 1100g/mol or more, most preferably 1200g/mol or more.
In other embodiments, the organic compound according to the invention has a solubility in toluene of not less than 2mg/ml, preferably not less than 3mg/ml, more preferably not less than 4mg/ml, most preferably not less than 5mg/ml at 25 ℃.
The invention also relates to a composition comprising at least one organic compound or polymer or mixture as described above, and at least one organic solvent; the at least one organic solvent is selected from aromatic or heteroaromatic, ester, aromatic ketone or aromatic ether, aliphatic ketone or aliphatic ether, alicyclic or olefinic compound, borate or phosphate compound, or mixture of two or more solvents.
In a preferred embodiment, a composition according to the invention is characterized in that the at least one organic solvent is chosen from aromatic or heteroaromatic based solvents.
Examples of aromatic or heteroaromatic-based solvents suitable for the present invention are, but 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 invention is characterized by comprising at least one organic compound or polymer or mixture as described above and at least one organic solvent, and may further comprise another organic solvent. Examples of other organic solvents include (but are not limited to): methanol, ethanol, 2-methoxyethanol, methylene chloride, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1, 4-dioxane, acetone, methyl ethyl ketone, 1,2 dichloroethane, 3-phenoxytoluene, 1-trichloroethane, 1, 2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethylsulfoxide, tetrahydronaphthalene, decalin, indene and/or mixtures thereof.
In some preferred embodiments, particularly suitable solvents for the present invention are solvents having Hansen (Hansen) solubility parameters within the following ranges:
δ d (Dispersion force) at 17.0MPa 1/2 ～23.2MPa 1/2 In particular in the range of 18.5MPa 1/2 ～21.0MPa 1/2 Is defined by the range of (2);
δ p (polar force) at 0.2MPa 1/2 ～12.5MPa 1/2 In particular in the range of 2.0MPa 1/2 ～6.0MPa 1/2 Is defined by the range of (2);
δ h (Hydrogen bonding force) at 0.9MPa 1/2 ～14.2MPa 1/2 In particular in the range of 2.0MPa 1/2 ～6.0MPa 1/2 Is not limited in terms of the range of (a).
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 the embodiment of the present invention may comprise 0.01 to 10wt% of the organic compound according to the present invention or a polymer or a mixture thereof, preferably 0.1 to 15wt%, more preferably 0.2 to 5wt%, most preferably 0.25 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 the use of an organic compound, polymer, mixture or composition as described above for the preparation of an organic electronic device, which may be selected from, but is not limited to, organic Light Emitting Diodes (OLEDs), organic photovoltaic cells (OPVs), organic light emitting cells (OLEEC), 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 Diode), and the like, particularly preferably OLEDs. In the embodiment of the invention, the organic compound or the high polymer is preferably used for a light emitting layer of an OLED device.
The invention further relates to an organic electronic device comprising at least one organic compound or polymer or mixture as described above or prepared from a composition as described above. Further, the organic electronic device comprises at least one functional layer comprising or being prepared from an organic compound or polymer or mixture as described above. The functional layer is selected from a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an emitting layer (EML), an Electron Blocking Layer (EBL), an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), and a Hole Blocking Layer (HBL).
In a preferred embodiment, the organic electronic device according to the invention comprises at least one hole injection layer or hole transport layer comprising or being prepared from an organic compound or polymer or mixture as described above.
Generally, the organic electronic device of the present invention comprises at least one cathode, one anode and one functional layer between the cathode and the anode, wherein the functional layer comprises at least one organic compound as described above. 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.
In certain preferred embodiments, the hole injection layer or hole transport layer of the electroluminescent device comprises an organic compound or polymer as described above.
In the light emitting device, especially the OLED, the light emitting device comprises a substrate, an anode, at least one light emitting layer and a cathode.
The substrate may be opaque or transparent. A transparent substrate may be used to fabricate a transparent light emitting device. See, for example, bulovic et al Nature1996,380, p29, and Gu et al, appl. Phys. Lett.1996,68, p2606. The substrate may be rigid or elastic. The substrate may be plastic, metal, semiconductor wafer or glass. Preferably, the substrate has a smooth surface. Substrates without surface defects are a particularly desirable choice. In a preferred embodiment, the substrate is flexible, optionally in the form of a polymer film or plastic, having a glass transition temperature Tg of 150℃or higher, preferably over 200℃and more preferably over 250℃and most preferably over 300 ℃. Examples of suitable flexible substrates are poly (ethylene terephthalate) (PET) and polyethylene glycol (2, 6-naphthalene) (PEN).
The anode may comprise a conductive metal or metal oxide, or a conductive polymer. The anode can easily inject holes into a Hole Injection Layer (HIL) or a Hole Transport Layer (HTL) or a light emitting layer. In one embodiment, the absolute value of the difference between the work function of the anode and the HOMO level or valence band level of the emitter in the light emitting layer or of the p-type semiconductor material as HIL or HTL or Electron Blocking Layer (EBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2eV. Examples of anode materials include, but are not limited to: al, cu, au, ag, mg, fe, co, ni, mn, pd, pt, ITO aluminum doped zinc oxide (AZO), and the like. Other suitable anode materials are known and can be readily selected for use by one of ordinary skill in the art. The anode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like. In certain embodiments, the anode is patterned. Patterned ITO conductive substrates are commercially available and can be used to prepare devices according to the present invention.
The cathode may comprise a conductive metal or metal oxide. The cathode can easily inject electrons into the EIL or ETL or directly into the light emitting layer. In one embodiment, the work function of the cathode and the emitter in the light-emitting layer are either as an Electron Injection Layer (EIL) or an Electron Transport Layer (ETL) or holesThe absolute value of the difference in LUMO or conduction band levels of the n-type semiconductor material of the barrier layer (HBL) is less than 0.5eV, preferably less than 0.3eV, and most preferably less than 0.2eV. In principle, all materials which can be used as cathode of an OLED are possible as cathode materials for the device according to the invention. Examples of cathode materials include, but are not limited to: al, au, ag, ca, ba, mg, liF/Al, mgAg alloy and BaF 2 /Al, cu, fe, co, ni, mn, pd, pt, ITO, etc. The cathode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.
The OLED may further include other functional layers such as a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), 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.
The light-emitting device according to the present invention has a light-emitting wavelength of 300nm to 1200nm, preferably 350nm to 1000nm, more preferably 400nm to 900 nm.
The invention also relates to the use of an electroluminescent device according to the invention for the preparation of 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
The synthetic method of the organic compound according to the present invention is exemplified, but the present invention is not limited to the following examples.
Example 1 Synthesis of Compound P-1
Synthesis of compound A2:
compound A1 (2.02 g,10 mmol), sodium periodate (NaIO 4 17.6g,81.8 mmol), ruthenium trichloride (RuCl) 3. XH 2 O,0.25g, 1.2 mmol), acetonitrile 40ml, dichloromethane 40ml, and distilled water 50ml were stirred overnight at 30-40 degrees Celsius, the reaction product was cooled to room temperature, and 200ml of distilled water was added, then the precipitate formed was filtered under reduced pressure, the filtrate was extracted with dichloromethane, and anhydrous magnesium sulfate was added thereto to remove water, then the solvent was removed under reduced pressure, the residue was passed through a silica gel column using dichloromethane as an eluent to obtain a product, then the solvent was removed under reduced pressure and the product was dried under vacuum to prepare the desired solid compound A2 (0.80 g, 31%), MS: [ M+H ] + ＝263。
Synthesis of Compound P-1:
titanium tetrachloride (9.34 g,50 mmol), malononitrile (2.64 g,40 mmol), compound A2 (2.63 g,10 mmol) was stirred under reflux under nitrogen for 24 hours using dry pyridine/dichloromethane as solvent, then quenched with cold concentrated hydrochloric acid, concentrated with dichloromethane, then dried over anhydrous sodium sulfate, distilled under reduced pressure, and the residue recrystallized from DCM/MeOH to give Compound P-1 (1.72 g, 38%), MS: [ M+H] + ＝455。
EXAMPLE 2 Synthesis of Compound P-2
Synthesis of compound A3:
the compound A2 (2.62 g,10 mmol) produced in example 1 was dissolved in 80ml DMF,7.4g (41.6 mmol) NBS was dissolved in 73ml DMF solvent, and the NBS solution was added dropwise to the substrate solution at a rate of 3-5 drops per second, followed by stirring. At normal temperature, stopping the reaction after the dripping is completed, dripping 30ml of water into the reaction liquid, recrystallizing, and filtering to obtain the productA3(3.54g，85％)，MS:[M+H] + ＝418。
Synthesis of compound A4:
titanium tetrachloride (9.34 g,50 mmol), malononitrile (2.64 g,40 mmol), compound A3 (4.18 g,10 mmol) were stirred at reflux with nitrogen dry pyridine/dichloromethane as solvent for 24 hours, then quenched with cold concentrated hydrochloric acid, concentrated with dichloromethane, then dried over anhydrous sodium sulfate, distilled under reduced pressure, and the residue recrystallized from DCM/MeOH to give Compound A4 (1.51 g, 26%) MS: [ M+H ] + ＝584。
Synthesis of Compound P-2:
compound A4 (5.84 g,10 mmol), 4-cyanobenzylboronic acid (2.94 g,20 mmol), potassium carbonate (4.8 g,35 mmol) and tetrakis (triphenylphosphine) palladium (312 mg,0.27 mmol) were weighed into a 250mL two-necked flask, 150mL 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 was cooled to room temperature, water was added thereto, extraction was performed with ethyl acetate, the organic phase was washed with brine, dried over sodium sulfate, and the organic solvent was distilled off under reduced pressure, followed by column chromatography on silica gel to give Compound P-2 (5.45 g, 83%), MS: [ M+H] + ＝657。
EXAMPLE 3 Synthesis of Compound P-3
Synthesis of compound A2: reference is made to example 1.
Synthesis of Compound P-3:
titanium tetrachloride (9.34 g,50 mmol), compound A5 (4.36 g,40 mmol), compound A2 (2.63 g,10 mmol) was stirred under reflux under nitrogen for 24 hours using dried pyridine/dichloromethane as solvent, then quenched with cold concentrated hydrochloric acid, concentrated with dichloromethane, then dried over anhydrous sodium sulfate, distilled under reduced pressure, and the residue was recrystallized from DCM/MeOH to give Compound P-3 (2.57 g, 41%) MS: [ M+H] + ＝627。
EXAMPLE 4 Synthesis of Compound P-4
Synthesis of compound A2: reference is made to example 1.
Synthesis of Compound P-4:
titanium tetrachloride (9.34 g,50 mmol), compound A6 (6.08 g,40 mmol), compound A2 (2.63 g,10 mmol) were stirred under reflux in a nitrogen atmosphere with dry pyridine/dichloromethane as solvent for 24 hours, then quenched with cold concentrated hydrochloric acid, concentrated with dichloromethane, then dried over anhydrous sodium sulfate, distilled under reduced pressure, and the residue recrystallized from DCM/MeOH to give Compound P-4 (4.30 g, 54%), MS: [ M+H] + ＝798。
EXAMPLE 5 Synthesis of Compound P-5
Synthesis of compound A2: reference is made to example 1.
Synthesis of Compound P-5:
titanium tetrachloride (9.34 g,50 mmol), compound A7 (7.12 g,40 mmol), compound A2 (2.63 g,10 mmol) was stirred at reflux with nitrogen-dried pyridine/dichloromethane as solvent for 24 hours, then quenched with cold concentrated hydrochloric acid, concentrated with dichloromethane, then dried over anhydrous sodium sulfate, distilled under reduced pressure, and the residue recrystallized from DCM/MeOH to give Compound P-5 (2.43 g, 27%) MS: [ M+H] + ＝903。
EXAMPLE 6 Synthesis of Compound P-6
Synthesis of compound A9:
compound A8 (2.04 g,10 mmol), sodium periodate (NaIO 4 17.6g,81.8 mmol), ruthenium trichloride (RuCl. XH) 2 O,0.25g 1.2 mmol), acetonitrile 40ml, dichloromethane 40ml, and distilled water 50ml were stirred overnight at 30-40 degrees Celsius, and the reaction product was cooled to room Warm, and 200ml of distilled water was added, then the formed precipitate was filtered under reduced pressure, the filtrate was extracted with methylene chloride, and anhydrous magnesium sulfate was added thereto to remove water, then the solvent was removed under reduced pressure, the residue was passed through a silica gel column using methylene chloride as an eluent to obtain a product, then the solvent was removed under reduced pressure and the product was dried under vacuum to prepare the desired solid compound A9 (1.19 g, 45%), MS: [ M+H] + ＝265。
Synthesis of Compound P-6:
titanium tetrachloride (9.34 g,50 mmol), malononitrile (2.64 g,40 mmol), compound A9 (2.65 g,10 mmol) was stirred under reflux for 24 hours with dry pyridine/dichloromethane as solvent, then quenched with cold concentrated hydrochloric acid, concentrated with dichloromethane, then dried over anhydrous sodium sulfate, distilled under reduced pressure, and the residue recrystallized from DCM/MeOH to give Compound P-6 (2.23 g, 49%) MS: [ M+H] + ＝457。
EXAMPLE 7 Synthesis of Compound P-7
Synthesis of compound a 11:
compound A10 (3.10 g,10 mmol), sodium periodate (NaIO 4 17.6g,81.8 mmol), ruthenium trichloride (RuCl) 3 .XH 2 O,0.25g, 1.2 mmol), acetonitrile 40ml, dichloromethane 40ml, and distilled water 50ml were stirred overnight at 30-40 degrees Celsius, the reaction product was cooled to room temperature, and 200ml of distilled water was added, then the precipitate formed was filtered under reduced pressure, the filtrate was extracted with dichloromethane, and anhydrous magnesium sulfate was added thereto to remove water, then the solvent was removed under reduced pressure, the residue was passed through a silica gel column using dichloromethane as an eluent to obtain a product, then the solvent was removed under reduced pressure and the product was dried under vacuum to prepare the desired solid compound A11 (1.59 g, 43%), MS: [ M+H ] + ＝370。
Synthesis of Compound P-7:
titanium tetrachloride (9.34 g,50 mmol), malononitrile (2.64 g,40 mmol), A11 (3.70 g,10 mmol) were dried under nitrogenReflux stirring of dry pyridine/dichloromethane as solvent for 24H followed by quenching with cold concentrated hydrochloric acid, concentration of dichloromethane, drying over anhydrous sodium sulfate, distillation under reduced pressure, and recrystallisation of the residue with DCM/MeOH gave Compound P-7 (4.12 g, 73%), MS: [ M+H ]] + ＝563。
EXAMPLE 8 Synthesis of Compound P-8
Synthesis of compound a 13:
sodium tert-butoxide (2.43 g,25 mmol), p-bromophenylboronic acid (4.00 g,20 mmol), compound A12 (5.13 g,10 mmol), pd (PPh) were added under nitrogen, dry tetrahydrofuran, at room temperature 3 ) 4 (3.4 g,3 mmol) and copper iodide (3.9 g,20 mmol) were stirred at 60℃for 12 hours, then quenched with cold concentrated hydrochloric acid, concentrated with dichloromethane, then dried over anhydrous sodium sulfate, distilled under reduced pressure, and the residue recrystallized from DCM/MeOH to give Compound A13 (5.78 g, 87%), MS: [ M+H] + =665. Synthesis of Compound P-8:
sodium tert-butoxide (2.43 g,25 mmol), malononitrile (2.64 g,40 mmol) were stirred under nitrogen, dry tetrahydrofuran for 15min, and Compound A13 (6.65 g,10 mmol), pd (PPh 3 ) 4 (3.4 g,3 mmol) and copper iodide (3.9 g,20 mmol) were stirred at 60℃for 12 hours, then quenched with cold concentrated hydrochloric acid, concentrated with dichloromethane, then dried over anhydrous sodium sulfate, distilled under reduced pressure, the residue recrystallized with DCM/MeOH to give the crude product, which was dissolved with glacial acetic acid, then cooled to 0℃and then added with a mixture of nitric acid and hydrobromic acid, stirred at room temperature after the addition was completed, quenched with distilled water, and stirred continuously after precipitation of the solid, after which an orange solid compound P-8 (4.30 g, 71%) MS: [ M+H) was obtained] + ＝606。
EXAMPLE 9 Synthesis of Compound P-9
Synthesis of compound A9: reference is made to example 6.
Synthesis of Compound P-9:
titanium tetrachloride (4.67 g,25 mmol), nitroamide (2.48 g,40 mmol), compound A9 (2.64 g,10 mmol) were stirred at reflux with nitrogen-dried pyridine/dichloromethane as solvent for 24 hours, then quenched with cold concentrated hydrochloric acid, concentrated with dichloromethane, then dried over anhydrous sodium sulfate, distilled under reduced pressure, and the residue recrystallized from DCM/MeOH to give Compound P-9 (1.98 g, 45%) MS: [ M+H ]] + ＝441
EXAMPLE 10 Synthesis of Compound P-10
Synthesis of compound a 15:
sodium tert-butoxide (2.43 g,25 mmol), compound A14 (4.40 g,20 mmol), A3 (4.17 g,10 mmol) and Pd (PPh) were added under nitrogen, dry tetrahydrofuran at room temperature 3 ) 4 (3.4 g,3 mmol) and copper iodide (3.9 g,20 mmol) were stirred at 60℃for 12 hours, then quenched with cold concentrated hydrochloric acid, concentrated with dichloromethane, then dried over anhydrous sodium sulfate, distilled under reduced pressure, and the residue recrystallized from DCM/MeOH to give Compound A15 (4.49 g, 74%), MS: [ M+H] + ＝608。
Synthesis of Compound P-10:
titanium tetrachloride (4.67 g,25 mmol), aminoacetonitrile (0.84 g,20 mmol), compound A15 (6.08 g,10 mmol) were stirred at reflux for 24 hours with nitrogen-dried pyridine/dichloromethane as solvent, then quenched with cold concentrated hydrochloric acid, concentrated with dichloromethane, then dried over anhydrous sodium sulfate, distilled under reduced pressure, and the residue recrystallized from DCM/MeOH to give Compound P-10 (3.94 g, 56%), MS: [ M+H ]] + ＝704。
Preparation and characterization of OLED devices
ITO// HIL (10 nm)/HT-1 (120 nm)/HT-2 (10 nm)/BH: BD (25 nm)/ET: liq30 nm)/Liq (1 nm)/Al (100 nm), the preparation steps are as follows:
a. cleaning the conductive glass substrate, namely cleaning the conductive glass substrate by using various solvents, such as chloroform, ketone and isopropanol, and then performing ultraviolet ozone plasma treatment;
b. HIL (10 nm), HT-1 (120 nm), HT-2 (10 nm), EML (20 nm), ETL (30 nm): the ITO substrate was transferred into a vacuum vapor deposition apparatus and evaporated under high vacuum (1X 10-6 mbar) using resistive heating, HT-1 and P-1 at 98:2 to form 10nm of HIL (hole injection layer), and then sequentially evaporating to obtain 120nm of HT-1 and 10nm of HT-2 layers. BH and BD then follow 97:3 to form a 25nm light-emitting layer by co-evaporation. Then, the ET and the LiQ are placed in different evaporation units to be respectively co-deposited in a proportion of 50 weight percent, an electron transport layer of 30nm is formed on the light-emitting layer, then, the LiQ of 1nm is deposited on the electron transport layer as an electron injection layer, and finally, an Al cathode with a thickness of 100nm is deposited on the electron injection layer
c. Encapsulation the device was encapsulated with an ultraviolet curable resin in a nitrogen glove box.
All devices use different compounds as dopants (P-dopant) except HIL, and other embodiments are identical. The current-voltage (J-V) characteristics of each OLED device were characterized by a characterization apparatus while recording important parameters such as efficiency, lifetime, and external quantum efficiency.
TABLE 2
As can be seen from the above, when the organic compound according to the invention is used as a P-dopa material for an organic electronic device, the device efficiency and the service life of the organic compound are improved to a certain extent, particularly the service life of the organic compound is improved by at least 18% in the prior art.
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 (5)

1. An organic compound represented by the general formula (1):
wherein:
the general formula (1) is selected from any one of formulas (2-1) - (2-3):
wherein:
R 1 independently at each occurrence, selected from H, D, nitro, nitroso, CF 3 Cl, br, F, I, cyano;
R 4 independently at each occurrence selected from nitro, nitroso, CF 3 Cl, br, F, I, cyano, trihaloformyl;
each occurrence is independently selected from the following groups:
2. a mixture comprising an organic compound according to claim 1 and at least one organic functional material selected from the group consisting of a hole injecting material, a hole transporting material, an electron injecting material, an electron blocking material, a hole blocking material, a light-emitting body, a host material, and an organic dye.
3. A composition comprising an organic compound according to claim 1 or a mixture according to claim 2, and at least one organic solvent.
4. An organic electronic device comprising at least one functional layer comprising an organic compound according to claim 1 or a mixture according to claim 2 or prepared from a composition according to claim 3.
5. The organic electronic device of claim 4, wherein the functional layer is a hole injection layer or a hole transport layer.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109638171A (en) * 2017-12-22 2019-04-16 广州华睿光电材料有限公司 Organic mixture, high polymer, composition and application thereof
CN109705100A (en) * 2017-12-22 2019-05-03 广州华睿光电材料有限公司 The organic optical compounds of carbazoles containing naphthalene, mixture, composition and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109638171A (en) * 2017-12-22 2019-04-16 广州华睿光电材料有限公司 Organic mixture, high polymer, composition and application thereof
CN109705100A (en) * 2017-12-22 2019-05-03 广州华睿光电材料有限公司 The organic optical compounds of carbazoles containing naphthalene, mixture, composition and application thereof

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