CN114716437A - Organic compound, mixture, composition and organic electronic device - Google Patents

Organic compound, mixture, composition and organic electronic device Download PDF

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CN114716437A
CN114716437A CN202011531543.8A CN202011531543A CN114716437A CN 114716437 A CN114716437 A CN 114716437A CN 202011531543 A CN202011531543 A CN 202011531543A CN 114716437 A CN114716437 A CN 114716437A
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CN114716437B (en
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张晨
李涛
何锐锋
宋晶尧
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Guangzhou Chinaray Optoelectronic Materials Ltd
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    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
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Abstract

The invention relates to an organic compound, a mixture, a composition and an organic electronic device. The organic compound has the structure shown in the formula (1), shows excellent hole transport property and stability, can be used as a hole transport layer material in an organic electroluminescent device, and can improve electroluminescent efficiency and prolong the service life of the device.

Description

Organic compound, mixture, composition and organic electronic device
Technical Field
The invention relates to the technical field of organic electroluminescence, in particular to an organic compound, a mixture, a composition and an organic electronic device.
Background
The organic photoelectric material has diversity in synthesis, relatively low manufacturing cost and excellent optical and electrical properties. Organic Light Emitting Diodes (OLEDs) have a wide viewing angle, a fast response time, a low operating voltage, a thin panel thickness, and the like in the field of application of optoelectronic devices such as flat panel displays and lighting, and thus have a wide potential for development.
The organic electroluminescence phenomenon refers to a phenomenon of converting electric energy into light energy using an organic substance. An organic electroluminescent element utilizing an organic electroluminescent phenomenon generally has a structure including a positive electrode, a negative electrode, and an organic functional layer therebetween. In order to improve the efficiency and lifetime of the organic electroluminescent element, the organic functional layer has a multi-layer structure, each layer containing a different organic substance. Specifically, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like may be included. In such an organic electroluminescent element, when a voltage is applied between the two electrodes, holes are injected from the positive electrode into the organic functional layer, electrons are injected from the negative electrode into the organic functional layer, and when the injected holes and electrons meet each other, excitons are formed, and light is emitted when the excitons transition back to the ground state. The organic electroluminescent element has the characteristics of self-luminescence, high brightness, high efficiency, low driving voltage, wide viewing angle, high contrast and the like.
In order to realize an efficient organic electroluminescent device, development of a transport material is important in addition to development of a high-performance light emitting material. At present, most of transmission materials are micromolecular materials based on carbazole derivatives, and the defects of unbalanced hole and electron transmission still exist, so that the service life of devices using the compounds is short. In order to realize color display, red, green and blue devices are generally required, and a red device has a light-emitting layer material with HOMO and LUMO orbital energy levels different from those of green and blue devices, and a red light-emitting layer material with a triplet energy level significantly lower than those of green and blue devices, and a red device generally has a hole transport material with an energy level different from that of the green and blue devices. In order to allow sufficient recombination of positive negative charge carriers in the light-emitting layer, the hole transport material immediately adjacent to the light-emitting layer should also have an appropriate LUMO level to block the flow of electrons from the light-emitting layer to the hole transport material. In order to improve the efficiency and lifetime of organic electroluminescent devices, especially red OLED devices, new hole transport materials are in urgent need to be developed.
Disclosure of Invention
Based on this, the object of the present invention is to provide an organic compound, a mixture, a composition and an organic electronic device, which improve the efficiency and lifetime of the device.
The technical scheme is as follows:
an organic compound having a structure represented by general formula (1):
Figure BDA0002852243910000011
wherein:
R1、R2、R3each independently selected from: a hydrogen atom, D, or a straight-chain alkyl group having 1 to 20C atoms, a straight-chain alkoxy group having 1 to 20C atoms, a straight-chain thioalkoxy group having 1 to 20C atoms, a branched or cyclic alkyl group having 3 to 20C atoms, a branched or cyclic alkoxy group having 3 to 20C atoms, 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 haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group or an isothiocyanate group, a hydroxyl group, a nitro group, an alkenyl group, an amine group, a CF, a hydroxyl group, an isocyanate group or an isothiocyanate group, a hydroxyl group, a nitro group, an alkenyl group, an amine group, a CF3Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic group having from 6 to 60 ring atoms, or a substituted or unsubstituted heteroaromatic group having from 5 to 60 ring atoms, or a substituted or unsubstituted aryloxy group having from 6 to 60 ring atoms, or a substituted or unsubstituted heteroaryloxy group having from 5 to 60 ring atoms, or a combination of these groups;
R1、R2、R3at least one of them is selected from the structural formula (1-1):
Figure BDA0002852243910000021
L1selected from a single bond, or a substituted or unsubstituted aromatic or heteroaromatic group having 6 to 40 ring atoms;
Ar1、Ar2independently selected from a substituted or unsubstituted aromatic group having 6 to 40 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 40 ring atoms or a non-aromatic ring system;
indicates the attachment site;
n1selected from 0, 1,2 or 3; n is2Selected from 0, 1,2,3 or 4; n is a radical of an alkyl radical3Selected from 0, 1,2,3 or 4; n is a radical of an alkyl radical1+n2+n3≥1。
The invention also provides a mixture which comprises the organic compound and at least one organic functional material, wherein the organic functional material is at least one selected from a hole injection material, a hole transport material, an electron injection material, an electron blocking material, a hole blocking material, a light emitting material, a host material and an organic dye.
The invention also provides a composition comprising the organic compound or the mixture and at least one organic solvent.
The invention also provides an organic electronic device comprising at least one functional layer comprising the above organic compound, or the above mixture, or prepared from the above composition.
Compared with the prior art, the invention has the following beneficial effects:
the organic compound provided by the invention has excellent hole transport property and stability, and can be used as a hole transport layer material in an organic electroluminescent device, so that the electroluminescent efficiency can be improved, and the service life of the device can be prolonged.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used 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 present invention, "substituted" means that a hydrogen atom in a substituent is substituted by a substituent.
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: c1-30An alkyl group, a cycloalkyl group having 3 to 20 ring atoms, a heterocyclic group having 3 to 20 ring atoms, an aryl group having 6 to 20 ring atoms, a heteroaryl group having 5 to 20 ring atoms, a silane group, a carbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a haloformyl group, a formyl group, -NRR', a cyano group, an isocyano group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a trifluoromethyl group, a nitro group or a halogen, and the above groups may be further substituted with a substituent acceptable in the art; 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 6 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 6 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.
"aryl or aromatic group" means an aromatic hydrocarbon group derived by removing one hydrogen atom from an aromatic ring compound, and may be a monocyclic aromatic group, or a fused ring aromatic group, or a polycyclic aromatic group, at least one of which is an aromatic ring system for polycyclic ring species. For example, "substituted or unsubstituted aryl group having 6 to 60 ring atoms" means an aryl group containing 6 to 60 ring atoms, preferably an aryl group having 6 to 30 ring atoms, more preferably an aryl group having 6 to 18 ring atoms, particularly preferably an aryl group having 6 to 14 ring atoms, and the aryl group is optionally further substituted; suitable examples include, but are not limited to: benzene, biphenyl, terphenyl, naphthalene, anthracene, fluoranthene, phenanthrene, triphenylene, perylene, tetracene, pyrene, benzopyrene, acenaphthylene, fluorene and derivatives thereof. It will be appreciated that a plurality of aryl groups may also be interrupted by short non-aromatic units (e.g. < 10% of non-H atoms such as C, N or O atoms), such as in particular acenaphthene, fluorene or 9, 9-diarylfluorene, triarylamine, diarylether systems should also be included in the definition of aryl groups.
"heteroaryl or heteroaromatic group" means that on the basis of an aryl group at least one carbon atom is replaced by a non-carbon atom which may be a N atom, an O atom, an S atom, etc. For example, "substituted or unsubstituted heteroaryl having 5 to 60 ring atoms" refers to heteroaryl having 5 to 60 ring atoms, preferably 6 to 30 ring atoms, more preferably 6 to 18 ring atoms, particularly preferably 6 to 14 ring atoms, and heteroaryl is optionally further substituted, suitable examples including but not limited to: triazines, pyridines, pyrimidines, imidazoles, furans, thiophenes, benzofurans, benzothiophenes, indoles, carbazoles, pyrroloimidazoles, pyrrolopyrroles, thienopyrroles, thienothiophenes, furopyrroles, furofurans, thienofurans, benzisoxazoles, benzisothiazoles, benzimidazoles, quinolines, isoquinolines, phthalazines, quinoxalines, phenanthridines, primates, quinazolines, quinazolinones, dibenzothiophenes, dibenzofurans, carbazoles, and derivatives thereof.
"amino" refers to a derivative of ammonia having the formula-N (X)2Wherein each "X" is independently H, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclyl, or the like. Non-limiting types of amine groups include-NH2-N (alkyl)2NH (alkyl), -N (cycloalkyl)2NH (cycloalkyl), -N (heterocyclyl)2NH (heterocyclyl), -N (aryl)2NH (aryl), -N (alkyl) (heterocyclyl), -N (cycloalkyl) (heterocyclyl), -N (aryl) (heteroaryl), -N (alkyl) (heteroaryl), and the like.
"arylalkyl" refers to a hydrocarbyl radical derived from an alkyl radical having at least one hydrogen atom bonded to a carbon atom replaced by an aryl radical. Wherein the aryl moiety may include 5 to 20 carbon atoms and the alkyl moiety may include 1 to 9 carbon atoms. Suitable examples include, but are not limited to: benzyl, 2-phenyleth-1-yl, naphthylmethyl, 2-naphthyleth-1-yl, naphthobenzyl and 2-naphthophenyleth-1-yl.
The term "alkoxy" refers to a group having an-O-alkyl group, i.e., an alkyl group as defined above attached to the parent core structure via an oxygen atom. Phrases encompassing this term, suitable examples include, but are not limited to: methoxy (-O-CH)3or-OMe), ethoxy (-O-CH)2CH3or-OEt) and tert-butoxy (-O-C (CH)3)3or-OtBu).
In the present invention, "+" attached to a single bond represents a connection site.
In the context of the present invention, a single bond to which a substituent is attached extends through the corresponding ring, meaning that the substituent may be attached at an optional position on the ring, for example
Figure BDA0002852243910000031
Any substitutable site of R and benzene ring; such as
Figure BDA0002852243910000032
To represent
Figure BDA0002852243910000033
Form a ring with optionally two adjacent C atoms of the benzene ring, in the same way
Figure BDA0002852243910000034
And the like.
In the present invention, when the same group contains a plurality of substituents of the same symbol, the substituents may be the same or different from each other, for example
Figure BDA0002852243910000041
6R on the benzene ring1May be the same as or different from each other.
In the present invention, the abbreviations for the substituents correspond to: n-, sec-, i-iso-, t-tert-, o-, m-, p-, Me-methyl-, Et-ethyl-, Pr-propyl-, Bu-butyl-, Am-n-pentyl-, Hxhexyl-, Cy-cyclohexyl-.
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. These energy levels are 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 09W (Gaussian Inc.), specific simulation methods can be found in WO2011141110 or as described in the examples below.
Note that HOMO, LUMO, ET1Depending on the measurement or calculation method used, or even for the same method, different methods of evaluation, e.g. on the CV curveThe starting point and the peak point may 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.
The technical scheme is as follows:
an organic compound having a structure represented by general formula (1):
Figure BDA0002852243910000042
wherein:
R1、R2、R3each independently selected from: a hydrogen atom, D, or a straight-chain alkyl group having 1 to 20C atoms, a straight-chain alkoxy group having 1 to 20C atoms, a straight-chain thioalkoxy group having 1 to 20C atoms, a branched or cyclic alkyl group having 3 to 20C atoms, a branched or cyclic alkoxy group having 3 to 20C atoms, 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 haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group or an isothiocyanate group, a hydroxyl group, a nitro group, an alkenyl group, an amine group, a CF, a hydroxyl group, an isocyanate group or an isothiocyanate group, a hydroxyl group, a nitro group, an alkenyl group, an amine group, a CF3Cl, Br, F, crosslinkable radicals, or substituted or unsubstituted aromatic radicals having from 6 to 60 ring atoms, or substituted or unsubstituted heteroaromatic radicals having from 5 to 60 ring atoms, or substituted or unsubstituted aryloxy radicals having from 6 to 60 ring atoms, or substituted or unsubstituted heteroaryloxy radicals having from 5 to 60 ring atoms, or the derivatives of these radicalsCombining;
R1、R2、R3at least one of them is selected from the structural formula (1-1):
Figure BDA0002852243910000051
L1selected from a single bond, or a substituted or unsubstituted aromatic or heteroaromatic group having 6 to 40 ring atoms;
Ar1、Ar2independently selected from a substituted or unsubstituted aromatic group having 6 to 40 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 40 ring atoms or a non-aromatic ring system;
indicates the attachment site;
n1selected from 0, 1,2 or 3; n is2Selected from 0, 1,2,3 or 4; n is a radical of an alkyl radical3Selected from 0, 1,2,3 or 4; n is1+n2+n3≥1。
In one embodiment, R is3Has a structure represented by the formula (1-1); further, n3 is selected from 1 or 2.
Further, the organic compound has a structure as shown in any one of formulas (2-1) to (2-3):
Figure BDA0002852243910000052
further, the organic compound has a structure represented by any one of formulas (3-1) to (3-5):
Figure BDA0002852243910000053
preferably, the organic compound has a structure as shown in formula (3-1) or (3-2).
Preferably, R is as defined in the present invention1、R2Each independently selected from: hydrogen atom, D, or a straight-chain alkyl group having 1 to 10C atoms, a branched-chain alkyl group having 3 to 10C atoms, or cyclicAn alkyl group, or a substituted or unsubstituted aromatic group having 6 to 30 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms.
Further, R in the invention1、R2Each independently selected from: a hydrogen atom, D, or a straight chain alkyl group having 1 to 8C atoms, a branched or cyclic alkyl group having 3 to 8C atoms, or an aromatic or heteroaromatic group having 6 to 20 ring atoms.
Further, R in the formula (3-1) or (3-2) of the present invention1、R2Selected from the same structures; further, R of the formula (3-1) or (3-2) of the present invention1、R2Are all selected from phenyl, naphthyl or tert-butyl.
In a more preferred embodiment, Ar is1、Ar2Independently selected from a substituted or unsubstituted aromatic group having 6 to 30 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms. Further, Ar1、Ar2At least one of which is selected from a fused ring aromatic group or a heteroaromatic group having 10 to 20 ring atoms which may be substituted or unsubstituted.
In a more preferred embodiment, Ar is1、Ar2Independently selected from a substituted or unsubstituted cyclic aromatic group having 6 to 20 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms.
In one embodiment, Ar is1、Ar2Is independently selected from any one of the groups shown in (B-1) to (B-6):
Figure BDA0002852243910000061
wherein:
X1selected from N or CR4；
Y1Selected from O, S, NR5Or CR5R6；
R4-R6At each occurrence, is independently selected from: hydrogen atomD, or a straight-chain alkyl group having 1 to 20C atoms, a straight-chain alkoxy group having 1 to 20C atoms, a straight-chain thioalkoxy group having 1 to 20C atoms, a branched or cyclic alkyl group having 3 to 20C atoms, a branched or cyclic alkoxy group having 3 to 20C atoms, 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 haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group or isothiocyanate group, a hydroxyl group, a nitro group, an alkenyl group, an amine group, CF3, Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic group having 6 to 60 ring atoms, or a substituted or unsubstituted heteroaromatic group having from 5 to 60 ring atoms, or a substituted or unsubstituted aryloxy group having from 6 to 60 ring atoms or a substituted or unsubstituted heteroaryloxy group having from 5 to 60 ring atoms, or a combination of these groups;
R5and R6Not forming a ring or connecting into a ring;
Ar3independently selected from substituted or unsubstituted aromatic or heteroaromatic groups having from 6 to 20 ring atoms.
Preferably Ar in (B-3)3Any one selected from the following groups:
Figure BDA0002852243910000062
more preferably, (B-3) is selected from any one of the following groups:
Figure BDA0002852243910000063
ar is1、Ar2Is independently selected from any one of the following groups:
Figure BDA0002852243910000071
n is selected from 0, 1,2 or 3.
In one embodiment, R4Independently selected from: a hydrogen atom, D, or a straight chain alkyl group having 1 to 10C atoms, a branched or cyclic alkyl group having 3 to 10C atoms, or a substituted or unsubstituted aromatic group having 6 to 30 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms.
Further, R4At each occurrence, is independently selected from: hydrogen atom, D, methyl, tert-butyl, cyclohexyl, adamantyl or phenyl or naphthyl.
Further, Ar1、Ar2Independently selected from the group consisting of:
Figure BDA0002852243910000072
said L1Each occurrence is independently selected from a single bond or any one of the following groups:
Figure BDA0002852243910000073
wherein:
X2at each occurrence, is independently selected from CR7Or N;
Y2at each occurrence, independently selected from NR8、CR8R9O or S;
R7-R9at each occurrence, is independently selected from: a hydrogen atom, D, a straight-chain alkyl group having 1 to 20C atoms, a branched or cyclic alkyl group having 3 to 20C atoms, or a substituted or unsubstituted aromatic group having 6 to 20 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms, or a combination of these groups.
In one embodiment, L1Is selected fromA bond, or a substituted or unsubstituted cyclic structure having benzene, naphthalene, anthracene, phenanthrene, perylene, tetracene, pyrene, benzopyrene, triphenylene, acenaphthylene, fluorene, dibenzofuran, dibenzothiophene.
Further, said L1At each occurrence, the groups are respectively and independently selected from single bond or any one of the following groups:
Figure BDA0002852243910000081
further, L1Selected from a single bond, or a substituted or unsubstituted phenyl group, or a substituted or unsubstituted naphthyl group.
In a preferred embodiment, in the formula (1)
Figure BDA0002852243910000082
Any one selected from the following groups:
Figure BDA0002852243910000083
more preferably still, the first and second liquid crystal compositions are,
Figure BDA0002852243910000091
y in (1)1Selected from O, S, NR5Or CR5R6；
Examples of organic compounds of the invention are listed below, but are not limited to:
Figure BDA0002852243910000092
Figure BDA0002852243910000101
Figure BDA0002852243910000111
Figure BDA0002852243910000121
the organic compounds according to the invention can be used as functional materials in functional layers of electronic devices. The functional layers include, but are not limited to, a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Transport Layer (ETL), an Electron Injection Layer (EIL), an Electron Blocking Layer (EBL), a Hole Blocking Layer (HBL), and an emission layer (EML).
In one embodiment, the organic compounds according to the invention are used in hole transport layers.
The invention further relates to a mixture comprising at least one organic compound as described above, and at least one further organic functional material, which can be selected from the group consisting of Hole Injection Materials (HIM), Hole Transport Materials (HTM), Electron Transport Materials (ETM), Electron Injection Materials (EIM), Electron Blocking Materials (EBM), Hole Blocking Materials (HBM), light emitting materials (Emitter), Host materials (Host) and organic dyes. Various organic functional materials are described in detail, for example, in WO2010135519a1, US20090134784a1 and WO 2011110277a1, the entire contents of this 3 patent document being hereby incorporated by reference.
In one embodiment, the further organic functional material is selected from electron transport materials, which are used as co-hosts in electronic devices.
The invention also relates to a composition comprising at least one organic compound or mixture as described above, and at least one organic solvent; the at least one organic solvent is selected from aromatic or heteroaromatic, 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, according to a composition of the invention, 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 solvents based on aromatic ketones 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 solvents based on aromatic ethers 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, fenchytone, 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 present invention comprises at least one organic compound or mixture as described above and at least one organic solvent, and may further comprise another organic solvent. 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, dimethylsulfoxide, 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:
delta d (dispersion force) is within the range of 17.0-23.2 MPa1/2, especially within the range of 18.5-21.0 MPa 1/2;
δ p (polar force) is in the range of 0.2-12.5 MPa1/2, especially in the range of 2.0-6.0 MPa 1/2;
delta h (hydrogen bonding force) is in the range of 0.9-14.2 MPa1/2, especially in the range of 2.0-6.0 MPa 1/2.
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 at least 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 compound or mixture according to the present invention, 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, improving adhesion, and the like. The printing technology and the requirements related to the solution, such as solvent and concentration, viscosity, etc.
The invention also provides the use of an organic compound, mixture or composition as described above in an organic electronic device.
The technical scheme is as follows:
an organic electronic device comprising at least one functional layer comprising an organic compound, mixture or 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); preferably, the functional layer is selected from a hole transport layer or an electron blocking layer.
In some more preferred embodiments, the organic functional layer includes at least a light-emitting layer and two hole transport layers, and the second hole transport layer is provided between the first hole transport layer and the light-emitting layer, and the second hole transport layer includes an organic compound represented by formula (1).
In one embodiment, the Organic electronic device according to the present invention can be selected from, but is 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 spintronics, Organic sensors, Organic Plasmon Emitting diodes (Organic plasma Emitting diodes), and the like, and particularly preferably is an OLED. In the embodiment of the present invention, the organic compound is preferably used for a hole transport layer of an OLED device.
In one embodiment, the organic electronic device according to the present invention is a red organic electronic device.
In one embodiment, the organic electronic device according to the present invention comprises a first electrode, a second electrode, one or more organic functional layers between the first electrode and the second electrode, the functional layers comprising at least two functional layers: one of the functional layers is a hole transport layer or an electron blocking layer, which contains an organic compound represented by the above formula (1);
the other functional layer is a light-emitting layer containing a metal complex represented by general formula (4):
Figure BDA0002852243910000151
wherein:
q is selected from 1 or 2;
Ar5(ii) at multiple occurrences, is independently selected from substituted or unsubstituted heteroaromatic groups having from 5 to 40 ring atoms;
Ar6when present, is independently selected from a substituted or unsubstituted aromatic group having 6 to 40 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 40 ring atoms;
R10-R11at each occurrence, each is independently selected from: a hydrogen atom, D, a straight chain alkyl group having 1 to 20C atoms, a branched or cyclic alkyl group having 3 to 20C atoms, a substituted or unsubstituted aromatic group having 6 to 60 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, or a combination of these groups.
In one embodiment, Ar5When occurring for multiple times, the derivative is independently selected from quinoline or isoquinoline and derivatives thereof.
In one embodiment, Ar6And when occurring multiple times, is independently selected from phenyl and its derivatives.
Preferably, the metal complex has a structure represented by any one of general formulae (5-1) to (5-3):
Figure BDA0002852243910000152
wherein:
a is selected from 0, 1,2,3,4, 5 or 6, b is selected from 0, 1,2,3 or 4;
R12-R13at each occurrence, each is independently selected from: d, a straight-chain alkyl group having 1 to 20C atoms, a branched or cyclic alkyl group having 3 to 20C atoms, a substituted or unsubstituted aromatic group having 6 to 60 ring atoms, aSubstituted or unsubstituted heteroaromatic groups having 5 to 60 ring atoms, or combinations of these groups.
In one embodiment, at least one R12Or R13Selected from a linear alkyl group having 1 to 20C atoms, or a branched or cyclic alkyl group having 3 to 20C atoms.
In one embodiment, at least one R13Selected from a linear alkyl group having 1 to 20C atoms, or a branched or cyclic alkyl group having 3 to 20C atoms. Further, at least one R12Selected from a linear alkyl group having 1 to 20C atoms, or a branched or cyclic alkyl group having 3 to 20C atoms.
The metal complex according to the general formula (4) is preferably selected from, but not limited to, the following structures, which may be optionally substituted:
Figure BDA0002852243910000161
Figure BDA0002852243910000171
the light-emitting device according to the present invention emits light at a wavelength of 550 to 700nm, preferably 600 to 650nm, more preferably 600 to 640 nm.
The invention also relates to the use of the electroluminescent device according to the invention in various electronic devices, including, but not limited to, display devices, lighting devices, light sources, sensors, etc.
The 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
1. Synthesis of Compounds
Example 1: synthesis of Compound 1
Figure BDA0002852243910000172
Synthesis of intermediates 1 to 3: 1-1(30mmol), 1-2(30mmol) and cesium carbonate (40mmol) were added to dry DMF (200ml) and stirred at 130 ℃ for 6 h. After cooling, the reaction solution was poured into a large amount of water and filtered under suction. The intermediate 1-3 is obtained by sequentially carrying out column chromatography and recrystallization on the filter cake, and the yield is 71%.
Synthesis of intermediates 1 to 5: 1-3(20mmol) was dissolved in dry THF, cooled to-78 ℃ under a nitrogen atmosphere, and n-butyllithium solution (2M, 10ml) was slowly added dropwise with stirring for 2 h. A solution of 1-4(20mmol) in THF was added under nitrogen, then allowed to return to room temperature naturally and the reaction was continued for 12 h. Adding a proper amount of diluted hydrochloric acid into the reaction solution, and continuing the reaction for 0.5 h. Most of the solvent was then removed by rotary evaporation. The product was extracted with dichloromethane and washed three times with water. Collecting organic phase, removing solvent by rotary evaporation, dissolving the obtained crude product in mixed solvent of hydrochloric acid/acetic acid (volume ratio is 1:9), heating to 70 ℃, and stirring for 4 h. After cooling, the reaction solution was poured into a large amount of water and filtered under suction. And washing filter residues with water, a saturated sodium carbonate solution and water for several times in sequence, and recrystallizing to obtain an intermediate 1-5 with a yield of 75%.
Synthesis of intermediates 1 to 6: intermediate 1-5(15mmol) was dissolved in DMF (150ml) and pinacol diborate (15mmol), Pd (dppf) Cl was added2(0.2mmol), tricyclohexylphosphine (0.6mmol) and potassium acetate (35mmol) were reacted at 130 ℃ under nitrogen for 12 h. After cooling, the reaction was poured into a large amount of water and stirred for 1 h. And (4) carrying out suction filtration, and purifying the obtained solid crude product by column chromatography to obtain an intermediate 1-6 with a yield of 62%.
Synthesis of Compound 1: 1-6(12mmol), 1-7(12mmol), Pd (PPh)3)4(0.1mmol) and potassium carbonate (20mmol) were added to 150ml of 1, 4-dioxane/water (volume ratio 9:1) mixed solvent and refluxed for 8h under nitrogen atmosphere. After cooling, most of the solvent was distilled off under reduced pressure, and the remaining substance was dissolved with dichloromethane and washed with water three times. Collecting organic phase, and rotary steamingThe solvent is removed, and the crude product is subjected to column chromatography and recrystallization to obtain the compound 1 with the yield of 90 percent. Ms (asap): 721.
EXAMPLE 2 Synthesis of Compound 2
Figure BDA0002852243910000181
Synthesis of intermediate 2-2 reference was made to the synthesis of 1-3, except that 1-1 was replaced with 2-1, yield 74%.
Synthesis of intermediate 2-3 reference was made to the synthesis of 1-5, except that 1-3 was replaced with 2-2, yield 70%.
Synthesis of Compound 2: mixing 2-3(10mmol), 2-4(10mmol), Pd (dba)2(0.2mmol), tri-tert-butylphosphine (0.6mmol) and sodium tert-butoxide (20mmol) were added to dry toluene (150ml) and stirred at 110 ℃ for 6h under a nitrogen atmosphere. After cooling, the solvent was removed by rotary evaporation, the residue was dissolved with dichloromethane and washed three times with water. The organic phases were combined and the solvent was removed by rotary evaporation. The obtained crude product is subjected to column chromatography and recrystallization to obtain the compound 2, and the yield is 80%. Ms (asap): 763.
EXAMPLE 3 Synthesis of Compound 3
Figure BDA0002852243910000191
Synthesis of compound 3 reference was made to the synthesis of compound 2 except that 2-3 was replaced with 1-5 and 2-4 was replaced with 3-1, yield 80%. Ms (asap): 741.
EXAMPLE 4 Synthesis of Compound 4
Figure BDA0002852243910000192
Synthesis of intermediate 4-2 reference was made to the synthesis of 1-3, except that 1-2 was replaced with 4-1, yield 72%.
Synthesis of intermediate 4-3 reference was made to the synthesis of 1-5, except that 1-3 was replaced with 4-2, yield 75%.
Synthesis of compound 4 the synthesis of compound 2 was referenced except that 2-3 was replaced with 4-3 and 2-4 was replaced with 4-4, with a yield of 82%. Ms (asap): 697.
EXAMPLE 5 Synthesis of Compound 5
Figure BDA0002852243910000201
Synthesis of intermediate 5-1 reference was made to the synthesis of 1-3, except that 1-1 was replaced with 2-1 and 1-2 was replaced with 4-1, yield 70%.
Synthesis of intermediate 5-2 reference was made to the synthesis of 1-5, except that 1-3 was replaced with 5-1, yield 75%.
Synthesis of compound 5 the synthesis of compound 2 was referenced, except that 2-3 was replaced with 5-2 and 2-4 was replaced with 5-3, 84% yield. Ms (asap): 733.
EXAMPLE 6 Synthesis of Compound 6
Figure BDA0002852243910000202
Synthesis of compound 6 the synthesis of compound 2 was referenced, except that 2-3 was replaced with 4-3 and 2-4 was replaced with 4-4, 83% yield. Ms (asap): 695.
EXAMPLE 7 Synthesis of Compound 7
Figure BDA0002852243910000211
Synthesis of intermediate 7-3: mixing 7-1(30mmol), 7-2(30mmol), Pd (PPh)3)4(0.3mmol) and potassium carbonate (40mmol) were added to 250ml of 1, 4-dioxane/water (volume ratio 9:1) mixed solvent, and stirred at 80 ℃ for 6 hours under nitrogen atmosphere. After cooling, most of the solvent was distilled off under reduced pressure, and the remaining reaction solution was dissolved with methylene chloride and washed with water three times. Collecting organic phase, removing solvent by rotary evaporation, and performing column chromatography and recrystallization on the obtained crude product to obtain 7-3 with yield of 85%.
Synthesis of intermediate 7-4: 7-3(24mmol) was dissolved in 120ml triethyl phosphite and heated to 120 ℃ and stirred for 7 h. After cooling, the solvent was removed by distillation under reduced pressure, and the crude product was purified by column chromatography to give 7-4 with a yield of 80%.
Synthesis of intermediates 7-5: 7-4(19mmol), iodobenzene (19mmol), cuprous iodide (30mmol), trans 1, 2-cyclohexanediamine (60mmol), potassium phosphate (35mmol) were added to dry toluene and stirred at 100 ℃ for 5h under a nitrogen atmosphere. After cooling, filtration was carried out. Most of the solvent was removed by rotary evaporation, and the residue was dissolved in dichloromethane and washed three times with water. The organic phases were combined and the solvent was removed by rotary evaporation. The crude product is purified by column chromatography to obtain 7-5 with a yield of 75%.
Synthesis of intermediates 7-6 reference was made to the synthesis of 1-5 except that 1-3 was replaced with 7-5 in 72% yield.
Synthesis of compound 7 reference was made to the synthesis of compound 2 except that 2-3 was replaced with 7-6 in 81% yield. Ms (asap): 651.
EXAMPLE 8 Synthesis of Compound 8
Figure BDA0002852243910000212
Synthesis of intermediate 8-2 reference was made to the synthesis of 7-3, except that 7-2 was replaced with 8-1, yield 83%.
Synthesis of intermediate 8-3 reference was made to the synthesis of 7-4, except that 7-3 was replaced with 8-2, yield 80%.
Synthesis of intermediate 8-5 reference was made to the synthesis of 1-3, except that 1-1 was replaced with 8-3 and 1-2 was replaced with 8-4, yield 80%.
Synthesis of intermediates 8-6 reference was made to the synthesis of 1-5 except that 1-3 was replaced with 8-5 in 75% yield.
Synthesis of intermediates 8-7 reference was made to the synthesis of 1-6 except that 1-5 was replaced with 8-6 in 63% yield.
Synthesis of compound 8 the synthesis of compound 1 was referenced, except that 1-6 was replaced with 8-7 and 1-7 was replaced with 8-8, yield 90%. Ms (asap): 697.
EXAMPLE 9 Synthesis of Compound 9
Figure BDA0002852243910000221
Synthesis of intermediate 9-3: mixing 9-1(30mmol), 9-2(30mmol), Pd (dba)2(0.2mmol), tri-tert-butylphosphine (0.6mmol) and sodium tert-butoxide (40mmol) were added to dry toluene (180ml) and stirred at 70 ℃ for 4h under a nitrogen atmosphere. After cooling, the solvent was removed by rotary evaporation, dissolved with dichloromethane and washed three times with water. The organic phases were combined and the solvent was removed by rotary evaporation. The crude product is subjected to column chromatography and recrystallization to obtain 9-3 with the yield of 77%.
Synthesis of intermediate 9-5 reference was made to the synthesis of 9-3, except 9-1 was replaced with 9-3 and 9-2 was replaced with 9-4, yield 80%.
Synthesis of intermediate 9-8 reference was made to the synthesis of 7-3, except that 7-1 was replaced with 9-7 and 7-2 was replaced with phenylboronic acid in 86% yield.
Synthesis of intermediate 9-9 reference was made to the synthesis of 7-4, except that 7-3 was replaced with 9-8, yield 81%.
Synthesis of intermediates 9-10 reference was made to the synthesis of 7-5, except that 7-4 was replaced with 9-9, yield 74%
Synthesis of intermediates 9-11 reference was made to the synthesis of 1-5 except that 1-3 was replaced with 9-10 in 73% yield.
Synthesis of intermediates 9-12 reference was made to the synthesis of 1-6 except that 1-5 was replaced with 9-11 in 60% yield.
Synthesis of compound 9 reference was made to the synthesis of compound 1 except that 1-6 was replaced with 9-12 and 1-7 was replaced with 9-5, yield 70%. Ms (asap): 845.
EXAMPLE 10 Synthesis of Compound 10
Figure BDA0002852243910000222
Synthesis of intermediate 10-2 reference was made to the synthesis of 7-5, except that iodobenzene was replaced with 10-1 in 80% yield.
Synthesis of intermediate 10-3 reference was made to the synthesis of 1-5, except that 1-3 was replaced with 10-2, yield 75%.
Synthesis of compound 10: mixing 10-3(12mmol), 10-4(24mmol), Pd (dba)2(0.2mmol), tri-tert-butylphosphine (0.6mmol) and sodium tert-butoxide (40mmol) were added to dry toluene (180ml) and stirred at 110 ℃ for 6h under a nitrogen atmosphere. After cooling, the solvent was removed by rotary evaporation, the residue was dissolved with dichloromethane and washed three times with water. The organic phases were combined and the solvent was removed by rotary evaporation. The crude product is subjected to column chromatography and recrystallization to obtain a compound 10 with the yield of 80%. Ms (asap): 712.
EXAMPLE 11 Synthesis of Compound 11
Figure BDA0002852243910000231
Synthesis of intermediate 11-2 reference was made to the synthesis of 1-3, except that 1-1 was replaced with 11-1 and 1-2 was replaced with 4-1, with a yield of 70%.
Synthesis of intermediate 11-3 reference was made to the synthesis of 1-5, except that 1-3 was replaced with 11-2, yield 72%.
Synthesis of compound 11 reference was made to the synthesis of compound 2 except that 2-3 was replaced with 11-3 and 2-4 was replaced with 11-4, yield 80%. Ms (asap): 813.
EXAMPLE 12 Synthesis of Compound 12
Figure BDA0002852243910000232
Synthesis of intermediate 12-1 reference was made to the synthesis of 1-6, except that 1-5 was replaced with 2-3, yield 60%.
Synthesis of compound 12 reference was made to the synthesis of compound 1 except that 1-6 was replaced with 12-1 and 1-7 was replaced with 12-2, yield 90%. Ms (asap): 809.
EXAMPLE 13 Synthesis of Compound 13
Figure BDA0002852243910000233
Synthesis of compound 13 reference was made to the synthesis of compound 1 except that 1-7 was replaced with 13-1 in 86% yield. Ms (asap): 671.
EXAMPLE 14 Synthesis of Compound 14
Figure BDA0002852243910000241
Synthesis of compound 14 the synthesis of compound 2 was referenced, except that 2-3 was replaced with 4-3 and 2-4 was replaced with 14-1, with a yield of 70%. Ms (asap): 710.
2. preparing and detecting a device:
device example 1
The structure of the device is ITO/hole injection layer (10 nm)/first hole transport layer (60 nm)/second hole transport layer (60 nm)/host material RH1 red light guest/ETM Liq/LiF/Al. Wherein the mass ratio of the main material RH1 to RD2 is 95: 5. The specific preparation process is as follows:
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. the hole injection layer is made of HT1/HATCN (97/3, w/w) on the ITO layer under high vacuum (1X 10)-6Millibar) hot evaporation;
c. evaporating 60 nm-thick HT1 as a first hole transport layer on the hole injection layer;
d. evaporating the compound 1 of the invention with the thickness of 60nm as a second hole transport layer on the first hole transport layer;
e. vacuum evaporating a 40nm light-emitting layer on the second hole transport layer; the luminescent layer comprises RH1 as a host material and RD1 as a guest material, and the two materials are co-evaporated by adopting multiple sources; wherein the evaporation rate of RD2 is controlled to be 5% of RH 1;
f. on the light-emitting layer, an ETM/Liq (1:1 mass ratio) mixture with a thickness of 25nm is evaporated to be used as an electron transport layer; evaporating LiF with the thickness of 0.5nm on the electron transport layer to be used as an electron injection layer; al with the thickness of 150nm is evaporated on the electron injection layer to be used as a cathode;
g. and (3) packaging, namely packaging the device in a nitrogen glove box by using ultraviolet hardening resin to obtain the OLED device 1.
Figure BDA0002852243910000242
Figure BDA0002852243910000251
OLED devices 2 to 29 were fabricated with reference to device example 1, except that the second hole transport layer material (compound 1) or the red guest material RD2 was changed to the compounds shown in table 1.
The current-voltage (J-V) characteristics of each OLED device were characterized by characterization equipment, while recording important parameters such as efficiency, lifetime, and external quantum efficiency. Table 2 shows the OLED device lifetime and external quantum efficiency comparison, where lifetime LT95 is the time at which the luminance drops to 95% of the initial luminance @1000nits at constant current. Here LT95, the external quantum efficiency, is calculated relative to comparative device example 1 (corresponding to comparative material 1), i.e. 100% external quantum efficiency with a lifetime of 1 for comparative device example 1. The results are shown in Table 1.
Table 1: OLED device Performance comparison
Figure BDA0002852243910000252
Figure BDA0002852243910000261
As can be seen from Table 1, the device external quantum efficiency and lifetime of device examples 1-25 are significantly higher than those of comparative device example 1 (corresponding to RD2 and Ref-1), comparative device example 2 (corresponding to RD1 and Ref-1), comparative device example 3 (corresponding to RD3 and Ref-1), and comparative device example 4 (corresponding to RD2, without the second hole transport layer).
The device performance of compounds 1-6, 10-14 was higher than that of compounds 7-9, indicating that R3The device performance of the compound selected from the general formula (1-1) is better than that of R alone1Or R2Selected from the compounds of the general formula (1-1). The device efficiencies and lifetimes of compound 2, compound 5, compound 11, compound 12 were relatively higher than the other device examples, illustrating when R3When selected from (1-1), R1And R2The existence of the group has the effect of improving the efficiency of the device. Therefore, the OLED device prepared by the organic mixture provided by the invention has obviously improved luminous efficiency and service life.
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 (14)

1. An organic compound having a structure represented by general formula (1):
Figure FDA0002852243900000011
wherein:
R1、R2、R3each independently selected from: a hydrogen atom, D, or a linear alkyl group having 1 to 20C atomsStraight-chain alkoxy having 1 to 20C atoms, straight-chain thioalkoxy having 1 to 20C atoms, branched or cyclic alkyl having 3 to 20C atoms, branched or cyclic alkoxy having 3 to 20C atoms, branched or cyclic thioalkoxy having 3 to 20C atoms, or silyl, or keto having 1 to 20C atoms, or alkoxycarbonyl having 2 to 20C atoms, or aryloxycarbonyl having 7 to 20C atoms, cyano, haloformyl, formyl, isocyano, isocyanate, thiocyanate or isothiocyanate, hydroxyl, nitro, alkenyl, amine, CF3Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic group having from 6 to 60 ring atoms, or a substituted or unsubstituted heteroaromatic group having from 5 to 60 ring atoms, or a substituted or unsubstituted aryloxy group having from 6 to 60 ring atoms or a substituted or unsubstituted heteroaryloxy group having from 5 to 60 ring atoms, or a combination of these groups;
R1、R2、R3at least one of them is selected from the structural formula (1-1):
Figure FDA0002852243900000012
L1selected from a single bond, or a substituted or unsubstituted aromatic or heteroaromatic group having 6 to 40 ring atoms;
Ar1、Ar2independently selected from a substituted or unsubstituted aromatic group having 6 to 40 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 40 ring atoms or a non-aromatic ring system;
indicates the attachment site;
n1selected from 0, 1,2 or 3; n is2Selected from 0, 1,2,3 or 4; n is3Selected from 0, 1,2,3 or 4; n is1+n2+n3≥1。
2. The organic compound according to claim 1, wherein the organic compound has a structure represented by any one of formulas (2-1) to (2-3):
Figure FDA0002852243900000013
3. the organic compound according to claim 2, wherein the organic compound has a structure represented by any one of formulas (3-1) to (3-5):
Figure FDA0002852243900000021
4. the organic compound of any one of claims 1 to 3, wherein R is1、R2Each independently selected from: a hydrogen atom, D, or a straight chain alkyl group having 1 to 10C atoms, a branched or cyclic alkyl group having 3 to 10C atoms, or a substituted or unsubstituted aromatic group having 6 to 30 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms.
5. The organic compound of claim 4, wherein R is1、R2Each independently selected from: phenyl, naphthyl or tert-butyl.
6. The organic compound according to any one of claims 1 to 3, wherein Ar is Ar1、Ar2Is independently selected from any one of the groups shown in (B-1) to (B-6):
Figure FDA0002852243900000022
wherein:
X1selected from N or CR4；
Y1Selected from O, S, NR5Or CR5R6；
R4-R6At each occurrence, is independently selected from: a hydrogen atom, D, or a straight-chain alkyl group having 1 to 20C atoms, a straight-chain alkoxy group having 1 to 20C atoms, a straight-chain thioalkoxy group having 1 to 20C atoms, a branched or cyclic alkyl group having 3 to 20C atoms, a branched or cyclic alkoxy group having 3 to 20C atoms, 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 haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group or an isothiocyanate group, a hydroxyl group, a nitro group, an alkenyl group, an amine group, CF3, Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic group having 6 to 60 ring atoms, or a substituted or unsubstituted heteroaromatic group having from 5 to 60 ring atoms, or a substituted or unsubstituted aryloxy group having from 6 to 60 ring atoms, or a substituted or unsubstituted heteroaryloxy group having from 5 to 60 ring atoms, or a combination of these groups;
R5and R6Not forming a ring or connecting into a ring;
Ar3independently selected from substituted or unsubstituted aromatic or heteroaromatic groups having from 6 to 20 ring atoms.
7. The organic compound of claim 6, wherein Ar is Ar1、Ar2Is independently selected from any one of the following groups:
Figure FDA0002852243900000031
n is selected from 0, 1,2 or 3.
8. The organic compound according to any one of claims 1 to 3,said L1Each occurrence is independently selected from a single bond or any one of the following groups:
Figure FDA0002852243900000032
wherein:
X2at each occurrence, is independently selected from CR7Or N;
Y2at each occurrence, independently selected from NR8、CR8R9O or S;
R7-R9at each occurrence, is independently selected from: a hydrogen atom, D, a straight chain alkyl group having 1 to 20C atoms, a branched or cyclic alkyl group having 3 to 20C atoms, or a substituted or unsubstituted aromatic group having 6 to 20 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms, or a combination of these groups.
9. The organic compound according to claim 1, wherein in the general formula (1)
Figure FDA0002852243900000033
Any one selected from the following groups:
Figure FDA0002852243900000041
10. a mixture comprising one organic compound according to any one of claims 1 to 9 and at least one organic functional material selected from at least one of a hole injecting material, a hole transporting material, an electron injecting material, an electron blocking material, a hole blocking material, a light emitting material, a host material and an organic dye.
11. A composition comprising at least one organic compound according to any one of claims 1 to 9, or a mixture according to claim 10, and at least one organic solvent.
12. An organic electronic device comprising at least one functional layer comprising an organic compound according to any one of claims 1 to 9, or a mixture according to claim 10, or prepared from a composition according to claim 11.
13. The organic electronic device according to claim 12, comprising a first electrode, a second electrode, one or more organic functional layers between the first electrode and the second electrode, characterized in that said functional layers comprise at least two functional layers:
one of the functional layers is a hole transport layer or an electron blocking layer comprising an organic compound according to any one of claims 1 to 9, or a mixture according to claim 10, or prepared from a composition according to claim 11;
the other functional layer is a light-emitting layer containing a metal complex represented by general formula (4):
Figure FDA0002852243900000051
wherein:
q is selected from 1 or 2;
Ar5(ii) at multiple occurrences, is independently selected from substituted or unsubstituted heteroaromatic groups having from 5 to 40 ring atoms;
Ar6when present, is independently selected from a substituted or unsubstituted aromatic group having 6 to 40 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 40 ring atoms;
R10-R11at each occurrence, is independently selected from: hydrogen atom, D, having 1 to 20A linear alkyl group of C atoms, a branched or cyclic alkyl group of 3 to 20C atoms, or a substituted or unsubstituted aromatic group of 6 to 60 ring atoms, or a substituted or unsubstituted heteroaromatic group of 5 to 60 ring atoms, or a combination of these groups.
14. The organic electronic device according to claim 13, wherein the light-emitting layer comprises a metal complex represented by any one of the structures of the general formulae (5-1) to (5-3):
Figure FDA0002852243900000052
wherein:
a is selected from 0, 1,2,3,4, 5 or 6, b is selected from 0, 1,2,3 or 4;
R12-R13at each occurrence, each is independently selected from: d, a straight-chain alkyl group having 1 to 20C atoms, a branched or cyclic alkyl group having 3 to 20C atoms, or a substituted or unsubstituted aromatic group having 6 to 60 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, or a combination of these groups.
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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
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