CN114716437B - Organic compounds, mixtures, compositions and organic electronic devices - Google Patents

Organic compounds, mixtures, compositions and organic electronic devices Download PDF

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CN114716437B
CN114716437B CN202011531543.8A CN202011531543A CN114716437B CN 114716437 B CN114716437 B CN 114716437B CN 202011531543 A CN202011531543 A CN 202011531543A CN 114716437 B CN114716437 B CN 114716437B
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CN114716437A (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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    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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Abstract

The present invention relates to an organic compound, mixture, composition and organic electronic device. The organic compound has a structure shown in a formula (1), has 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 compounds, mixtures, compositions and organic electronic devices
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
Organic photoelectric materials have a variety of synthesis, relatively low manufacturing cost and excellent optical and electrical properties. Organic Light Emitting Diodes (OLEDs) have advantages of wide viewing angle, fast reaction time, low operating voltage, thin panel thickness, etc. in applications of optoelectronic devices such as flat panel displays and illumination, and thus have a wide development potential.
The organic electroluminescence refers to a phenomenon in which electric energy is converted into light energy using an organic substance. An organic electroluminescent element utilizing the organic electroluminescent phenomenon generally has a structure in which a positive electrode and a negative electrode have an organic functional layer interposed therebetween. In order to improve the efficiency and lifetime of the organic electroluminescent device, the organic functional layers have a multi-layered structure, each layer containing a different organic material. Specifically, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like may be included. In such an organic electroluminescent element, when a voltage is applied between two electrodes, holes are injected from a positive electrode into an organic functional layer, electrons are injected from a negative electrode into the organic functional layer, and when the injected holes meet the electrons, excitons are formed, and light is emitted when the excitons transition back to a ground state. The organic electroluminescent element has the characteristics of self-luminescence, high brightness, high efficiency, low driving voltage, wide viewing angle, high contrast ratio and the like.
In order to realize a high-efficiency organic electroluminescent device, development of a transmission material is important in addition to development of a high-performance light-emitting material. At present, most of transmission materials are small molecular materials based on carbazole derivatives, and the defect of unbalanced hole and electron transmission still exists, so that the service life of devices applying the compounds is shorter. In order to realize color display, devices with three colors of red, green and blue are generally required, while red devices have different HOMO and LUMO orbital levels from those of the light-emitting layer materials of the green and blue devices, and the triplet energy level of the red light-emitting layer material is obviously lower than that of the green and blue materials, and the energy level of the hole transport material of the red device is usually different from that of the hole transport material of the green and blue devices. In order for positive and negative carriers to sufficiently recombine at the light-emitting layer, the hole-transporting material in close proximity to the light-emitting layer should also have a suitable LUMO level to block the flow of electrons from the light-emitting layer to the hole-transporting material. In order to improve the efficiency and the service life of the organic electroluminescent device, especially the efficiency and the service life of the red OLED device, a novel hole transport material is required to be developed.
Disclosure of Invention
Based on this, it is an object of the present invention 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 proposal is as follows:
an organic compound having a structure represented by the general formula (1):
wherein:
R 1 、R 2 、R 3 each independently selected from: hydrogen atom, D, or a linear alkyl group having 1 to 20C atoms, a linear alkoxy group having 1 to 20C atoms, a linear 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 sulfur group having 3 to 20C atomsThioalkoxy or cyclic thioalkoxy, 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, thiocyanate or isothiocyanate, hydroxy, nitro, alkenyl, amino, CF 3 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 5 to 60 ring atoms, or a substituted or unsubstituted aryloxy group having 6 to 60 ring atoms, or a substituted or unsubstituted heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups;
R 1 、R 2 、R 3 At least one of which is selected from the structural formulas (1-1):
L 1 selected from single bonds, or substituted or unsubstituted aromatic or heteroaromatic groups having 6 to 40 ring atoms;
Ar 1 、Ar 2 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, or a non-aromatic ring system;
* Represents a ligation site;
n 1 selected from 0,1,2 or 3; n is n 2 Selected from 0,1,2,3 or 4; n is n 3 Selected from 0,1,2,3 or 4; n is n 1 +n 2 +n 3 ≥1。
The invention also provides a mixture comprising the organic compound and at least one organic functional material, wherein the organic functional material is selected from at least one of a hole injection material, a hole transport material, an electron injection material, an electron blocking material, a hole blocking material, a luminescent material, a host material and an organic dye.
The invention also provides a composition comprising the above-described organic compound, or a mixture of the above, 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 a mixture of the above, 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 herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
In the present invention, "substituted" means that a hydrogen atom in a substituted group is substituted by a substituent.
In the present invention, "substituted or unsubstituted" means that the defined group may or may not be substituted. When a defined group is substituted, it is understood to be optionally substituted with groups acceptable in the art, including but not limited to: c (C) 1-30 Alkyl, cycloalkyl having 3 to 20 ring atoms, heterocyclyl having 3 to 20 ring atoms, aryl having 6 to 20 ring atoms, heteroaryl having 5 to 20 ring atoms, silaneA group, carbonyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, haloformyl, formyl, -NRR', cyano, isocyano, thiocyanate, isothiocyanate, hydroxy, trifluoromethyl, nitro or halogen, and which may be further substituted with substituents acceptable in the art; it is understood that R and R 'in-NRR' are each independently substituted with a group acceptable in the art, including but not limited to H, C 1-6 An 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; the C is 1-6 An alkyl group, a cycloalkyl group containing 3 to 8 ring atoms, a heterocyclic group containing 3 to 8 ring atoms, an aryl group containing 6 to 20 ring atoms, or a heteroaryl group containing 5 to 10 ring atoms is optionally further substituted with one or more of the following groups: c (C) 1-6 Alkyl, cycloalkyl having 3 to 8 ring atoms, heterocyclyl having 3 to 8 ring atoms, halogen, hydroxy, nitro or amino.
In the present invention, the "number of ring atoms" means the number of atoms among atoms constituting the ring itself of a structural compound (for example, a monocyclic compound, a condensed ring compound, a crosslinked compound, a carbocyclic compound, a heterocyclic compound) in which atoms are bonded to form a ring. When the ring is substituted with a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The same applies to the "number of ring atoms" described below, unless otherwise specified. For example, the number of ring atoms of the benzene ring is 6, the number of ring atoms of the naphthalene ring is 10, and the number of ring atoms of the thienyl group is 5.
"aryl or aromatic group" refers to an aromatic hydrocarbon group derived from an aromatic ring compound by removal of one hydrogen atom, which may be a monocyclic aryl group, or a fused ring aryl group, or a polycyclic aryl group, at least one of which is an aromatic ring system for a polycyclic 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, benzophenanthrene, perylene, naphthacene, pyrene, benzopyrene, acenaphthene, 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 acenaphthene, fluorene, or 9, 9-diaryl fluorene, triarylamine, diaryl ether systems in particular should also be included in the definition of aryl groups.
"heteroaryl or heteroaromatic group" means that at least one carbon atom is replaced by a non-carbon atom on the basis of an aryl group, which may be an N atom, an O atom, an S atom, or the like. For example, "substituted or unsubstituted heteroaryl having 5 to 60 ring atoms" refers to heteroaryl having 5 to 60 ring atoms, preferably heteroaryl having 6 to 30 ring atoms, more preferably heteroaryl having 6 to 18 ring atoms, particularly preferably heteroaryl having 6 to 14 ring atoms, and heteroaryl is optionally further substituted, suitable examples include, but are not limited to: triazine, pyridine, pyrimidine, imidazole, furan, thiophene, benzofuran, benzothiophene, indole, carbazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrole, furofuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, quinoline, isoquinoline, naphthyridine, quinoxaline, phenanthridine, primary pyridine, quinazoline, quinazolinone, dibenzothiophene, dibenzofuran, carbazole, and derivatives thereof.
"amine group" refers to a derivative of ammonia having the formula-N (X) 2 Wherein 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-NH 2 -N (alkyl) 2 -NH (alkyl), -N (cycloalkyl) 2 -NH (cycloalkyl), -N (heterocyclyl) 2 -NH (heterocyclyl), -N (aryl) 2 -NH (aryl), -N (alkyl) (heterocyclyl), -N (cycloalkyl) (heterocyclyl), -N (aryl) (heteroaryl), -N (alkyl) (heteroaryl), and the like.
"arylalkyl" refers to a hydrocarbon radical derived from an alkyl group in which at least one hydrogen atom bonded to a carbon atom is replaced with an aryl group. Wherein the aryl moiety may comprise from 5 to 20 carbon atoms and the alkyl moiety may comprise from 1 to 9 carbon atoms. Suitable examples include, but are not limited to: benzyl, 2-phenylethan-1-yl, naphthylmethyl, 2-naphthylethan-1-yl, naphthobenzyl and 2-naphthophenylethan-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 containing this term, suitable examples include, but are not limited to: methoxy (-O-CH) 3 or-OMe), ethoxy (-O-CH 2 CH 3 or-OEt) and t-butoxy (-O-C (CH) 3 ) 3 or-OtBu).
In the present invention, "x" linked to a single bond indicates a linking site.
In the present invention, a single bond to which a substituent is attached extends through the corresponding ring, meaning that the substituent may be attached to an optional position on the ring, e.g Any substitutable site of R and benzene ring; for example->Representation->With two optional adjacent C atoms of the benzene ring, form a parallel ring, likewise->Etc.
In the present invention, when the same group contains a plurality of substituents of the same symbol, each substituent may be the same or different from each other, for example6R on benzene ring 1 May be the same or different from each other.
In the present invention, the abbreviations of the substituents correspond to: n-n, sec-sec, i-iso, t-tert, o-o, m-m, p-pair, memethyl, et ethyl, pr propyl, bu butyl, am-n-pentyl, hx hexyl, cy cyclohexyl.
In the embodiment of the invention, the energy level structure, triplet state energy level E of the organic material T HOMO, LUMO play a key role. These energy levels are described below.
HOMO and LUMO energy levels can be measured by photoelectric effects such as XPS (X-ray photoelectron spectroscopy) and UPS (ultraviolet electron spectroscopy) or by cyclic voltammetry (hereinafter referred to as CV). Recently, quantum chemical methods, such as density functional theory (hereinafter abbreviated as DFT), have also become effective methods for calculating molecular orbital energy levels.
Triplet energy level E of organic material T1 This can be measured by low temperature Time resolved luminescence spectroscopy, or by quantum simulation calculations (e.g. by Time-dependent DFT), such as by commercial software Gaussian 09W (Gaussian inc.), specific simulation methods can be seen in WO2011141110 or as described in the examples below.
Note that HOMO, LUMO, E T1 Depending on the measurement method or calculation method used, even for the same method, different evaluation methods, e.g. starting points and peak points on the CV curve, may give different HOMO/LUMO values. Thus, a reasonable and meaningful comparison should be made with the same measurement method and the same evaluation method. In the description of the embodiments of the present invention, HOMO, LUMO, E T1 The values of (2) are based on a simulation of the Time-dependent DFT, but do not affect the application of other measurement or calculation methods.
In the invention, (HOMO-1) is defined as the second highest occupied orbital level, (HOMO-2) is the third highest occupied orbital level, and so on. (lumo+1) is defined as the second lowest unoccupied orbital level, (lumo+2) is the third lowest occupied orbital level, and so on.
The technical proposal is as follows:
an organic compound having a structure represented by the general formula (1):
wherein:
R 1 、R 2 、R 3 each independently selected from: a hydrogen atom, D, or a linear alkyl group having 1 to 20C atoms, a linear alkoxy group having 1 to 20C atoms, a linear 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 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, cyano, haloformyl, formyl, isocyano, isocyanate, thiocyanate or isothiocyanate group, hydroxy, nitro, alkenyl, amine, CF 3 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 5 to 60 ring atoms, or a substituted or unsubstituted aryloxy group having 6 to 60 ring atoms, or a substituted or unsubstituted heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups;
R 1 、R 2 、R 3 at least one of which is selected from the structural formulas (1-1):
L 1 selected from single bonds, or substituted or unsubstituted aromatic or heteroaromatic groups having 6 to 40 ring atoms;
Ar 1 、Ar 2 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, or a non-aromatic ring system;
* Represents a ligation site;
n 1 selected from 0,1,2 or 3; n is n 2 Selected from 0,1,2,3 or 4; n is n 3 Selected from 0,1,2,3 or 4; n is n 1 +n 2 +n 3 ≥1。
In one embodiment, R is 3 Has a structure shown in a 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):
still further, the organic compound has a structure as shown in any one of formulas (3-1) to (3-5):
preferably, the organic compound has a structure as shown in formula (3-1) or (3-2).
Preferably, R as described in the present invention 1 、R 2 Each independently selected from: a hydrogen atom, D, or a linear alkyl group having 1 to 10C atoms, a branched alkyl group having 3 to 10C atoms, or a cyclic 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 is as described in the invention 1 、R 2 Each independently selected from: a hydrogen atom, D, or a linear alkyl group having 1 to 8C atoms, a branched alkyl group having 3 to 8C atoms, or a cyclic alkyl group, or an aromatic group or a heteroaromatic group having 6 to 20 ring atoms.
Further, R as described in the formula (3-1) or (3-2) of the present invention 1 、R 2 Selected from the same structure; further, R as described in the formula (3-1) or (3-2) of the present invention 1 、R 2 Are each selected from phenyl, naphthyl or tert-butyl.
In a preferred embodiment, ar is 1 、Ar 2 Independently selected from substituted or unsubstituted having 6 to 30 ring atomsOr a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms. Further, ar 1 、Ar 2 At least one of which is selected from a condensed ring aromatic group or a heteroaromatic group having 10 to 20 ring atoms which are substituted or unsubstituted.
In a preferred embodiment, ar is 1 、Ar 2 Independently selected from a substituted or unsubstituted aromatic group having 6 to 20 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms.
In one embodiment, the Ar 1 、Ar 2 And (3) independently selected from any one of the groups shown in (B-1) - (B-6):
wherein:
X 1 selected from N or CR 4 ；
Y 1 Selected from O, S, NR 5 Or CR (CR) 5 R 6 ；
R 4 -R 6 Each occurrence is independently selected from: a hydrogen atom, D, or a linear alkyl group having 1 to 20C atoms, a linear alkoxy group having 1 to 20C atoms, a linear 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 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, cyano, haloformyl, formyl, isocyano, isocyanate, thiocyanate or isothiocyanate group, hydroxy, nitro, alkenyl, amine, 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 5 to 60 ring atoms, or a substituted or unsubstituted aryloxy group having 6 to 60 ring atoms Or, or a substituted or unsubstituted heteroaryloxy group having 5 to 60 ring atoms, or a combination of such groups;
R 5 and R is 6 Not forming a ring or being connected with each other to form a ring;
Ar 3 independently selected from substituted or unsubstituted aromatic or heteroaromatic groups having from 6 to 20 ring atoms.
Preferably Ar in (B-3) 3 Any one selected from the following groups:
more preferably, (B-3) is selected from any one of the following groups:
ar as described 1 、Ar 2 Independently selected from any one of the following groups:
n is selected from 0,1,2 or 3.
In one embodiment, R 4 Independently selected from: a hydrogen atom, D, or a linear alkyl group having 1 to 10C atoms, a branched alkyl group having 3 to 10C atoms, or a cyclic 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 4 Each occurrence is independently selected from: a hydrogen atom, D, methyl, tert-butyl, cyclohexyl, adamantyl or phenyl or naphthyl.
Further, ar 1 、Ar 2 Independently selected from the group consisting of:
the L is 1 Each occurrence is independently selected from a single bond or any one of the following groups:
Wherein:
X 2 each occurrence is independently selected from CR 7 Or N;
Y 2 each occurrence is independently selected from NR 8 、CR 8 R 9 O or S;
R 7 -R 9 each occurrence is independently selected from: a hydrogen atom, D, a linear 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, L 1 Selected from single bond, or substituted or unsubstituted benzene, naphthalene, anthracene, phenanthrene, perylene, naphthacene, pyrene, benzopyrene, triphenylene, acenaphthene, fluorene, dibenzofuran, dibenzothiophene ring structure.
Further, said L 1 Each occurrence is independently selected from a single bond or any one of the following groups:
further, L 1 Selected from a single bond, or a substituted or unsubstituted phenyl group, or a substituted or unsubstituted naphthyl group.
In a preferred embodiment, in formula (1)Any one of the following groups:
more preferably, the process is carried out,y in (3) 1 Selected from O, S, NR 5 Or CR (CR) 5 R 6 ；
Examples of the organic compounds of the present invention are listed below, but are not limited to:
The organic compound according to the present invention can be used as a functional material in a functional layer of an electronic device. 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), an emitting layer (EML).
In one embodiment, the organic compound according to the present invention is used in a hole transport layer.
The invention further relates to a mixture comprising at least one organic compound as described above, and at least one further organic functional material selected from the group consisting of a Hole Injection Material (HIM), a Hole Transport Material (HTM), an Electron Transport Material (ETM), an Electron Injection Material (EIM), an Electron Blocking Material (EBM), a Hole Blocking Material (HBM), a luminescent material (Emitter), a Host material (Host) and an organic dye. Various organic functional materials are described in detail in, for example, WO2010135519A1, US20090134784A1 and WO 2011110277A1, the entire contents of which 3 patent documents are hereby incorporated by reference.
In one embodiment, the another organic functional material is selected from electron transport materials, and is used as a co-host in an electronic device.
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, borate or phosphate compound, or mixture of two or more solvents.
In a preferred embodiment, a composition according to the invention, said at least one organic solvent is chosen from solvents based on aromatic or heteroaromatic groups.
Examples of aromatic or heteroaromatic-based solvents suitable for the present invention are, but are not limited to: para-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1, 4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, dipentylbenzene, tripentylbenzene, pentyltoluenes, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2,3, 4-tetramethylbenzene, 1,2,3, 5-tetramethylbenzene, 1,2,4, 5-tetramethylbenzene, butylbenzene, dodecylbenzene, dihexylbenzene, dibutylbenzene, p-diisopropylbenzene, cyclohexylbenzene, benzylbutylbenzene, dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, 1-methylnaphthalene, 1,2, 4-trichlorobenzene, 4-difluorodiphenyl methane, 1, 2-dimethoxy-4- (1-propenyl) benzene, diphenyl methane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, α -dichlorodiphenyl methane, 4- (3-phenylpropyl) pyridine, benzyl benzoate, 1-bis (3, 4-dimethylphenyl) ethane, 2-isopropylnaphthalene, 2-quinolinecarboxylic acid, ethyl ester, 2-methylfuran, etc.;
Examples of aromatic ketone-based solvents suitable for the present invention are, but are not limited to: 1-tetralone, 2- (phenylepoxy) tetralone, 6- (methoxy) tetralone, acetophenone, propiophenone, benzophenone, and derivatives thereof, such as 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylpropionophenone, 3-methylpropionophenone, 2-methylpropionophenone, and the like;
examples of aromatic ether-based solvents suitable for the present invention are, but are not limited to: 3-phenoxytoluene, butoxybenzene, p-anisaldehyde dimethyl acetal, tetrahydro-2-phenoxy-2H-pyran, 1, 2-dimethoxy-4- (1-propenyl) benzene, 1, 4-benzodioxane, 1, 3-dipropylbenzene, 2, 5-dimethoxytoluene, 4-ethylben-ther, 1, 3-dipropoxybenzene, 1,2, 4-trimethoxybenzene, 4- (1-propenyl) -1, 2-dimethoxybenzene, 1, 3-dimethoxybenzene, glycidyl phenyl ether, dibenzyl ether, 4-t-butyl anisole, trans-p-propenyl anisole, 1, 2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran, ethyl-2-naphthyl ether;
in some preferred embodiments, the composition according to the invention, said at least one solvent may be chosen from: aliphatic ketones such as 2-nonene, 3-nonene, 5-nonene, 2-decanone, 2, 5-adipone, 2,6, 8-trimethyl-4-nonene, fenchyl ketone, phorone, isophorone, di-n-amyl ketone and the like; or aliphatic ethers such as amyl ether, hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and the like.
In other preferred embodiments, the at least one solvent according to the compositions of the present invention may be chosen from ester-based solvents: alkyl octanoates, alkyl sebacates, alkyl stearates, alkyl benzoates, alkyl phenylacetates, alkyl cinnamates, alkyl oxalates, alkyl maleates, alkyl lactones, alkyl oleates, and the like. Particular preference is given to octyl octanoate, diethyl sebacate, diallyl phthalate and isononyl isononanoate.
The solvent may be used alone or as a mixture of two or more organic solvents.
In certain preferred embodiments, a composition according to the present invention comprises at least one organic compound or mixture as described above and at least one organic solvent, and may further comprise another organic solvent. Examples of other organic solvents include (but are not limited to): methanol, ethanol, 2-methoxyethanol, methylene chloride, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1, 4-dioxane, acetone, methyl ethyl ketone, 1,2 dichloroethane, 3-phenoxytoluene, 1-trichloroethane, 1, 2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethylsulfoxide, tetrahydronaphthalene, decalin, indene and/or mixtures thereof.
In some preferred embodiments, particularly suitable solvents for the present invention are solvents having Hansen (Hansen) solubility parameters within the following ranges:
δd (dispersion force) is in the range of 17.0 to 23.2MPa1/2, particularly in the range of 18.5 to 21.0MPa 1/2;
δp (polar force) is in the range of 0.2 to 12.5MPa1/2, particularly in the range of 2.0 to 6.0MPa 1/2;
δh (hydrogen bonding force) is in the range of 0.9 to 14.2MPa1/2, particularly in the range of 2.0 to 6.0MPa 1/2.
The composition according to the invention, wherein the organic solvent is selected taking into account its boiling point parameters. In the invention, the boiling point of the organic solvent is more than or equal to 150 ℃; preferably not less than 180 ℃; more preferably not less than 200 ℃; more preferably not less than 250 ℃; the optimal temperature is more than or equal to 300 ℃. Boiling points in these ranges are beneficial in preventing nozzle clogging of inkjet printheads. The organic solvent may be evaporated from the solvent system to form a film comprising the functional material.
In a preferred embodiment, the composition according to the invention is a solution.
In another preferred embodiment, the composition according to the invention is a suspension.
The compositions according to embodiments of the present invention may comprise from 0.01% to 10% by weight of a compound or mixture according to the present invention, preferably from 0.1% to 15% by weight, more preferably from 0.2% to 5% by weight, most preferably from 0.25% to 3% by weight.
The invention also relates to the use of said composition as a coating or printing ink for the production of organic electronic devices, particularly preferably by printing or coating.
Suitable Printing or coating techniques include, but are not limited to, ink jet Printing, spray Printing (nozle Printing), letterpress Printing, screen Printing, dip coating, spin coating, doctor blade coating, roller Printing, twist roller Printing, lithographic Printing, flexography, rotary Printing, spray coating, brush or pad Printing, slot die coating, and the like. Gravure printing, inkjet printing and inkjet printing are preferred. The solution or suspension may additionally include one or more components such as surface active compounds, lubricants, wetting agents, dispersants, hydrophobing agents, binders, etc., for adjusting viscosity, film forming properties, improving adhesion, etc. The printing technology and the related requirements of the solution, such as solvent, concentration, viscosity and the like.
The invention also provides the use of an organic compound, mixture or composition as described above in an organic electronic device.
The technical proposal is as follows:
an organic electronic device comprising at least one functional layer comprising an organic compound, mixture 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 emitting 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 a 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 an embodiment, the organic electronic device according to the present invention may be selected from, but not limited to, organic Light Emitting Diodes (OLED), organic photovoltaic cells (OPV), organic light emitting cells (OLEEC), organic Field Effect Transistors (OFET), organic light emitting field effect transistors, organic lasers, organic spintronics, organic sensors and organic plasmon emitting diodes (Organic Plasmon Emitting Diode), etc., particularly preferably OLED. In the embodiment of the 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 light organic electronic device.
In an embodiment, the organic electronic device according to the invention comprises a first electrode, a second electrode, one or more organic functional layers between the first electrode and the second electrode, said functional layers comprising at least two functional layers: one of the functional layers is a hole transporting 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 comprising a metal complex represented by the general formula (4):
wherein:
q is selected from 1 or 2;
Ar 5 independently selected from substituted or unsubstituted heteroaryl groups having 5 to 40 ring atoms;
Ar 6 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;
R 10 -R 11 each occurrence is independently selected from: a hydrogen atom, D, a linear alkyl group having 1 to 20C atoms, a linear alkyl group having 3 to 20C atomsA branched or cyclic alkyl group of 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, ar 5 And is independently selected from quinoline or isoquinoline and derivatives thereof at multiple occurrences.
In one embodiment, ar 6 And are independently selected from phenyl and derivatives thereof at multiple occurrences.
Preferably, the metal complex has a structure represented by any one of the general formulae (5-1) to (5-3):
wherein:
a is selected from 0,1,2,3,4,5 or 6, b is selected from 0,1,2,3 or 4;
R 12 -R 13 each occurrence is independently selected from: d, a linear 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, at least one R 12 Or R is 13 Selected from linear alkyl groups having 1 to 20C atoms, or branched or cyclic alkyl groups having 3 to 20C atoms.
In one embodiment, at least one R 13 Selected from linear alkyl groups having 1 to 20C atoms, or branched or cyclic alkyl groups having 3 to 20C atoms. Further, at least one R 12 Selected from linear alkyl groups having 1 to 20C atoms, or branched or cyclic alkyl groups having 3 to 20C atoms.
The metal complexes according to formula (4) are preferably selected from, but not limited to, the following structures, which may be optionally substituted:
the light emitting device according to the present invention has a light emitting 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 invention will be described in connection with preferred embodiments, but the invention is not limited to the embodiments described below, it being understood that the appended claims outline the scope of the invention and those skilled in the art, guided by the inventive concept, will recognize that certain changes made to the embodiments of the invention will be covered by the spirit and scope of the claims.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
1. Synthesis of Compounds
Example 1: synthesis of Compound 1
Synthesis of intermediate 1-3: 1-1 (30 mmol), 1-2 (30 mmol), cesium carbonate (40 mmol) were added to dry DMF (200 ml), warmed to 130℃and stirred for 6h. After cooling, the reaction solution was poured into a large amount of water and suction-filtered. The filter cake is subjected to column chromatography and recrystallization in sequence to obtain the intermediate 1-3, and the yield is 71%.
Synthesis of intermediates 1-5: 1-3 (20 mmol) was dissolved in dry THF, cooled to-78℃under nitrogen, n-butyllithium solution (2M, 10 ml) was slowly added dropwise and stirring continued for 2h. A solution of 1-4 (20 mmol) in THF was added under nitrogen, then allowed to spontaneously recover to room temperature and the reaction continued for 12h. And adding a proper amount of dilute hydrochloric acid into the reaction solution, and continuing the reaction for 0.5h. Most of the solvent was then removed by rotary evaporation. The product was extracted with dichloromethane and washed three times with water. The organic phase was collected, the solvent was removed by rotary evaporation, and the crude product obtained was dissolved in a hydrochloric acid/acetic acid (volume ratio 1:9) mixed solvent, and stirred for 4 hours at 70 ℃. After cooling, the reaction solution was poured into a large amount of water and suction-filtered. The filter residue is washed with water, saturated sodium carbonate solution and water for several times in sequence, and then the intermediate 1-5 is obtained through recrystallization, and the yield is 75%.
Synthesis of intermediates 1-6: intermediate 1-5 (15 mmol) was dissolved in DMF (150 ml) and pinacol diboronate (15 mmol), pd (dppf) Cl was added 2 (0.2 mmol), tricyclohexylphosphine (0.6 mmol) and potassium acetate (35 mmol) were reacted under nitrogen at 130℃for 12 hours. After cooling, the reaction solution was poured into a large amount of water and stirred for 1h. Suction filtration, and purifying the obtained solid crude product by column chromatography to obtain the intermediate 1-6 with the yield of 62%.
Synthesis of Compound 1: 1 to 6 (12 mmol), 1 to 7 (12 mmol), pd (PPh) 3 ) 4 (0.1 mmol) and potassium carbonate (20 mmol) were added to 150ml of a 1, 4-dioxane/water (volume ratio: 9:1) mixed solvent, and refluxed under nitrogen atmosphere for 8 hours. After cooling, most of the solvent was distilled off under reduced pressure, and the remaining material was dissolved with methylene chloride and washed three times with water. The organic phase is collected, the solvent is removed by rotary evaporation, and the obtained 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
The synthesis of intermediate 2-2 was referenced to the synthesis of 1-3, except that 1-1 was replaced with 2-1 in 74% yield.
The synthesis of intermediate 2-3 was referenced to the synthesis of 1-5, except that 1-3 was replaced with 2-2 in 70% yield.
Synthesis of Compound 2: 2-3 (10 mmol), 2-4 (10 mmol), pd (dba) 2 (0.2 mmol), tri-t-butylphosphine (0.6 mmol), sodium t-butoxide (20 mmol) were added to dry toluene (150 ml), and stirred under nitrogen at 110℃for 6h.After cooling, the solvent was removed by rotary evaporation, and 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 the compound 2 with the yield of 80%. MS (ASAP): 763.
EXAMPLE 3 Synthesis of Compound 3
Synthesis of Compound 3 referring to the synthesis of Compound 2, except that 2-3 was replaced with 1-5 and 2-4 was replaced with 3-1, the yield was 80%. MS (ASAP): 741.
EXAMPLE 4 Synthesis of Compound 4
The synthesis of intermediate 4-2 was referenced to the synthesis of 1-3, except that 1-2 was replaced with 4-1 in 72% yield.
The synthesis of intermediate 4-3 was referenced to the synthesis of 1-5, except that 1-3 was replaced with 4-2 in 75% yield.
Synthesis of Compound 4 referring to the synthesis of Compound 2, except that 2-3 was replaced with 4-3 and 2-4 was replaced with 4-4, the yield was 82%. MS (ASAP): 697.
EXAMPLE 5 Synthesis of Compound 5
The synthesis of intermediate 5-1 was referenced to the synthesis of 1-3, except that 1-1 was replaced with 2-1 and 1-2 was replaced with 4-1 in 70% yield.
The synthesis of intermediate 5-2 was referenced to the synthesis of 1-5, except that 1-3 was replaced with 5-1 in 75% yield.
Synthesis of Compound 5 referring to the synthesis of Compound 2, except that 2-3 was replaced with 5-2 and 2-4 was replaced with 5-3, the yield was 84%. MS (ASAP): 733.
EXAMPLE 6 Synthesis of Compound 6
Synthesis of Compound 6 reference the synthesis of Compound 2, except that 2-3 was replaced with 4-3 and 2-4 was replaced with 4-4 in 83% yield. MS (ASAP): 695.
EXAMPLE 7 Synthesis of Compound 7
Synthesis of intermediate 7-3: 7-1 (30 mmol), 7-2 (30 mmol), pd (PPh) 3 ) 4 (0.3 mmol) and potassium carbonate (40 mmol) were added to 250ml of a 1, 4-dioxane/water (volume ratio 9:1) mixed solvent, and stirred under nitrogen atmosphere at 80℃for 6h. After cooling, most of the solvent was distilled off under reduced pressure, and the remaining reaction solution was dissolved with methylene chloride and washed three times with water. The organic phase is collected, the solvent is removed by rotary evaporation, and the obtained crude product is subjected to column chromatography and recrystallization to obtain 7-3 with the yield of 85 percent.
Synthesis of intermediate 7-4: 7-3 (24 mmol) was dissolved in 120ml of triethyl phosphite, heated to 120℃and stirred for 7h. After cooling, the solvent was distilled off under reduced pressure, and the obtained crude product was purified by column chromatography to give 7-4 in 80% yield.
Synthesis of intermediate 7-5: 7-4 (19 mmol), iodobenzene (19 mmol), cuprous iodide (30 mmol), trans-1, 2-cyclohexanediamine (60 mmol), potassium phosphate (35 mmol) were added to dry toluene and stirred under nitrogen at 100℃for 5h. After cooling, filtration was performed. Most of the solvent was removed by rotary evaporation, and 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 was purified by column chromatography to give 7-5 in 75% yield.
The synthesis of intermediate 7-6 was referenced to the synthesis of 1-5, except that 1-3 was replaced with 7-5 in 72% yield.
Synthesis of Compound 7 reference 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
The synthesis of intermediate 8-2 was referenced to the synthesis of 7-3, except that 7-2 was replaced with 8-1 in 83% yield.
The synthesis of intermediate 8-3 was referenced to the synthesis of 7-4, except that 7-3 was replaced with 8-2 in 80% yield.
The synthesis of intermediate 8-5 was referenced to the synthesis of 1-3, except that 1-1 was replaced with 8-3 and 1-2 was replaced with 8-4 in 80% yield.
The synthesis of intermediate 8-6 was referenced to the synthesis of 1-5, except that 1-3 was replaced with 8-5 in 75% yield.
The synthesis of intermediate 8-7 was referenced to the synthesis of 1-6, except that 1-5 was replaced with 8-6 in 63% yield.
Synthesis of Compound 8 referring to the synthesis of Compound 1, except that 1-6 was replaced with 8-7 and 1-7 was replaced with 8-8, the yield was 90%. MS (ASAP): 697.
EXAMPLE 9 Synthesis of Compound 9
Synthesis of intermediate 9-3: 9-1 (30 mmol), 9-2 (30 mmol), pd (dba) 2 (0.2 mmol), tri-t-butylphosphine (0.6 mmol), sodium t-butoxide (40 mmol) were added to dry toluene (180 ml), and stirred under nitrogen at 70℃for 4 hours. 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, and the yield is 77%.
The synthesis of intermediate 9-5 was referenced to the synthesis of 9-3, except that 9-1 was replaced with 9-3 and 9-2 was replaced with 9-4 in 80% yield.
The synthesis of intermediate 9-8 was referenced 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.
The synthesis of intermediate 9-9 was referenced to the synthesis of 7-4, except that 7-3 was replaced with 9-8 in 81% yield.
Synthesis of intermediate 9-10 referring to the synthesis of 7-5, except that 7-4 was replaced with 9-9 in 74% yield
The synthesis of intermediate 9-11 was referenced to the synthesis of 1-5, except that 1-3 was replaced with 9-10 in 73% yield.
The synthesis of intermediate 9-12 was referenced to the synthesis of 1-6, except that 1-5 was replaced with 9-11 in 60% yield.
Synthesis of Compound 9 reference the synthesis of Compound 1, except that 1-6 was replaced with 9-12 and 1-7 was replaced with 9-5 in 70% yield. MS (ASAP): 845.
EXAMPLE 10 Synthesis of Compound 10
The synthesis of intermediate 10-2 was referenced to the synthesis of 7-5, except that iodobenzene was replaced with 10-1 in 80% yield.
The synthesis of intermediate 10-3 was referenced to the synthesis of 1-5, except that 1-3 was replaced with 10-2 in 75% yield.
Synthesis of Compound 10: 10-3 (12 mmol), 10-4 (24 mmol), pd (dba) 2 (0.2 mmol), tri-t-butylphosphine (0.6 mmol), sodium t-butoxide (40 mmol) were added to dry toluene (180 ml), and stirred under nitrogen at 110℃for 6h. After cooling, the solvent was removed by rotary evaporation, and 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 the compound 10 with the yield of 80%. MS (ASAP): 712.
EXAMPLE 11 Synthesis of Compound 11
The synthesis of intermediate 11-2 was referenced to the synthesis of 1-3, except that 1-1 was replaced with 11-1, 1-2 was replaced with 4-1, and the yield was 70%.
The synthesis of intermediate 11-3 was referenced to the synthesis of 1-5, except that 1-3 was replaced with 11-2 in 72% yield.
Synthesis of Compound 11 referring to the synthesis of Compound 2, except that 2-3 was replaced with 11-3 and 2-4 was replaced with 11-4, the yield was 80%. MS (ASAP): 813.
EXAMPLE 12 Synthesis of Compound 12
The synthesis of intermediate 12-1 was referenced to the synthesis of 1-6, except that 1-5 was replaced with 2-3 in 60% yield.
Synthesis of Compound 12 referring to the synthesis of Compound 1, except that 1-6 was replaced with 12-1 and 1-7 was replaced with 12-2, the yield was 90%. MS (ASAP): 809.
EXAMPLE 13 Synthesis of Compound 13
Synthesis of Compound 13 reference 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
Synthesis of Compound 14 referring to the synthesis of Compound 2, except that 2-3 was replaced with 4-3 and 2-4 was replaced with 14-1, the yield was 70%. MS (ASAP): 710.
2. preparing and detecting a device:
device example 1
The device structure is ITO/hole injection layer (10 nm)/first hole transport layer (60 nm)/second hole transport layer (60 nm)/host material RH 1:red light object/ETM:Liq/LiF/Al. Wherein the mass ratio of the main materials RH1 and RD2 is 95:5. The 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, and then performing ultraviolet ozone plasma treatment;
b. the hole injection layer is formed by HT1/HATCN (97/3,w/w) on the ITO layer under high vacuum (1×10) -6 Millibar) by thermal evaporation;
c. evaporating HT1 with the thickness of 60nm on the hole injection layer as a first hole transport layer;
d. evaporating the compound 1 with the thickness of 60nm on the first hole transport layer to serve as a second hole transport layer;
e. vacuum evaporating a 40nm light-emitting layer on the second hole transport layer; the light-emitting layer comprises RH1 as a host material and RD1 as a guest material, wherein the two materials are subjected to multi-source co-evaporation; wherein the evaporation rate of RD2 is controlled to be 5% of RH 1;
f. evaporating an ETM/Liq (1:1 mass ratio) mixture with the thickness of 25nm on the light-emitting layer to serve as an electron transport layer; evaporating LiF with the wavelength of 0.5nm on the electron transport layer to serve as an electron injection layer; evaporating Al with the thickness of 150nm on the electron injection layer to serve as a cathode;
g. encapsulation the device was encapsulated with an ultraviolet hardening resin in a nitrogen glove box to produce an OLED device 1.
The OLED devices 2 to 29 were prepared by referring to device example 1, except that the second hole transport layer material (compound 1) or red light guest material RD2 was replaced with a compound shown in table 1.
The current-voltage (J-V) characteristics of each OLED device were characterized by a characterization apparatus while recording important parameters such as efficiency, lifetime, and external quantum efficiency. Table 2 shows the lifetime and external quantum efficiency comparisons of OLED devices, where lifetime LT95 is the time at which luminance drops to 95% of the initial luminance @1000nits at constant current. Here, LT95, external quantum efficiency was calculated with respect to comparative device example 1 (corresponding material comparative example 1), i.e., with the lifetime of comparative device example 1 being 1, external quantum efficiency was 100%. The results are shown in Table 1.
Table 1: comparison of OLED device Performance
As can be seen from table 1, device external quantum efficiencies and lifetimes of device examples 1-25 were 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 R 3 The device performance of the compound selected from the general formula (1-1) is better than that of R alone 1 Or R is 2 Selected from the compounds of the general formula (1-1). Compound 2, compound 5, compound 11, compound 12 have a relatively higher device efficiency and lifetime than the other device examples, indicating that when R 3 R is selected from (1-1) 1 And R is 2 The presence of the groups has an effect on the efficiency of the device. Therefore, the luminous efficiency and the service life of the OLED device prepared by the organic mixture are obviously improved.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims (10)

1. An organic compound having a structure represented by the general formula (1):
wherein:
R 1 、R 2 、R 3 one of them is selected from the structural formula (1-1) or R 1 、R 2 One of R 3 Selected from the structural formula (1-1):
Ar 1 、Ar 2 and is independently selected from any one of the following groups:
Ar 3 any one selected from the following groups:
X 1 selected from CR 4 ；
Y 1 Selected from O, S, NR 5 Or CR (CR) 5 R 6 ；
R 4 Each occurrence is independently selected from R 4 Independently selected from: a hydrogen atom, adamantyl, or phenyl;
R 5 -R 6 each occurrence is independently selected from: methyl, or phenyl;
* Represents a ligation site;
L 1 each occurrence is independently selected from a single bond or any one of the following groups:
X 2 each occurrence is independently selected from CR 7 ，R 7 Selected from hydrogen atoms;
R 1 、R 2 、R 3 at least one not selected from the structural formulae (1-1), each occurrence of which is independently selected from: a hydrogen atom, a tert-butyl group, or a phenyl group;
n 1 selected from 0 or 1; n is n 2 Selected from 0 or 1; n is n 3 Selected from 0 or 1, n 1 +n 2 +n 3 ≥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):
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):
4. the organic compound according to claim 1, wherein Ar is 1 、Ar 2 Independently selected from any one of the following groups:
n is selected from 0 or 1.
5. The organic compound according to claim 1, wherein the compound of the formula (1)Any one of the following groups:
6. a mixture comprising an organic compound according to any one of claims 1 to 5, 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.
7. A composition comprising at least one organic compound according to any one of claims 1 to 5, or a mixture according to claim 6, and at least one organic solvent.
8. An organic electronic device comprising at least one functional layer comprising an organic compound according to any one of claims 1 to 5, or a mixture according to claim 6, or prepared from a composition according to claim 7.
9. The organic electronic device of claim 8, comprising a first electrode, a second electrode, one or more organic functional layers between the first electrode and the second electrode, wherein the functional layers comprise at least two functional layers:
Wherein one functional layer is a hole transporting layer or an electron blocking layer comprising the organic compound according to any one of claims 1 to 5, or the mixture according to claim 6, or prepared from the composition according to claim 7;
the other functional layer is a light-emitting layer comprising a metal complex represented by the general formula (4):
wherein:
q is selected from 1 or 2;
Ar 5 independently at each occurrence a substituted or unsubstituted heteroaromatic group having from 5 to 40 ring atoms;
Ar 6 independently at each occurrence, 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;
R 10 -R 11 each occurrence is independently selected from: a hydrogen atom, D, a linear 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.
10. The organic electronic device according to claim 9, wherein the light-emitting layer comprises a metal complex represented by any one of structures of general formulae (5-1) to (5-3):
Wherein:
a is selected from 0,1,2,3,4,5 or 6, b is selected from 0,1,2,3 or 4;
R 12 -R 13 each occurrence is independently selected from: d, a linear 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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CN110746405A (en) * 2018-12-14 2020-02-04 广州华睿光电材料有限公司 Pyrrole group-containing compound and application thereof in organic electronic device
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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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