CN112876382A - Organic compounds, mixtures, compositions and uses thereof - Google Patents

Organic compounds, mixtures, compositions and uses thereof Download PDF

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CN112876382A
CN112876382A CN202011095656.8A CN202011095656A CN112876382A CN 112876382 A CN112876382 A CN 112876382A CN 202011095656 A CN202011095656 A CN 202011095656A CN 112876382 A CN112876382 A CN 112876382A
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CN112876382B (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 invention relates to an organic compound, a mixture, a composition and application thereof, in particular to application in an organic light-emitting diode. The organic compound disclosed by the invention has excellent hole transport property and stability as shown in a general formula (1), can be used as a hole injection layer material in an organic electroluminescent element, and can also be doped in a hole injection layer or a hole transport layer as a dopant, so that the organic compound can be driven by low voltage, the electroluminescent efficiency can be improved, and the service life of a device can be prolonged.
Figure DDA0002723655370000011

Description

Organic compounds, mixtures, compositions and uses thereof
The present application claims priority of the chinese patent application with application number 201911202496.X entitled "a pyrenequinone organic compound and its use" filed in 2019, 11, 29, month, the entire contents of which are incorporated herein by reference.
Technical Field
The invention 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 advantages of being versatile, low cost to manufacture, and good in optical and electrical performance.
The organic light emitting diode consists of three parts, namely an anode, a cathode and an organic layer between the anode and the cathode. 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 light emission of the organic light emitting diode is as follows: 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 the injected holes and electrons meet to form excitons, which emit light when they 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 improve the recombination efficiency of the injected holes and electrons, further improvement in the structure, material, and the like of the organic light emitting diode is required.
Currently, merck company utilizes aromatic diamine derivatives or aromatic fused ring diamine derivatives as hole transport materials of organic light emitting diodes to improve the efficiency of injecting holes, but at this time, the organic light emitting diodes can fully emit light by increasing the use voltage, which leads to the problems of reduced service life and increased power consumption of the organic light emitting diodes.
Such problems have recently been solved by doping the hole transport layer of organic light emitting diodes with electron acceptors, such as Tetracyanoquinodimethane (TCNQ) or 2,3,5, 6-tetrafluoro-tetracyano-1, 4-benzoquinodimethane (F4TCNQ) (Chemical Science 2018,9(19), 4468-: the operation is unstable in the manufacturing process of the organic light emitting diode, the stability is insufficient when the organic light emitting diode is driven, the life is reduced, or the above compound is diffused in the device to contaminate the device when the organic light emitting diode is manufactured by vacuum deposition.
Therefore, there is a need for further improvement of an electron acceptor, i.e., a P-dopant, doped in the hole transport layer, particularly a dopant that can realize a low voltage and a long lifetime of the organic light emitting diode.
Disclosure of Invention
In view of the defects of the prior art, the invention provides an organic compound, a mixture, a composition and application thereof, and aims to provide a novel organic photoelectric functional material to improve the efficiency and the service life of a device.
The technical scheme of the invention is as follows:
an organic compound represented by the general formula (1):
Figure BDA0002723655350000011
wherein:
x is independently selected from CR at each occurrence1Or N;
each occurrence of Y is independently selected from CR2R3、NR2、SiR2R3Or a substituted or unsubstituted aromatic group containing 6 to 60 ring atoms or a substituted or unsubstituted heteroaromatic group containing 5 to 60 ring atoms, or a substituted or unsubstituted non-aromatic ring system group containing 3 to 30 ring atoms;
R1independently at each occurrence, H, D, or a straight-chain alkyl group having 1 to 20C atoms, or a straight-chain alkyloxy group having 1 to 20C atoms, or a straight-chain 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, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group, or an isothiocyanate group having 7 to 20C atomsEster group, hydroxyl group, nitro group, CF3Cl, 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;
R2-R3each occurrence independently selected from nitro, nitroso, CF3Cl, Br, F, I, cyano, alkoxy, or a keto 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, isocyanate, thiocyanate or isothiocyanate group, hydroxyl, 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.
The invention further relates to a mixture comprising one of the above-mentioned organic compounds and at least one organic functional material selected from the group consisting of hole-injecting materials, hole-transporting materials, electron-injecting materials, electron-blocking materials, hole-blocking materials, light-emitting bodies, host materials or organic dyes.
The invention further relates to a composition comprising one of the above organic compounds or mixtures, and at least one organic solvent.
The invention further relates to an organic electronic device comprising at least one functional layer comprising an organic compound or mixture as described above, or prepared from a composition as described above.
Compared with the prior art, the invention has the following beneficial effects:
the organic compound has a pyrenequinone structure, has excellent hole transport property and stability, can be used as a hole injection layer material in an organic electroluminescent element, and can also be used as a dopant 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 a device can be prolonged.
Drawings
Fig. 1 is a structural view 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
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying 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 in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In the compounds of the invention, when any variable (e.g. R)1、R2Etc.) occur more than one time in any constituent, then the definition of each occurrence is independent of the definition of each other occurrence. Also, combinations of substituents and variables are permissible only if such combinations result in stable compounds.
In the present invention, the Host material, the Matrix material, the Host material and the Matrix material have the same meaning and may be interchanged.
In the present invention, the composition, printing ink, and ink have the same meaning and may be interchanged.
In the present invention, "substituted" means that a hydrogen atom in a substituent is substituted by a substituent.
In the present invention, in the case of the present invention,when the same substituent occurs more than once, it can be independently selected from different groups. As shown in the general formula, the compound contains a plurality of R1Then R is1Can be independently selected from different groups.
In the present invention, "substituted or unsubstituted" means that the defined group may or may not be substituted. When a defined group is substituted, it is understood to be optionally substituted with art-acceptable groups including, but not limited to: c1-30Alkyl, 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, isocyanate, thiocyanate, isothiocyanate, hydroxy, trifluoromethyl, nitro or halogen, and the above groups may be further substituted with art-acceptable substituents; it is understood that R and R 'in-NRR' are each independently substituted with art-acceptable groups including, but not limited to, H, C1-6An alkyl group, a cycloalkyl group having 3 to 8 ring atoms, a heterocyclic group having 3 to 8 ring atoms, an aryl group having 5 to 20 ring atoms or a heteroaryl group having 5 to 10 ring atoms; said C is1-6Alkyl, cycloalkyl containing 3 to 8 ring atoms, heterocyclyl containing 3 to 8 ring atoms, aryl containing 5 to 20 ring atoms or heteroaryl containing 5 to 10 ring atoms are optionally further substituted by one or more of the following: c1-6Alkyl, cycloalkyl having 3 to 8 ring atoms, heterocyclyl having 3 to 8 ring atoms, halogen, hydroxy, nitro or amino.
In the present invention, the "number of ring atoms" represents the number of atoms among atoms constituting the ring itself of a structural compound (for example, a monocyclic compound, a condensed ring compound, a crosslinked compound, a carbocyclic compound, and a heterocyclic compound) in which atoms are bonded in a ring shape. When the ring is substituted with a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The "number of ring atoms" described below is the same unless otherwise specified. For example, the number of ring atoms of the benzene ring is 6, the number of ring atoms of the naphthalene ring is 10, and the number of ring atoms of the thienyl group is 5.
In the present invention, "alkyl" may mean a linear, branched and/or cyclic alkyl group. The carbon number of the alkyl group may be 1 to 50, 1 to 30, 1 to 20, 1 to 10, or 1 to 6. Phrases containing the term, e.g., "C1-9Alkyl "refers to an alkyl group containing 1 to 9 carbon atoms, which may be independently at each occurrence C1Alkyl radical, C2Alkyl radical, C3Alkyl radical, C4Alkyl radical, C5Alkyl radical, C6Alkyl radical, C7Alkyl radical, C8Alkyl or C9An alkyl group. Non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl, 4-methylcyclohexyl, 4-tert-butylcyclohexyl, n-heptyl, 1-methylheptyl, 2-dimethylheptyl, 2-ethylheptyl, 2-butylheptyl, n-octyl, tert-octyl, 2-ethyloctyl, 2-butyloctyl, 2-hexyloctyl, tert-butyl, 2-isobutyl, 2-ethylbutyl, 3-dimethylbutyl, 2-methylh, 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.
An aromatic group refers to a hydrocarbon group containing at least one aromatic ring. A heteroaromatic group refers to an aromatic hydrocarbon group that contains at least one heteroatom. The heteroatoms are preferably selected from Si, N, P, O, S and/or Ge, particularly preferably from Si, N, P, O and/or S. By fused ring aromatic group is meant that the rings of the aromatic group may have two or more rings in which two carbon atoms are shared by two adjacent rings, i.e., fused rings. The fused heterocyclic aromatic group means a fused ring aromatic hydrocarbon group containing at least one hetero atom. For the purposes of the present invention, aromatic or heteroaromatic radicals include not only aromatic ring systems but also non-aromatic ring systems. Thus, for example, systems such as pyridine, thiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, pyrazine, pyridazine, pyrimidine, triazine, carbene, and the like, are also considered aromatic or heterocyclic aromatic groups for the purposes of this invention. For the purposes of the present invention, fused-ring aromatic or fused-heterocyclic aromatic ring systems include not only systems of aromatic or heteroaromatic groups, but also systems in which a plurality of aromatic or heterocyclic aromatic groups may also be interrupted by short non-aromatic units (< 10% of non-H atoms, preferably less than 5% of non-H atoms, such as C, N or O atoms). Thus, for example, systems such as 9, 9' -spirobifluorene, 9, 9-diarylfluorene, triarylamines, diaryl ethers, etc., are also considered fused aromatic ring systems for the purposes of this invention.
In a certain preferred embodiment, said aromatic group is selected from: benzene, naphthalene, anthracene, fluoranthene, phenanthrene, triphenylene, perylene, tetracene, pyrene, benzopyrene, acenaphthene, fluorene, and derivatives thereof; the heteroaromatic group is selected from the group consisting of triazines, pyridines, pyrimidines, imidazoles, furans, thiophenes, benzothiophenes, indoles, carbazoles, pyrroloimidazoles, pyrrolopyrroles, thienopyrroles, thienothiophenes, furopyrroles, furofurans, thienofurans, benzisoxazoles, benzisothiazoles, benzimidazoles, quinolines, isoquinolines, phthalazines, quinoxalines, phenanthridines, primadines, quinazolines, quinazolinones, dibenzothiophenes, dibenzofurans, carbazoles, and derivatives thereof.
In the embodiment of the present invention, the energy level structure of the organic material, the triplet state energy level ETHOMO, LUMO play a key role. The determination of these energy levels is described below.
The HOMO and LUMO energy levels can be measured by the photoelectric effect, for example XPS (X-ray photoelectron spectroscopy) and UPS (ultraviolet photoelectron spectroscopy) or by cyclic voltammetry (hereinafter referred to as CV). Recently, quantum chemical methods, such as the density functional theory (hereinafter abbreviated as DFT), have become effective methods for calculating the molecular orbital level.
Triplet energy level E of organic materialT1Can be measured by low temperature Time resolved luminescence spectroscopy, or can be obtained by quantum simulation calculations (e.g., by Time-dependent DFT), such as by commercial software Gaussian 03W (Gaussian Inc.), specific simulation methods can be found in WO2011141110 or as described in the examples below.
Note that HOMO, LUMO, ET1The absolute value of (c) depends on the measurement method or calculation method used, and even for the same method, different methods of evaluation, for example starting point and peak point on the CV curve, can give different HOMO/LUMO values. Thus, a reasonably 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, ET1Is based on the simulation of the Time-dependent DFT but does not affect the application of other measurement or calculation methods.
In the present invention, (HOMO-1) is defined as the second highest occupied orbital level, (HOMO-2) is defined as 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 of formula (I):
Figure BDA0002723655350000041
wherein:
x is independently selected from CR at each occurrence1Or N;
each occurrence of Y is independently selected from CR2R3、NR2、SiR2R3Or a substituted or unsubstituted aromatic radical containing 6 to 60 ring atoms or a substituted or unsubstituted hetero radical containing 5 to 60 ring atomsAn aromatic group, or a substituted or unsubstituted non-aromatic ring system group containing 3 to 30 ring atoms;
R1independently at each occurrence, H, D, or a straight-chain alkyl group having 1 to 20C atoms, or a straight-chain alkyloxy group having 1 to 20C atoms, or a straight-chain 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, a cyano group, a carbamoyl group, a haloformyl group, an isocyano group, an isocyanate group, a thiocyanate group or an isothiocyanate group, a hydroxyl group, a nitro group, a CF3Cl, 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;
R2-R3each occurrence independently selected from nitro, nitroso, CF3Cl, Br, F, I, cyano, alkoxy, or a keto 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, isocyanate, thiocyanate or isothiocyanate group, hydroxyl, 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 CR2R3、NR2Or substituted or unsubstituted aromatic groups containing 6 to 60C atoms or heteroaromatic groups containing 5 to 60 ring atoms or non-aromatic ring system groups containing 3 to 30 ring atoms.
In one embodiment, at least one Y is selected from CR2R3(ii) a In one embodiment, at least two Y are selected from CR2R3(ii) a In one embodiment, at least three Y are selected from CR2R3(ii) a In one embodiment, Y is selected from CR2R3。
In one embodiment, at least one Y is selected from NR2(ii) a In one embodiment, at least two Y are selected from NR2(ii) a In one embodiment, at least three Y are selected from NR2(ii) a In one embodiment, Y is selected from NR2。
In one embodiment, at least two Y are selected from the same group.
In one embodiment, each occurrence of Y is simultaneously selected from the same group.
In one embodiment, R2-R3Each occurrence independently selected from nitro, nitroso, CF3Cl, Br, F, I, cyano, or alkoxycarbonyl 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, R2-R3Each occurrence independently selected from nitro, nitroso, CF3Cl, Br, F, I, cyano, or by nitro, nitroso, CF3Cl, Br, F, I or cyano-substituted aromatic or heteroaromatic groups having 5 to 60 ring atoms.
In one embodiment, R2-R3At least one of which is selected from nitro, nitroso, CF3Cl, Br, F, I, cyano-substituted aromatic or heteroaromatic groups having 5 to 60 ring atoms.
In one embodiment, R2-R3Is selected from nitro, nitroso, CF3Cl, Br, F, I, cyano-substituted aromatic or heteroaromatic groups having 5 to 60 ring atoms.
In one embodiment, Y is selected from CR2R3(ii) a Preferably, Y is selected from the following groups:
Figure BDA0002723655350000051
in one embodiment, Y is selected from NR2(ii) a Preferably, Y is selected from:
Figure BDA0002723655350000061
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:
Figure BDA0002723655350000062
in one embodiment, X is selected from CR1；
In one embodiment, R1Selected from H, D, cyano, isocyano, nitro, CF3Cl, 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, R1Is selected from H.
In one embodiment, at least one R1Selected from cyano, isocyano, nitro, CF3Cl, 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 R1Selected from substituted or unsubstituted aromatic or heteroaromatic groups having from 5 to 30 ring atoms; preferably, at least one R1Selected from nitro, nitroso, CF3A Cl, Br, F, I or cyano-substituted aromatic or heteroaromatic group; more preferably, at least one R1Selected from substituted or unsubstituted benzene; more preferably, at least one R1Selected from nitro groupsNitroso group, CF3Cl, Br, F, I or cyano-substituted benzene.
Preferably, at least two R1Selected from substituted or unsubstituted aromatic or heteroaromatic groups having from 5 to 30 ring atoms; preferably, at least two R1Selected from nitro, nitroso, CF3A Cl, Br, F, I or cyano-substituted aromatic or heteroaromatic group; more preferably, at least two R1Selected from substituted or unsubstituted benzene; more preferably, at least two R1Selected from nitro, nitroso, CF3Cl, Br, F, I or cyano-substituted benzene.
In one embodiment, formula (1) is selected from any one of formulae (2-1) to (2-3):
Figure BDA0002723655350000063
wherein:
R4independently at each occurrence, H, D, or a straight-chain alkyl group having 1 to 20C atoms, or a straight-chain alkyloxy group having 1 to 20C atoms, or a straight-chain 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, a cyano group, a carbamoyl group, a haloformyl group, an isocyano group, an isocyanate group, a thiocyanate group or an isothiocyanate group, a hydroxyl group, a nitro group, a CF3Cl, 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, R4Each occurrence is independently selected from H, nitro, nitroso, CF3Cl, Br, F, I, cyano, or by nitro, nitroso, CF3Cl, Br, F, I, cyano-substituted aromatic or heteroaromatic groups having 5 to 60 ring atoms; more preferably, R4Each occurrence is independently selected from nitro, nitroso, CF3F, I or cyano.
In some of these embodiments, R1Each occurrence is independently selected from H, nitro, nitroso, CF3Cl, Br, F, I, cyano, or by nitro, nitroso, CF3Cl, 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)1Are all selected from H;
in one embodiment, at least one R in formula (2-1)1Selected from nitro, nitroso, CF3Cl, Br, F, I, cyano, or by nitro, nitroso, CF3Cl, Br, F, I or cyano-substituted aromatic or heteroaromatic groups having 5 to 60 ring atoms.
In one embodiment, R in formula (2-1)1Are all selected from nitro, nitroso, CF3Cl, Br, F, I, cyano, or by nitro, nitroso, CF3Cl, 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)1Are all selected from H;
in one embodiment, at least one R in formula (2-2)1Selected from nitro, nitroso, CF3Cl, Br, F, I, cyano, or by nitro, nitroso, CF3Cl, Br, F, I or cyano-substituted aromatic or heteroaromatic groups having 5 to 60 ring atoms.
In one embodiment, R in formula (2-2)1Are all selected from nitro, nitroso, CF3Cl, Br, F, I, cyano, or by nitro, nitroso, CF3Cl, Br, F, I or cyano-substituted having 5 to 60An aromatic or heteroaromatic group of a ring atom.
In one embodiment, formula (1) is selected from formula (2-3);
in one embodiment, R in formula (2-3)1Are all selected from H;
in one embodiment, at least one R in formula (2-3)1Selected from nitro, nitroso, CF3Cl, Br, F, I, cyano, or by nitro, nitroso, CF3Cl, Br, F, I or cyano-substituted aromatic or heteroaromatic groups having 5 to 60 ring atoms.
In one embodiment, R in formula (2-3)1Are all selected from nitro, nitroso, CF3Cl, Br, F, I, cyano, or by nitro, nitroso, CF3Cl, 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)4Selected from nitro, nitroso, CF3Cl, Br, F, I, cyano, or by nitro, nitroso, CF3Cl, Br, F, I or cyano-substituted aromatic or heteroaromatic groups having 5 to 60 ring atoms.
In one embodiment, R in formula (2-3)4Are all selected from nitro, nitroso, CF3Cl, Br, F, I, cyano, or by nitro, nitroso, CF3Cl, 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 CR2R3Or NR2。R2And R3The definition is the same as above.
In one embodiment, the organic compound according to the present invention is selected from the following structures, but is not limited thereto:
Figure BDA0002723655350000081
Figure BDA0002723655350000091
Figure BDA0002723655350000101
the invention also relates to the organic compound as an organic ferromagnetic material, the organic ferromagnetic compound refers to an organic material with ferromagnetism, also called an organic ferromagnetic material, the traditional ferromagnetic materials are all inorganic materials such as alloy and oxide containing iron group or rare earth group metal elements, the ferromagnetism of the traditional ferromagnetic materials is derived from atomic magnetic moment, the traditional ferromagnetic materials are composed of two parts of electron orbit magnetic moment and electron spin magnetic moment, the inorganic magnetic materials have the defects of large density, difficult processing and forming and the like, in the radical anion salt or the di-anion salt of the quinone organic compound, the LUMO energy level is low, the ground state is stable, and a stable unfilled electron layer exists, the stable magnetic moment source can be provided, so the quinone organic compound is represented as magnetism and can be applied to the ferromagnetic materials (particularly, the documents refer to Angew.
The organic compounds according to the invention can be used as functional materials in functional layers of electronic devices. The organic functional layer includes, but is not limited to, a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Transport Layer (ETL), an Electron Injection Layer (EIL), an Electron Blocking Layer (EBL), a Hole Blocking Layer (HBL), and an emission layer (EML).
In a particularly preferred embodiment, the organic compounds according to the invention are used in a Hole Injection Layer (HIL) or a Hole Transport Layer (HTL).
In a very preferred embodiment, the organic compounds according to the invention are used as p-type doping materials in Hole Injection Layers (HILs) or Hole Transport Layers (HTLs).
In certain embodiments, the organic compound according to the invention, T thereof1More preferably, it is not less than 0.3eV, still more preferably not less than 0.6eV, particularly preferably not less than 0.8 eV. T is1Represents the triplet energy level of the compound.
Functional materials require good thermal stability. In general, the organic compounds according to the invention have a glass transition temperature Tg of 100 ℃ or higher, in a preferred embodiment 120 ℃ or higher, in a more preferred embodiment 140 ℃ or higher, in a more preferred embodiment 160 ℃ or higher, and in a most preferred embodiment 180 ℃ or higher.
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 ≦ -5.30eV, more preferably ≦ -5.50eV, and most preferably ≦ -5.60 eV. LUMO represents the lowest unoccupied orbital level of the compound.
In certain preferred embodiments, the organic compound according to the invention (HOMO- (HOMO-1)). gtoreq.0.2 eV, preferably gtoreq.0.25 eV, more preferably gtoreq.0.3 eV, more preferably gtoreq.0.35 eV, very preferably gtoreq.0.4 eV, most preferably gtoreq.0.45 eV. HOMO represents the highest occupied orbital level of the 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 has the structure of an organic compound as described above, the linking site of the organic compound to other structures in the repeating unit may be any position in the organic compound that can be linked.
The polymer has the functional characteristics of any of the above 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 main body material (Host) and an organic dye. Various organic functional materials are described in detail, for example, in WO2010135519a1, US20090134784a1 and WO2011110277a1, the entire contents of this 3 patent document being hereby incorporated by reference.
In some preferred embodiments, the mixture, wherein the organic functional material is selected from 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 another organic functional material.
In certain preferred embodiments, the mixture wherein the LUMO of the organic compound is equal to or lower than the HOMO +0.1eV of another organic functional material.
In certain particularly preferred embodiments, the mixture wherein the LUMO of the organic compound is 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 a dopant selected from the organic compounds mentioned above, in a molar ratio of dopant to host of from 1:1 to 1: 100000.
Details of HIM/HTM/EBM, and Host (Host material/matrix material) are described in WO2018095395A 1.
It is another object of the present invention to provide a material solution for printing OLEDs.
In certain embodiments, the organic compounds according to the present 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, and most preferably 1200g/mol or more.
In other embodiments, the organic compounds according to the invention have a solubility in toluene of 2mg/ml or more, preferably 3mg/ml or more, more preferably 4mg/ml or more, most preferably 5mg/ml or more 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, or boric acid ester or phosphoric acid ester compound, or a mixture of two or more solvents.
In a preferred embodiment, a composition according to the invention is characterized in that said at least one organic solvent is chosen from aromatic or heteroaromatic-based solvents.
Examples of aromatic or heteroaromatic based solvents suitable for the present invention are, but not limited to: p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1, 4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, dipentylbenzene, tripentylbenzene, pentyltoluene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2,3, 4-tetramethylbenzene, 1,2,3, 5-tetramethylbenzene, 1,2,4, 5-tetramethylbenzene, butylbenzene, dodecylbenzene, dihexylbenzene, dibutylbenzene, p-diisopropylbenzene, cyclohexylbenzene, benzylbutylbenzene, dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, 1-methylnaphthalene, 1,2, 4-trichlorobenzene, 4-difluorodiphenylmethane, 1, 2-dimethoxy-4- (1-propenyl) benzene, diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, α -dichlorodiphenylmethane, 4- (3-phenylpropyl) pyridine, benzyl benzoate, 1-bis (3, 4-dimethylphenyl) ethane, 2-isopropylnaphthalene, quinoline, isoquinoline, methyl 2-furancarboxylate, ethyl 2-furancarboxylate, and the like;
examples of aromatic ketone-based solvents suitable for the present invention are, but not limited to: 1-tetralone, 2- (phenylepoxy) tetralone, 6- (methoxy) tetralone, acetophenone, propiophenone, benzophenone, and derivatives thereof, such as 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylpropiophenone, 3-methylpropiophenone, 2-methylpropiophenone, and the like;
examples of aromatic ether-based solvents suitable for the present invention are, but not limited to: 3-phenoxytoluene, butoxybenzene, p-anisaldehyde dimethylacetal, tetrahydro-2-phenoxy-2H-pyran, 1, 2-dimethoxy-4- (1-propenyl) benzene, 1, 4-benzodioxan, 1, 3-dipropylbenzene, 2, 5-dimethoxytoluene, 4-ethylphenetole, 1, 3-dipropoxybenzene, 1,2, 4-trimethoxybenzene, 4- (1-propenyl) -1, 2-dimethoxybenzene, 1, 3-dimethoxybenzene, glycidylphenyl ether, dibenzyl ether, 4-t-butylanisole, trans-p-propenylanisole, 1, 2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, methyl ether, 2-phenoxytetrahydrofuran, ethyl-2-naphthyl ether;
in some preferred embodiments, the at least one organic solvent may be selected from: aliphatic ketones such as 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 2, 5-hexanedione, 2,6, 8-trimethyl-4-nonanone, fenchylone, phorone, isophorone, di-n-amyl ketone, etc.; or aliphatic ethers such as amyl ether, hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and the like.
In other preferred embodiments, the at least one organic solvent may be selected from ester-based solvents: alkyl octanoates, alkyl sebacates, alkyl stearates, alkyl benzoates, alkyl phenylacetates, alkyl cinnamates, alkyl oxalates, alkyl maleates, alkyl lactones, alkyl oleates, and the like. Octyl octanoate, diethyl sebacate, diallyl phthalate, isononyl isononanoate are particularly preferred.
The solvents mentioned may be used alone or as a mixture of two or more organic solvents.
In certain preferred embodiments, a composition according to the 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 another organic solvent include (but are not limited to): methanol, ethanol, 2-methoxyethanol, methylene chloride, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1, 4-dioxane, acetone, methyl ethyl ketone, 1, 2-dichloroethane, 3-phenoxytoluene, 1,1, 1-trichloroethane, 1,1,2, 2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydronaphthalene, decalin, indene, and/or mixtures thereof.
In some preferred embodiments, particularly suitable solvents for the present invention are those having Hansen (Hansen) solubility parameters within the following ranges:
δd(Dispersion force) 17.0MPa1/2～23.2MPa1/2In particular in the range of 18.5MPa1/2～21.0MPa1/2A range of (d);
δp(polar force) at 0.2MPa1/2～12.5MPa1/2In particular in the range of 2.0MPa1/2～6.0MPa1/2A range of (d);
δh(hydrogen bonding force) of 0.9MPa1/2～14.2MPa1/2In particular in the range of 2.0MPa1/2～6.0MPa1/2The range of (1).
The compositions according to the invention, in which the organic solvent is selected taking into account its boiling point parameter. In the invention, the boiling point of the organic solvent is more than or equal to 150 ℃; preferably equal to or more than 180 ℃; more preferably more than or equal to 200 ℃; more preferably more than or equal to 250 ℃; most preferably more than or equal to 275 ℃ or more than or equal to 300 ℃. Boiling points in these ranges are beneficial for preventing nozzle clogging in inkjet print heads. The organic solvent may be evaporated from the solvent system to form a thin film comprising the functional material.
In a preferred embodiment, the composition according to the invention is a solution.
In another preferred embodiment, the composition according to the invention is a suspension.
The compositions of the embodiments of the present invention may comprise from 0.01 wt% to 10 wt% of the organic compound according to the present invention or a polymer or mixture thereof, preferably from 0.1 wt% to 15 wt%, more preferably from 0.2 wt% to 5 wt%, and most preferably from 0.25 wt% to 3 wt%.
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 a printing or coating production process.
Suitable Printing or coating techniques include, but are not limited to, ink jet Printing, letterpress, screen Printing, dip coating, spin coating, doctor blade coating, roll Printing, twist roll Printing, lithographic Printing, flexographic Printing, rotary Printing, spray coating, brush or pad Printing, slot die coating, and the like. Gravure printing, jet printing and ink jet printing are preferred. The solution or suspension may additionally include one or more components such as surface active compounds, lubricants, wetting agents, dispersants, hydrophobing agents, binders, and the like, for adjusting viscosity, film forming properties, enhancing adhesion, and the like. The printing technology and the requirements related to the solution, such as solvent and concentration, viscosity, etc.
The present invention also provides 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 not limited to, Organic Light Emitting Diodes (OLEDs), Organic photovoltaic cells (OPVs), Organic light Emitting cells (OLEECs), Organic Field Effect Transistors (OFETs), Organic light Emitting field effect transistors (efets), Organic lasers, Organic spintronic devices, Organic sensors and Organic Plasmon Emitting diodes (Organic plasma Emitting diodes), etc., particularly preferably OLEDs. In the embodiment of the present 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. Furthermore, the organic electronic device comprises at least one functional layer comprising an organic compound or a polymer or a mixture as described above, or prepared from a composition as described above. The functional layer is selected from a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an emission layer (EML), an Electron Blocking Layer (EBL), an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), and a Hole Blocking Layer (HBL).
In a preferred embodiment, the organic electronic device according to the present invention comprises at least one hole injection layer or hole transport layer, wherein the hole injection layer or hole transport layer comprises an organic compound or polymer or mixture as described above, or is prepared from a composition as described above.
In general, the organic electronic device of the present invention comprises at least a cathode, an anode and a functional layer disposed between the cathode and the anode, wherein the functional layer comprises at least one organic compound as described above. The Organic electronic device can be selected from, but not limited to, Organic Light Emitting Diodes (OLEDs), Organic photovoltaic cells (OPVs), Organic light Emitting cells (OLEECs), Organic Field Effect Transistors (OFETs), Organic light Emitting field effect transistors (fets), Organic lasers, Organic spintronic devices, Organic sensors, Organic Plasmon Emitting diodes (Organic Plasmon Emitting diodes), and the like, and particularly preferred are Organic electroluminescent devices such as OLEDs, OLEECs, Organic light Emitting field effect transistors.
In certain preferred embodiments, the electroluminescent device comprises a hole injection layer or a hole transport layer comprising an organic compound or polymer as described above.
In the above-mentioned light emitting device, especially an OLED, it 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, p 2606. The substrate may be rigid or flexible. The substrate may be plastic, metal, semiconductor wafer or glass. Preferably, the substrate has a smooth surface. A substrate free of surface defects is a particularly desirable choice. In a preferred embodiment, the substrate is flexible, and may be selected from polymeric films or plastics having a glass transition temperature Tg of 150 deg.C or greater, preferably greater than 200 deg.C, more preferably greater than 250 deg.C, and most preferably greater than 300 deg.C. 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 an emission 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 the p-type semiconductor material acting as a HIL or HTL or Electron Blocking Layer (EBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2 eV. 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 pattern structured. 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 absolute value of the difference between the work function of the cathode and the LUMO level or conduction band level of the emitter in the light-emitting layer or of the n-type semiconductor material as Electron Injection Layer (EIL) or Electron Transport Layer (ETL) or Hole Blocking Layer (HBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2 eV. In principle, all materials which can be used as cathodes in OLEDs 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, BaF2Al, 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 also comprise further 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). Suitable materials for use in these functional layers are described in detail above and in WO2010135519a1, US20090134784a1 and WO2011110277a1, the entire contents of these 3 patent documents being hereby incorporated by reference.
The light-emitting device according to the present invention emits light at a wavelength of 300nm to 1200nm, preferably 350nm to 1000nm, and more preferably 400nm to 900 nm.
The invention also relates to the use of the 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 present invention will be described in connection with preferred embodiments, but the present invention is not limited to the following embodiments, and it should be understood that the appended claims outline the scope of the present invention and those skilled in the art, guided by the inventive concept, will appreciate that certain changes may be made to the embodiments of the invention, which are intended to be covered by the spirit and scope of the appended claims.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The method for synthesizing the organic compound according to the present invention is exemplified, but the present invention is not limited to the following examples.
Example 1 Synthesis reaction of Compound P-1
Figure BDA0002723655350000141
Synthesis of compound a 2:
compound A1(2.02g, 10mmol), sodium periodate (NaIO)417.6g, 81.8mmol), ruthenium trichloride (RuCl)3.XH2O, 0.25g, 1.2mmol), acetonitrile 40ml, dichloromethane 40ml, and distilled water 50ml were stirred at 30-40 deg.C overnight, 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 in vacuo to prepare the desired solid compound A2(0.80g, 31%), MS: [ M + H ], [ M + H ]]+＝263。
Synthesis of Compound P-1:
titanium tetrachloride (9.34g, 50mmol), malononitrile (2.64g, 40mmol), compound A2(2.63g, 10mmol) were stirred under reflux in a nitrogen atmosphere using dry pyridine/dichloromethane as solvent24H, then quenched with cold concentrated HCl, concentrated with dichloromethane, then dried over anhydrous sodium sulfate, distilled under reduced pressure, and the residue recrystallized with DCM/MeOH to give Compound P-1(1.72g, 38%), MS: [ M + H ]]+＝455。
Example 2 Synthesis reaction of Compound P-2
Figure BDA0002723655350000151
Synthesis of compound a 3:
compound A2(2.62g,10mmol) obtained in example 1 was dissolved in 80ml of DMF,7.4g (41.6mmol) of NBS was dissolved in 73ml of DMF solvent, and the NBS solution was added dropwise to the substrate solution at a rate of 3 to 5 drops per second with stirring. At normal temperature, after the dropwise addition, the reaction was stopped, 30ml of water was added dropwise to the reaction solution, recrystallization and suction filtration were carried out to obtain A3(3.54g, 85%) as a product of MS: [ M + H ]]+＝418。
Synthesis of compound a 4:
titanium tetrachloride (9.34g, 50mmol), malononitrile (2.64g, 40mmol), Compound A3(4.18g, 10mmol) in nitrogen dried pyridine/dichloromethane solvent was stirred at reflux for 24 hours, then quenched with cold concentrated hydrochloric acid, dichloromethane concentrated, then dried over anhydrous sodium sulfate, distilled under reduced pressure, and the residue recrystallized with DCM/MeOH to give Compound A4(1.51g, 26%), MS: [ M + H ])]+＝584。
Synthesis of Compound P-2:
compound A4(5.84g, 10mmol), 4-cyanophenylboronic acid (2.94g, 20mmol), potassium carbonate (4.8g, 35mmol), tetrakis (triphenylphosphine) palladium (312mg, 0.27mmol) were weighed into a 250mL two-necked flask, 150mL of a mixed solvent of toluene and methanol was added, nitrogen gas was purged three times, the temperature was raised to 90 ℃, and the mixture was stirred overnight. Cooling the reaction solution to room temperature, adding water, extracting with ethyl acetate, washing the organic phase with brine, drying with sodium sulfate, distilling under reduced pressure to remove the organic solvent, mixing with silica gel, and performing column chromatography to obtain compound P-2(5.45g, 83%), MS: [ M + H ]]+＝657。
Example 3 Synthesis reaction of Compound P-3
Figure BDA0002723655350000152
Synthesis of compound a 2: refer to example 1.
Synthesis of Compound P-3:
titanium tetrachloride (9.34g, 50mmol), Compound A5(4.36g, 40mmol), Compound A2(2.63g, 10mmol) were stirred under reflux under nitrogen atmosphere using dried pyridine/dichloromethane as solvent for 24 hours, then quenched with cold concentrated hydrochloric acid, dichloromethane concentrated, then dried over anhydrous sodium sulfate, distilled under reduced pressure, and the residue recrystallized with DCM/MeOH to give Compound P-3(2.57g, 41%), MS: [ M + H ]]+＝627。
Example 4 Synthesis reaction of Compound P-4
Figure BDA0002723655350000161
Synthesis of compound a 2: refer to example 1.
Synthesis of Compound P-4:
titanium tetrachloride (9.34g, 50mmol), compound A6(6.08g, 40mmol), compound A2(2.63g, 10mmol) in dry pyridine/dichloromethane solvent under nitrogen atmosphere were stirred at reflux for 24H, then quenched with cold concentrated hydrochloric acid, dichloromethane concentrated, then dried over anhydrous sodium sulfate, distilled under reduced pressure, and the residue recrystallized with DCM/MeOH to give compound P-4(4.30g, 54%), MS: [ M + H ])]+＝798。
Example 5 Synthesis reaction of Compound P-5
Figure BDA0002723655350000162
Synthesis of compound a 2: refer to example 1.
Synthesis of Compound P-5:
titanium tetrachloride (9.34g, 50mmol), Compound A7(7.12g, 40mmol), Compound A2(2.63g, 10mmol) were placed under nitrogenGas dried pyridine/dichloromethane as solvent was stirred under reflux for 24 hours, then quenched with cold concentrated hydrochloric acid, dichloromethane concentrated, then dried over anhydrous sodium sulfate, distilled under reduced pressure, and the residue recrystallized with DCM/MeOH to give compound P-5(2.43g, 27%) MS: [ M + H% ] (M + H) ]]+＝903。
Example 6 Synthesis of Compound P-6
Figure BDA0002723655350000163
Synthesis of compound a 9:
compound A8(2.04g, 10mmol), sodium periodate (NaIO)417.6g, 81.8mmol), ruthenium trichloride (RuCl. XH)2O, 0.25g of 1.2mmol), acetonitrile 40ml, dichloromethane 40ml, and distilled water 50ml were stirred at 30-40 ℃ overnight, the reaction product was cooled to room temperature, 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 in vacuo to prepare the desired solid compound A9(1.19g, 45%), MS: [ M + H ], (M + H)]+＝265。
Synthesis of Compound P-6:
titanium tetrachloride (9.34g, 50mmol), malononitrile (2.64g, 40mmol), compound A9(2.65g, 10mmol) in a nitrogen atmosphere, dried pyridine/dichloromethane as solvent were stirred at reflux for 24 hours, then quenched with cold concentrated hydrochloric acid, dichloromethane concentrated, then dried over anhydrous sodium sulfate, distilled under reduced pressure, and the residue recrystallized with DCM/MeOH to give compound P-6(2.23g, 49%), MS: [ M + H ])]+＝457。
Example 7 Synthesis of Compound P-7
Figure BDA0002723655350000171
Synthesis of compound a 11:
compound A10(3.10g, 10mmol), sodium periodate (NaIO)417.6g, 81.8mmol), ruthenium trichloride (RuCl)3.XH2O, 0.25g, 1.2mmol), acetonitrile 40ml, dichloromethane 40ml, and distilled water 50ml were stirred at 30-40 deg.C overnight, 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 in vacuo to prepare the desired solid compound A11(1.59g, 43%), MS: [ M + H ], [ M + H ]]+＝370。
Synthesis of Compound P-7:
titanium tetrachloride (9.34g, 50mmol), malononitrile (2.64g, 40mmol), A11(3.70g, 10mmol) in nitrogen dried pyridine/dichloromethane solvent was stirred at reflux for 24 hours, then quenched with cold concentrated hydrochloric acid, dichloromethane concentrated, then dried over anhydrous sodium sulfate, distilled under reduced pressure, and the residue recrystallized with DCM/MeOH to give compound P-7(4.12g, 73%), MS: [ M + H ])]+＝563。
Example 8 Synthesis of Compound P-8
Figure BDA0002723655350000172
Synthesis of compound a 13:
under nitrogen, dry tetrahydrofuran, sodium tert-butoxide (2.43g, 25mmol), p-bromophenylboronic acid (4.00g, 20mmol), Compound A12(5.13g, 10mmol), Pd (PPh) were added at room temperature3)4(3.4g, 3mmol), cuprous iodide (3.9g, 20mmol) followed by stirring at 60 deg.C for 12H, then quenching with cold concentrated hydrochloric acid, dichloromethane concentration, then drying over anhydrous sodium sulfate, distillation under reduced pressure, and recrystallization of the residue with DCM/MeOH gave Compound A13(5.78g, 87%), MS: [ M + H ]]+665. Synthesis of Compound P-8:
sodium tert-butoxide (2.43g, 25mmol), malononitrile (2.64g, 40mmol) in nitrogen,stirring for 15min under dry tetrahydrofuran conditions, and adding Compound A13(6.65g, 10mmol), Pd (PPh) at room temperature3)4(3.4g, 3mmol), cuprous iodide (3.9g, 20mmol) followed by stirring at 60 ℃ for 12H, then quenching with cold concentrated hydrochloric acid, dichloromethane concentration, then drying over anhydrous sodium sulfate, distillation under reduced pressure, recrystallization of the residue with DCM/MeOH to give the crude product, dissolving the crude product with glacial acetic acid, then cooling to 0 ℃, then adding a mixture of nitric acid and hydrobromic acid, stirring at room temperature after addition is complete, quenching with distilled water, continuing stirring after solid precipitation to give an orange solid compound P-8(4.30g, 71%) MS: [ M + H ] MS]+＝606。
Example 9 Synthesis of Compound P-9
Figure BDA0002723655350000181
Synthesis of compound a 9: refer to example 6.
Synthesis of Compound P-9:
titanium tetrachloride (4.67g, 25mmol), nitramide (2.48g, 40mmol), Compound A9(2.64g, 10mmol) in nitrogen dried pyridine/dichloromethane solvent was stirred at reflux for 24H, then quenched with cold concentrated hydrochloric acid, dichloromethane concentrated, then dried over anhydrous sodium sulfate, distilled under reduced pressure, and the residue recrystallized with DCM/MeOH to give Compound P-9(1.98g, 45%), MS: [ M + H ]]+＝441
Example 10 Synthesis of Compound P-10
Figure BDA0002723655350000182
Synthesis of compound a 15:
under nitrogen, dry tetrahydrofuran, sodium tert-butoxide (2.43g, 25mmol), Compound A14(4.40g, 20mmol), A3(4.17g, 10mmol), Pd (PPh) were added at room temperature3)4(3.4g, 3mmol) and cuprous iodide (3.9g, 20mmol) were stirred at 60 ℃ for 12 hours, and then cooled concentrated HCl was addedQuenching, dichloromethane concentration, followed by drying over anhydrous sodium sulfate, distillation under reduced pressure, and recrystallization of the residue from DCM/MeOH gave Compound A15(4.49g, 74%) MS: [ M + H ]]+＝608。
Synthesis of Compound P-10:
titanium tetrachloride (4.67g, 25mmol), aminoacetonitrile (0.84g, 20mmol), Compound A15(6.08g, 10mmol) in nitrogen dried pyridine/dichloromethane solvent was stirred at reflux for 24H, then quenched with cold concentrated hydrochloric acid, dichloromethane concentrated, then dried over anhydrous sodium sulfate, distilled under reduced pressure, and the residue recrystallized with DCM/MeOH to give Compound P-10(3.94g, 56%), MS: [ M + H ])]+＝704。
Preparation and characterization of OLED device
ITO// HIL (10nm)/HT-1(120nm)/HT-2(10nm)/BH BD (25nm)/ET Liq30nm)/Liq (1nm)/Al (100nm), and the preparation method comprises the following specific steps:
Figure BDA0002723655350000191
a. cleaning the conductive glass substrate, namely cleaning the conductive glass substrate by using various solvents such as chloroform, ketone and isopropanol when the conductive glass substrate is used for the first time, and then carrying out ultraviolet ozone plasma treatment;
b. HIL (10nm), HT-1(120nm), HT-2(10nm), EML (20nm), ETL (30 nm): the ITO substrate is transferred into a vacuum vapor deposition apparatus and evaporated under high vacuum (1X 10-6 mbar) using resistance heating, HT-1 and P-1 are heated at a rate of 98: 2 to form a10 nm HIL (hole injection layer), and then successively evaporated to form 120nm HT-1 and 10nm HT-2 layers. Then BH and BD were measured at 97: 3 to form a 25nm light-emitting layer. Then, ET and LiQ were placed in different evaporation units and co-deposited at a ratio of 50 wt% to form an electron transport layer of 30nm on the light-emitting layer, LiQ of 1nm was deposited on the electron transport layer as an electron injection layer, and finally an Al cathode having a thickness of 100nm was deposited on the electron injection layer
c. Encapsulation the devices were encapsulated with uv curable resin in a nitrogen glove box.
All devices have the same embodiment except that the HIL uses different compounds as dopants (P-dopants). The current-voltage (J-V) characteristics of each OLED device were characterized by a characterization device, while recording important parameters such as efficiency, lifetime, and external quantum efficiency.
TABLE 2
Figure BDA0002723655350000192
From the above, it can be seen that when the organic compound according to the present invention is used as a P-dopant material in an organic electronic device, the device efficiency and lifetime thereof are improved to some extent, particularly, the lifetime thereof is improved by at least 18% in the prior art.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (12)

1. An organic compound represented by the general formula (1):
Figure FDA0002723655340000011
wherein:
x is independently selected from CR at each occurrence1Or N;
each occurrence of Y is independentlySelected from the group consisting of CR2R3、NR2、SiR2R3Or a substituted or unsubstituted aromatic group containing 6 to 60 ring atoms or a substituted or unsubstituted heteroaromatic group containing 5 to 60 ring atoms, or a substituted or unsubstituted non-aromatic ring system group containing 3 to 30 ring atoms;
R1independently at each occurrence, H, D, or a straight-chain alkyl group having 1 to 20C atoms, or a straight-chain alkyloxy group having 1 to 20C atoms, or a straight-chain 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, a cyano group, a carbamoyl group, a haloformyl group, an isocyano group, an isocyanate group, a thiocyanate group or an isothiocyanate group, a hydroxyl group, a nitro group, a CF3Cl, 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 group having 5 to 60 ring atoms or a heteroaryloxy group having 5 to 60 ring atoms, or a combination of these systems;
R2-R3each occurrence independently selected from nitro, nitroso, CF3Cl, Br, F, I, cyano, alkoxy, or a keto group having 1 to 20C atoms, or an alkoxycarbonyl group having 2 to 20C atoms, or an aryloxycarbonyl group having 7 to 20C atoms, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group or an isothiocyanate group, a hydroxyl 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 group having 5 to 60 ring atoms or a heteroaryloxy group having 5 to 60 ring atoms, or a combination of these systems.
2. According to the rightThe organic compound of claim 1, wherein each occurrence of Y is independently selected from CR2R3Or NR2。
3. An organic compound according to claim 2, wherein R is2-R3Each occurrence independently selected from nitro, nitroso, CF3Cl, Br, F, I, cyano, or by nitro, nitroso, CF3Cl, B, F, I or cyano-substituted aromatic or heteroaromatic groups having 5 to 60 ring atoms.
4. An organic compound according to claim 2, wherein R is2-R3At least one of which is selected from nitro, nitroso, CF3Cl, Br, F, I or cyano-substituted aromatic or heteroaromatic groups having 5 to 60 ring atoms.
5. An organic compound according to claim 1, characterized in that: y is selected from the following groups:
Figure FDA0002723655340000021
6. the organic compound according to claim 1, wherein the general formula (1) is selected from any one of formulae (2-1) to (2-3):
Figure FDA0002723655340000022
wherein:
R4independently at each occurrence, is selected from H, D, or a straight chain alkyl group having 1 to 20C atoms, or a straight chain alkoxy group having 1 to 20C atoms, or a straight chain thioalkoxy group having 1 to 20C atoms, or a branched or cyclic alkyl group having 3 to 20C atomsOr a branched or cyclic thioalkoxy group having 3 to 20C atoms, or a silyl group, or a keto group having 1 to 20C atoms, or an alkoxycarbonyl group having 2 to 20C atoms, or an aryloxycarbonyl group having 7 to 20C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group or an isothiocyanate group, a hydroxyl group, a nitro group, a CF group3Cl, 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.
7. The organic compound according to claim 6, wherein in the formula (2-3), at least one R is4Selected from nitro, nitroso, CF3Cl, Br, F, I, cyano, or by nitro, nitroso, CF3Cl, Br, F, I or cyano-substituted aromatic or heteroaromatic groups having 5 to 60 ring atoms.
8. The organic compound of any one of claims 1-7, wherein R is1Each occurrence is independently selected from H, nitro, nitroso, CF3Cl, Br, F, I, cyano, or by nitro, nitroso, CF3Cl, Br, F, I or cyano-substituted aromatic or heteroaromatic groups having 5 to 60 ring atoms.
9. A mixture comprising an organic compound according to any one of claims 1 to 8 and at least one organic functional material selected from hole injecting materials, hole transporting materials, electron injecting materials, electron blocking materials, hole blocking materials, light emitters, host materials or organic dyes.
10. A composition comprising an organic compound according to any one of claims 1 to 8 or a mixture according to claim 9, and at least one organic solvent.
11. An organic electronic device comprising at least one functional layer comprising an organic compound according to any one of claims 1 to 8 or a mixture according to claim 9, or prepared from a composition according to claim 10.
12. The organic electronic device according to claim 11, wherein the functional layer is a hole injection layer or a hole transport layer.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113461693A (en) * 2021-06-30 2021-10-01 上海天马微电子有限公司 Organic compound, hole injection material and application thereof
CN113583507A (en) * 2021-06-29 2021-11-02 成都灵睿奥创科技有限公司 Organic semiconductor ink, preparation method and application
KR102401913B1 (en) * 2021-06-11 2022-05-25 최돈수 Light-emitting material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device

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

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102401913B1 (en) * 2021-06-11 2022-05-25 최돈수 Light-emitting material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device
KR20220167198A (en) * 2021-06-11 2022-12-20 최돈수 Light-emitting material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device
KR102573956B1 (en) 2021-06-11 2023-09-01 최돈수 Light-emitting material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device
CN113583507A (en) * 2021-06-29 2021-11-02 成都灵睿奥创科技有限公司 Organic semiconductor ink, preparation method and application
CN113461693A (en) * 2021-06-30 2021-10-01 上海天马微电子有限公司 Organic compound, hole injection material and application thereof
CN113461693B (en) * 2021-06-30 2023-03-24 上海天马微电子有限公司 Organic compound, hole injection material and application thereof

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