CN112625023A

CN112625023A - Sulfur-containing heterocycle substituted cyclopropane compound and application thereof

Info

Publication number: CN112625023A
Application number: CN202011000944.0A
Authority: CN
Inventors: 温华文; 杨曦; 刘爱香; 宋晶尧
Original assignee: Guangzhou Chinaray Optoelectronic Materials Ltd
Current assignee: Guangzhou Chinaray Optoelectronic Materials Ltd
Priority date: 2019-10-08
Filing date: 2020-09-22
Publication date: 2021-04-09

Abstract

The invention provides a sulfur-containing compositionHeterocyclic substituted cyclopropane compounds and their use in organic electroluminescent devices. The cyclopropane compound containing a thioheterocycle substitution has a structure represented by general formula (1). The compound provided by the invention contains a central structure of the sulfur heterocyclic ring substituted cyclopropane, and has excellent hole transport property and stability. When the organic electroluminescent material is used as a doping material, a blocking material, a charge injection material and the like in an organic semiconductor, particularly in an organic electronic device, the organic electroluminescent material can be driven by low voltage, the electroluminescent efficiency can be improved, and the service life of the device can be prolonged.

Description

Sulfur-containing heterocycle substituted cyclopropane compound and application thereof

The present application claims priority from chinese patent application filed on 2019, 10/08, under the name of "a sulfur-containing heterocycle-substituted cyclopropane compound and its use", chinese patent office, application No. 201910948275.0, the entire contents of which are incorporated herein by reference.

Technical Field

The invention relates to the field of electroluminescent materials, in particular to a sulfur-containing heterocycle substituted cyclopropane compound and application thereof.

Background

Organic Light Emitting Diodes (OLEDs) have great potential for applications in optoelectronic devices such as flat panel displays and lighting due to the versatility of organic semiconductor materials in synthesis, relatively low manufacturing costs, and excellent optical and electrical properties.

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 and a negative electrode and an organic layer therebetween. In order to improve the efficiency and lifetime of the organic electroluminescent element, the organic 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 layer, electrons are injected from the negative electrode into the organic layer, excitons are formed when the injected holes and electrons meet, 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, high responsiveness and the like.

In order to realize an efficient organic electroluminescent device, in addition to the development of a high-performance light emitting material, efficient injection transport of electrons and holes from a cathode and an anode, respectively, is a key among them. It has been known in recent years that the conductivity of organic semiconducting materials can be greatly influenced by doping the materials. For the hole-transporting matrix material, it may be composed of a host compound having good electron donor properties and a dopant compound having good electron acceptor properties. Strong electron acceptors, such as Tetracyanoquinodimethane (TCNQ) or 2,3,5, 6-tetrafluoro-tetracyano-1, 4-benzoquinodimethane (F4TCNQ), are now widely used for doping electron donor Materials (Chemical Science 2018,9(19), 4468-. The action mechanism is mainly that holes are generated through the interaction of an electron acceptor dopant and an electron donor host material, and the number and the mobility of the holes enable the conductivity of the substrate material to be obviously changed.

However, these current doping compounds have a number of drawbacks when used for doping, such as: the operation is unstable in the manufacturing process of the organic light emitting diode, the stability is insufficient when the organic light emitting diode is driven, the life is reduced, or the above compound is diffused in the device to contaminate the device when the organic light emitting diode is manufactured by vacuum deposition.

Disclosure of Invention

In view of the defects of the prior art, the invention aims to provide a sulfur-containing heterocyclic ring substituted cyclopropane and application thereof, and aims to provide a novel organic photoelectric functional material, improve the efficiency and the service life of a device.

The technical scheme of the invention is as follows:

an organic compound having a structure represented by general formula (1):

wherein:

ar is independently selected from any one or combination of (A-1) to (A-5) at multiple occurrences:

wherein: x is independently selected from CR at each occurrence₂Or N; (A-1) - (A-5) are selected from the following groups:

each occurrence of Y is independently selected from O, S, S (═ O)₂、CR₃R₄、C＝CR₃R₄、C＝O、C＝S、SiR₃R₄、NR₃；

n is independently selected from 0 or 1 or 2 at each occurrence;

R₁、R₂、R₃、R₄each occurrence is independently selected from H, D, F, Cl, Br, I, CF₃Cyano group, isocyano group, hydroxyl group, nitro group, formyl group, carbamoyl group, haloformyl group, isocyanate group, thiocyanate, isothiocyanate, silyl group, straight-chain alkyl group or alkoxy group or thioalkoxy group having 1 to 20 carbon atoms, branched alkyl group or alkoxy group or thioalkoxy group having 3 to 20 carbon atoms, or cyclic alkyl group having 3 to 20 carbon atomsA group or alkoxy or thioalkoxy group, a ketone group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, a crosslinkable group, a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 60 ring atoms, an aryloxy or heteroaromatic group having 5 to 60 ring atoms, or a combination of these groups;

n1 is selected from any integer of 0-3; n2 is selected from any integer of 0-2; n3 is selected from any integer of 0-4; n4 is selected from any integer of 0-5;

when Ar is selected from (A-1) and n is 0, X is selected from CR₂When R is₂Selected from cyano, nitro, CF₃Cl, Br, F, I, or by cyano, nitro, CF₃Aryl substituted by Cl, Br, F, I, or by cyano, nitro, CF₃Cl, Br, F, I substituted heteroaromatic groups.

A mixture comprising said organic compound, and at least one organic functional material selected from a hole injection material, a hole transport material, an electron injection material, an electron blocking material, a hole blocking material, a light emitter, a host material or an organic dye.

A composition comprising said organic compound or said mixture, and at least one organic solvent.

An organic electronic device comprising said organic compound or said mixture or prepared from said composition.

Has the advantages that:

the organic compound has excellent hole transport property and stability, can be used as a hole injection layer material in an organic electroluminescent element, and can also be used as a dopant to be doped in a hole injection layer or a hole transport layer, so that the organic compound can be driven by low voltage, the electroluminescent efficiency can be improved, and the service life of a device can be prolonged

Drawings

Fig. 1 is a schematic structural view of an organic light emitting device according to an embodiment of the present invention.

In the drawing, 101 denotes a substrate, 102 denotes an anode, 103 denotes a Hole Injection Layer (HIL), 104 denotes a Hole Transport Layer (HTL), 105 denotes a light-emitting layer, 106 denotes an Electron Injection Layer (EIL) or an Electron Transport Layer (ETL), and 107 denotes a cathode.

Detailed Description

In order that the invention may be more fully understood, reference will now be made to the accompanying examples. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

The invention provides an organic compound and application thereof in an organic electronic device. In order to make the objects, technical solutions and effects of the present invention clearer and clearer, the present invention is described in further detail below. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

In the present invention, "substituted" means that a hydrogen atom in a substituent is substituted by a substituent.

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.

An aromatic group refers to a hydrocarbon group containing at least one aromatic ring. A heteroaromatic group refers to an aromatic hydrocarbon group that contains at least one heteroatom. The heteroatoms are preferably selected from Si, N, P, O, S and/or Ge, particularly preferably from Si, N, P, O and/or S. By fused ring aromatic group is meant that the rings of the aromatic group may have two or more rings in which two carbon atoms are shared by two adjacent rings, i.e., fused rings. The fused heterocyclic aromatic group means a fused ring aromatic hydrocarbon group containing at least one hetero atom. For the purposes of the present invention, aromatic or heteroaromatic radicals include not only aromatic ring systems but also non-aromatic ring systems. Thus, systems such as pyridine, thiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, pyrazine, pyridazine, pyrimidine, triazine, carbene and the like are likewise considered for the purposes of the present invention to be aromatic or heterocyclic aromatic groups. For the purposes of the present invention, fused-ring aromatic or fused-heterocyclic aromatic ring systems include not only systems of aromatic or heteroaromatic groups, but also systems in which a plurality of aromatic or heterocyclic aromatic groups may also be interrupted by short non-aromatic units (< 10% of non-H atoms, preferably less than 5% of non-H atoms, such as C, N or O atoms). Thus, for example, systems such as 9, 9' -spirobifluorene, 9, 9-diarylfluorene, triarylamines, diaryl ethers, etc., are also considered fused aromatic ring systems for the purposes of the present invention.

In the embodiment of the present invention, the energy level structure of the organic material, the triplet energy level ET, HOMO, and 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.

The triplet energy level ET1 of the organic material may be measured by low temperature Time resolved luminescence spectroscopy, or may be obtained by quantum simulation calculations (e.g. by Time-dependent DFT), such as by commercial software Gaussian03W (Gaussian Inc.), specific simulation methods may be found in WO2011141110 or as described in the examples below.

It should be noted that the absolute values of HOMO, LUMO, ET1 depend on the measurement or calculation method used, and even for the same method, different methods of evaluation, e.g. starting point and peak point on the CV curve, 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, the values of HOMO, LUMO, ET1 are based on the simulation of Time-dependent DFT, but do 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 present invention provides an organic compound having a structure represented by general formula (1):

wherein:

n is independently selected from 0 or 1 or 2 at each occurrence;

R₁、R₂、R₃、R₄each occurrence is independently selected from H, D, F, Cl, Br, I, CF₃Cyano groups, isocyano groups, hydroxyl groups, nitro groups, formyl groups, carbamoyl groups, haloformyl groups, isocyanates, thiocyanates, isothiocyanates, silyl groups, straight-chain alkyl or alkoxy or thioalkoxy groups having 1 to 20 carbon atoms, branched alkyl or alkoxy or thioalkoxy groups having 3 to 20 carbon atoms, cyclic alkyl or alkoxy or thioalkoxy groups having 3 to 20 carbon atoms, ketone groups having 1 to 20 carbon atoms, alkoxycarbonyl groups having 2 to 20 carbon atoms, aryloxycarbonyl groups having 7 to 20 carbon atoms, crosslinkable groups, substituted or unsubstituted aromatic or heteroaromatic groups having 5 to 60 ring atoms, aryloxy or heteroaryloxy groups having 5 to 60 ring atoms, or combinations of these groups;

In one embodiment, n1 is selected from any integer from 1 to 3; in one embodiment, n2 is selected from any integer from 1 to 2; in one embodiment, n3 is selected from any integer from 1 to 4; in one embodiment, n4 is selected from any integer from 1 to 5;

when n is 0;

in a certain embodiment, X are all selected from CR₂(ii) a Preferably, at least one R₂Selected from cyano, nitro, CF₃Cl, Br, F, I, or by cyano, nitro, CF₃Aryl substituted by Cl, Br, F, I, or by cyano, nitro, CF₃Heteroaromatic groups substituted with Cl, Br, F, I; preferably, R₂Are all selected from cyano, nitro, CF₃Cl, Br, F, I, or by cyano, nitro, CF₃、Cl、Br, F, I substituted aromatic radical, or by cyano, nitro, CF₃Cl, Br, F, I substituted heteroaromatic groups.

In a certain preferred embodiment, at least one X is selected from N and at least one X is selected from CR₂(ii) a More preferably, at least one R₂Selected from cyano, nitro, CF₃Cl, Br, F, I, or by cyano, nitro, CF₃Aryl substituted by Cl, Br, F, I, or by cyano, nitro, CF₃Heteroaromatic groups substituted with Cl, Br, F, I; more preferably, R₂Are all selected from cyano, nitro, CF₃Cl, Br, F, I, or by cyano, nitro, CF₃Aryl substituted by Cl, Br, F, I, or by cyano, nitro, CF₃Cl, Br, F, I substituted heteroaromatic groups.

When n is 1 or 2;

in a certain preferred embodiment, X are all selected from CR₂(ii) a More preferably, at least one R₂Selected from cyano, nitro, CF₃Cl, Br, F, I, or by cyano, nitro, CF₃Aryl substituted by Cl, Br, F, I, or by cyano, nitro, CF₃Heteroaromatic groups substituted with Cl, Br, F, I; more preferably, R₂Are all selected from cyano, nitro, CF₃Cl, Br, F, I, or by cyano, nitro, CF₃Aryl substituted by Cl, Br, F, I, or by cyano, nitro, CF₃Cl, Br, F, I substituted heteroaromatic groups.

In a certain preferred embodiment, at least one X is selected from N and at least one X is selected from CR₂(ii) a More preferably, at least one R₂Selected from cyano, nitro, CF₃Cl, Br, F, I, or by cyano, nitro, CF₃Aryl substituted by Cl, Br, F, I, or by cyano, nitro, CF₃Heteroaromatic groups substituted with Cl, Br, F, I; more preferably, R₂Are all selected from cyano, nitro, CF₃Cl, Br, F, I, or by cyano, nitro, CF₃Aryl substituted by Cl, Br, F, I, or by cyano, nitro, CF₃、Cl、Br、F. I substituted heteroaromatic groups.

In a certain preferred embodiment, Ar is preferably selected from (A-1), (A-3), (A-4) or (A-5).

In one embodiment, n is selected from 2.

In one embodiment, each occurrence of X in (A-1) is independently selected from CR₂(ii) a Further, at least one R₂Selected from cyano, nitro, CF₃Cl, Br, F, I, or by cyano, nitro, CF₃Aryl substituted by Cl, Br, F, I, or by cyano, nitro, CF₃Heteroaromatic groups substituted with Cl, Br, F, I; preferably, R₂Are all selected from cyano, nitro, CF₃Cl, Br, F, I, or by cyano, nitro, CF₃Aryl substituted by Cl, Br, F, I, or by cyano, nitro, CF₃Cl, Br, F, I substituted heteroaromatic groups.

In one embodiment, n in (A-1) is selected from 1 or 2.

In one embodiment, (A-1) is selected from the group consisting of:

in one embodiment, (A-2) is selected from

In one embodiment, (A-2) is selected from the group consisting of:

in one embodiment, (a-3) is selected from the group consisting of:

in one embodiment, (A-4) is selected from

In one embodiment, (a-4) is selected from the group consisting of:

in one embodiment, (a-5) is selected from the group consisting of:

in a certain preferred embodiment, when Ar is present multiple times, it is simultaneously selected from (A-1) or simultaneously selected from (A-2) or simultaneously selected from (A-3) or simultaneously selected from (A-4) or simultaneously selected from (A-5).

In a certain preferred embodiment, when Ar is present multiple times, Ar is selected from groups of the same structure.

In a certain preferred embodiment, R₂When occurring for multiple times, at least one is independently selected from cyano, nitro and CF₃Cl, Br, F, I, or by cyano, nitro, CF₃Aryl substituted by Cl, Br, F, I, or by cyano, nitro, CF₃Cl, Br, F, I substituted heteroaromatic groups.

In a certain preferred embodiment, R₂When occurring for multiple times, the compounds are independently selected from cyano, nitro and CF₃Cl, Br, F, I, or by cyano, nitro, CF₃Aryl substituted by Cl, Br, F, I, or by cyano, nitro, CF₃Cl, Br, F, I substituted heteroaromatic groups.

In a certain preferred embodiment, R₁When occurring for multiple times, at least one is independently selected from cyano, nitro and CF₃Cl, Br, F, I, or by cyano, nitro, CF₃Aryl substituted by Cl, Br, F, I, or by cyano, nitro, CF₃Cl, Br, F, I substituted heteroaromatic groups.

In a certain preferred embodiment, formula (1) is selected from any one of the following structures:

wherein n1 is selected from any integer of 0-3; n2 is selected from any integer of 0-2; n3 is selected from any integer from 0 to 4.

In a certain preferred embodiment, the general formula (1) is selected from any one of the following formulae (2-1) to (2-9):

in a certain preferred embodiment, formula (1) is further selected from any one of the following structures:

wherein n1 is selected from any integer of 0-3; n2 is selected from any integer of 0-2; n3 is selected from any integer from 0 to 4. In a certain preferred embodiment, R₁And when the two groups occur, the compound is selected from CN.

Examples of organic compounds according to the invention are listed below, but are not limited to:

the organic compounds according to the invention can be used as functional materials in functional layers of electronic devices. The organic functional layer includes, but is not limited to, a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Transport Layer (ETL), an Electron Injection Layer (EIL), an Electron Blocking Layer (EBL), a Hole Blocking Layer (HBL), and an emission layer (EML).

In a particularly preferred embodiment, the organic compounds according to the invention are used in a Hole Injection Layer (HIL) or a Hole Transport Layer (HTL).

In a very preferred embodiment, the organic compounds according to the invention are used as p-type doping materials in Hole Injection Layers (HILs) or Hole Transport Layers (HTLs).

In certain embodiments, the organic compound according to the invention, T thereof₁More preferably, it is not less than 0.3eV, still more preferably not less than 0.6eV, particularly preferably not less than 0.8 eV.

Functional materials require good thermal stability. In general, the organic compounds according to the invention have a glass transition temperature Tg of 100 ℃ or higher, in a preferred embodiment 120 ℃ or higher, in a more preferred embodiment 140 ℃ or higher, in a more preferred embodiment 160 ℃ or higher, and in a most preferred embodiment 180 ℃ or higher.

An appropriate LUMO energy level is necessary as the p-type doping material. In certain embodiments, the organic compounds according to the invention have a LUMO ≦ -5.30eV, more preferably ≦ -5.50eV, and most preferably ≦ -5.60 eV.

In certain preferred embodiments, the organic compound according to the invention ((HOMO- (HOMO-1)). gtoreq.0.2 eV, preferably ≥ 0.25eV, more preferably ≥ 0.3eV, even more preferably ≥ 0.35eV, very preferably ≥ 0.4eV, most preferably ≥ 0.45 eV.

The present invention also provides a high polymer comprising at least one repeating unit comprising the organic compound described above.

The invention also provides a mixture, which comprises at least one organic compound or the high polymer and at least another organic functional material, wherein the at least another organic functional material can be selected from a Hole Injection Material (HIM), a Hole Transport Material (HTM), an Electron Transport Material (ETM), an Electron Injection Material (EIM), an Electron Blocking Material (EBM), a Hole Blocking Material (HBM), a luminescent material (Emitter), a main body material (Host) and an organic dye. Various organic functional materials are described in detail, for example, in WO2010135519a1, US20090134784a1 and WO2011110277a1, the entire contents of this 3 patent document being hereby incorporated by reference.

In some preferred embodiments, the mixture, wherein the another organic functional material is selected from a Hole Injection Material (HIM), a Hole Transport Material (HTM), and a Host material (Host).

In certain preferred embodiments, the mixture wherein the LUMO of the organic compound is equal to or lower than the HOMO +0.2eV of another organic functional material.

In certain preferred embodiments, the mixture wherein the LUMO of the organic compound is equal to or lower than the HOMO +0.1eV of another organic functional material.

In certain particularly preferred embodiments, the mixture wherein the LUMO of the organic compound is equal to or lower than the HOMO of another organic functional material.

In one embodiment, the mixture comprises at least one host material and one dopant, the dopant being an organic compound as described above, preferably the host material is selected from a Hole Injection Material (HIM) or a hole transport material, the molar ratio of dopant to host being from 1:1 to 1: 100000.

Details of HIM/HTM/EBM, and Host (Host material/matrix material) are described in WO2018095395A 1.

In certain embodiments, the compounds according to the invention have a molecular weight of 800g/mol or more, preferably 900g/mol or more, very preferably 1000g/mol or more, more preferably 1100g/mol or more, most preferably 1200g/mol or more.

In other embodiments, the compounds according to the invention have a solubility in toluene of 2mg/ml or more, preferably 3mg/ml or more, more preferably 4mg/ml or more, most preferably 5mg/ml or more at 25 ℃.

The invention also relates to a composition comprising at least one organic compound or polymer or mixture as described above, and at least one organic solvent; the organic solvent is selected from aromatic or heteroaromatic, ester, aromatic ketone or aromatic ether, aliphatic ketone or aliphatic ether, alicyclic or olefinic compound, or borate or phosphate compound, or a mixture of two or more solvents.

In a preferred embodiment, a composition according to the invention is characterized in that the organic solvent is chosen from aromatic or heteroaromatic-based solvents.

Examples of aromatic or heteroaromatic based solvents suitable for the present invention are, but not limited to: p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1, 4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, dipentylbenzene, tripentylbenzene, pentyltoluene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2,3, 4-tetramethylbenzene, 1,2,3, 5-tetramethylbenzene, 1,2,4, 5-tetramethylbenzene, butylbenzene, dodecylbenzene, dihexylbenzene, dibutylbenzene, p-diisopropylbenzene, cyclohexylbenzene, benzylbutylbenzene, dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, 1-methylnaphthalene, 1,2, 4-trichlorobenzene, 4-difluorodiphenylmethane, 1, 2-dimethoxy-4- (1-propenyl) benzene, diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, α -dichlorodiphenylmethane, 4- (3-phenylpropyl) pyridine, benzyl benzoate, 1-bis (3, 4-dimethylphenyl) ethane, 2-isopropylnaphthalene, quinoline, isoquinoline, methyl 2-furancarboxylate, ethyl 2-furancarboxylate, and the like;

examples of aromatic ketone-based solvents suitable for the present invention are, but not limited to: 1-tetralone, 2- (phenylepoxy) tetralone, 6- (methoxy) tetralone, acetophenone, propiophenone, benzophenone, and derivatives thereof, such as 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylpropiophenone, 3-methylpropiophenone, 2-methylpropiophenone, and the like;

examples of aromatic ether-based solvents suitable for the present invention are, but not limited to: 3-phenoxytoluene, butoxybenzene, p-anisaldehyde dimethylacetal, tetrahydro-2-phenoxy-2H-pyran, 1, 2-dimethoxy-4- (1-propenyl) benzene, 1, 4-benzodioxan, 1, 3-dipropylbenzene, 2, 5-dimethoxytoluene, 4-ethylphenetole, 1, 3-dipropoxybenzene, 1,2, 4-trimethoxybenzene, 4- (1-propenyl) -1, 2-dimethoxybenzene, 1, 3-dimethoxybenzene, glycidylphenyl ether, dibenzyl ether, 4-t-butylanisole, trans-p-propenylanisole, 1, 2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, methyl ether, 2-phenoxytetrahydrofuran, ethyl-2-naphthyl ether;

in some preferred embodiments, the organic solvent may be selected from: aliphatic ketones such as 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 2, 5-hexanedione, 2,6, 8-trimethyl-4-nonanone, fenchylone, phorone, isophorone, di-n-amyl ketone, etc.; or aliphatic ethers such as amyl ether, hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and the like.

In other preferred embodiments, the organic solvent may be selected from ester-based solvents: alkyl octanoates, alkyl sebacates, alkyl stearates, alkyl benzoates, alkyl phenylacetates, alkyl cinnamates, alkyl oxalates, alkyl maleates, alkyl lactones, alkyl oleates, and the like. Octyl octanoate, diethyl sebacate, diallyl phthalate, isononyl isononanoate are particularly preferred.

The solvents mentioned may be used alone or as a mixture of two or more organic solvents.

In certain preferred embodiments, a composition according to the invention is characterized by comprising at least one organic compound or polymer or mixture as described above and at least one organic solvent, and may further comprise another organic solvent. Examples of another organic solvent include (but are not limited to): methanol, ethanol, 2-methoxyethanol, methylene chloride, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1, 4-dioxane, acetone, methyl ethyl ketone, 1, 2-dichloroethane, 3-phenoxytoluene, 1,1, 1-trichloroethane, 1,1,2, 2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydronaphthalene, decalin, indene, and/or mixtures thereof.

In some preferred embodiments, particularly suitable solvents for the present invention are those having Hansen (Hansen) solubility parameters within the following ranges:

δ_d(dispersion force) of 17.0 to 23.2MPa^1/2In particular in the range of 18.5 to 21.0MPa^1/2A range of (d);

δ_p(polar force) is 0.2 to 12.5MPa^1/2In particular in the range of 2.0 to 6.0MPa^1/2A range of (d);

δ_h(hydrogen bonding force) of 0.9 to 14.2MPa^1/2In particular in the range of 2.0 to 6.0MPa^1/2The range of (1).

The compositions according to the invention, in which the organic solvent is selected taking into account its boiling point parameter. In the invention, the boiling point of the organic solvent is more than or equal to 150 ℃; preferably equal to or more than 180 ℃; more preferably more than or equal to 200 ℃; more preferably more than or equal to 250 ℃; most preferably more than or equal to 275 ℃ or more than or equal to 300 ℃. Boiling points in these ranges are beneficial for preventing nozzle clogging in inkjet print heads. The organic solvent may be evaporated from the solvent system to form a thin film comprising the functional material.

In a preferred embodiment, the composition according to the invention is a solution.

In another preferred embodiment, the composition according to the invention is a suspension.

The compositions of the embodiments of the present invention may contain from 0.01 to 10 wt%, preferably from 0.1 to 15 wt%, more preferably from 0.2 to 5 wt%, most preferably from 0.25 to 3 wt%, of the organic compound or polymer or mixture according to the present invention.

The invention also relates to the use of said composition as a coating or printing ink for the production of organic electronic devices, particularly preferably by a printing or coating production process.

Suitable Printing or coating techniques include, but are not limited to, ink jet Printing, letterpress, screen Printing, dip coating, spin coating, doctor blade coating, roll Printing, twist roll Printing, lithographic Printing, flexographic Printing, rotary Printing, spray coating, brush or pad Printing, slot die coating, and the like. Gravure printing, jet printing and ink jet printing are preferred. The solution or suspension may additionally include one or more components such as surface active compounds, lubricants, wetting agents, dispersants, hydrophobing agents, binders, and the like, for adjusting viscosity, film forming properties, enhancing adhesion, and the like. The printing technology and the requirements related to the solution, such as solvent and concentration, viscosity, etc.

The present invention also provides a use of the Organic compound, polymer, mixture or composition as described above in an Organic electronic device, which can be selected from, but not limited to, Organic Light Emitting Diodes (OLEDs), Organic photovoltaic cells (OPVs), Organic light Emitting cells (OLEECs), Organic Field Effect Transistors (OFETs), Organic light Emitting field effect transistors (efets), Organic lasers, Organic spintronic devices, Organic sensors, and Organic Plasmon Emitting diodes (Organic Plasmon Emitting diodes), etc., and particularly preferably is an OLED. In the embodiment of the present invention, the organic compound or the high polymer is preferably used for a light emitting layer of an OLED device.

The invention further relates to an organic electronic device comprising at least one organic compound or polymer or mixture as described above or prepared from the above composition. Furthermore, the organic electronic device comprises at least one functional layer comprising an organic compound or polymer or 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).

In a specific example, an organic electronic device comprises said organic compound or said mixture or is prepared from said composition.

In a particular example, at least one organic compound or polymer or mixture or composition as described above is contained. Furthermore, the organic electronic device comprises at least one functional layer, and the functional layer is prepared from the organic compound or the high polymer or the mixture or the composition. The functional layer is selected from a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an emission layer (EML), an Electron Blocking Layer (EBL), an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), and a Hole Blocking Layer (HBL).

In a preferred embodiment, the organic electronic device according to the invention comprises at least one hole injection layer or hole transport layer comprising an organic compound as described above.

In general, the organic electronic device of the present invention comprises at least a cathode, an anode and a functional layer disposed between the cathode and the anode, wherein the functional layer comprises at least one organic compound as described above. The Organic electronic device can be selected from, but not limited to, Organic Light Emitting Diodes (OLEDs), Organic photovoltaic cells (OPVs), Organic light Emitting cells (OLEECs), Organic Field Effect Transistors (OFETs), Organic light Emitting field effect transistors (fets), Organic lasers, Organic spintronic devices, Organic sensors, Organic Plasmon Emitting diodes (Organic Plasmon Emitting diodes), and the like, and particularly preferred are Organic electroluminescent devices such as OLEDs, OLEECs, Organic light Emitting field effect transistors.

In certain preferred embodiments, the electroluminescent device comprises a hole injection layer or a hole transport layer comprising an organic compound or polymer as described above.

The light emitting device, particularly an OLED, includes a substrate, an anode, at least one light emitting layer, and a cathode.

The substrate may be opaque or transparent. A transparent substrate may be used to fabricate a transparent light emitting device. See, for example, Bulovic et al Nature 1996,380, p29, and Gu et al, appl.Phys.Lett.1996,68, p 2606. The substrate may be rigid or elastic. The substrate may be plastic, metal, semiconductor wafer or glass. Preferably, the substrate has a smooth surface. A substrate free of surface defects is a particularly desirable choice. In a preferred embodiment, the substrate is flexible, and may be selected from a polymer film or plastic, having a glass transition temperature Tg of 150 ℃ or higher, preferably over 200 ℃, more preferably over 250 ℃, and most preferably over 300 ℃. Examples of suitable flexible substrates are poly (ethylene terephthalate) (PET) and polyethylene glycol (2, 6-naphthalene) (PEN).

The anode may comprise a conductive metal or metal oxide, or a conductive polymer. The anode can easily inject holes into a Hole Injection Layer (HIL) or a Hole Transport Layer (HTL) or an emission layer. In one embodiment, the absolute value of the difference between the work function of the anode and the HOMO level or valence band level of the emitter in the light emitting layer or the p-type semiconductor material acting as a HIL or HTL or Electron Blocking Layer (EBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2 eV. Examples of anode materials include, but are not limited to: al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, aluminum-doped zinc oxide (AZO), and the like. Other suitable anode materials are known and can be readily selected for use by one of ordinary skill in the art. The anode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like. In certain embodiments, the anode is pattern structured. Patterned ITO conductive substrates are commercially available and can be used to prepare devices according to the present invention.

The cathode may comprise a conductive metal or metal oxide. The cathode can easily inject electrons into the EIL or ETL or directly into the light emitting layer. In one embodiment, the absolute value of the difference between the work function of the cathode and the LUMO level or conduction band level of the emitter in the light-emitting layer or of the n-type semiconductor material as Electron Injection Layer (EIL) or Electron Transport Layer (ETL) or Hole Blocking Layer (HBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2 eV. In principle, all materials which can be used as cathodes in OLEDs are possible as cathode materials for the device according to the invention. Examples of cathode materials include, but are not limited to: al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF₂Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, etc. The cathode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.

The OLED may also comprise further functional layers, such as a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Blocking Layer (EBL), an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), a Hole Blocking Layer (HBL). Suitable materials for use in these functional layers are described in detail above and in WO2010135519a1, US20090134784a1 and WO2011110277a1, the entire contents of these 3 patent documents being hereby incorporated by reference.

The light-emitting device according to the present invention emits light at a wavelength of 300 to 1200nm, preferably 350 to 1000nm, and more preferably 400 to 900 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.

Referring to fig. 1, an embodiment of the invention provides an organic light emitting device. Taking the substrate 101 as the bottom layer, the organic light emitting device sequentially comprises from bottom to top: a substrate 101, an anode 102, a hole injection layer 103, a hole transport layer 104, a light emitting layer 105, an electron injection layer or electron transport layer 106, and a cathode 107.

The present invention will be described in connection with preferred embodiments, but the present invention is not limited to the following embodiments, and it should be understood that the appended claims outline the scope of the present invention and those skilled in the art, guided by the inventive concept, will appreciate that certain changes may be made to the embodiments of the invention, which are intended to be covered by the spirit and scope of the appended claims.

DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION

The synthesis of the compounds according to the invention is illustrated, but the invention is not limited to the following examples.

1. Organic compounds and synthetic procedures

Example 1: synthesis of Compound PD-1

Synthesis of intermediate 2

To a dry autoclave, under nitrogen, was added anhydrous tetrahydrofuran (230mL) and lithium hydride (0.88 g). Cooling to 10-15 ℃, dissolving the compound 1(4mmol) in anhydrous tetrahydrofuran (30mL), slowly dropwise adding into a reaction kettle (keeping the temperature below 15 ℃), stirring for 45min after dropwise adding, and cooling to 0-5 ℃; dissolving pentachlorocyclopropane (1mmol) in anhydrous tetrahydrofuran (11mL), slowly dropwise adding into the reaction kettle, and naturally heating to room temperature after dropwise adding is finished, and reacting for 44 h. After the completion of the TLC and MS monitoring reactions, water (30mL) was slowly added to the reaction vessel, the reaction solution was acidified with concentrated hydrochloric acid, ethyl acetate (30mL) was added, the mixture was stirred for 30min, and then the mixture was allowed to stand for liquid separation, the aqueous phase was extracted with ethyl acetate, the organic phases were combined, washed with saturated brine and saturated sodium bicarbonate solution in this order, dried, and rotary-evaporated. Dissolving the obtained solid in acetic acid (13mL), slowly dropwise adding the solid into a mixed acid of concentrated nitric acid (65%, 1mL) and concentrated bromic acid (3mL) (keeping the temperature below 40 ℃), cooling the mixed solution to below 20 ℃, and slowly adding water (the temperature is controlled to be 20-30 ℃). After the product was precipitated, it was stirred for 30min, filtered off with suction, and dried under nitrogen protection to obtain 251mg of intermediate 2 with a yield of 53%.

Synthesis of Compound PD-1

30% hydrogen peroxide (0.3mL) was added to a 100mL three-necked flask, trifluoroacetic anhydride (0.6 mL) was added dropwise under ice-cooling, and stirred for 30min, followed by addition of 15mL of a dichloromethane solution of intermediate 2(0.18mmol) and reaction overnight. Slowly pouring the reaction liquid into ice water, adjusting the pH value of sodium bicarbonate to 9, extracting with ethyl acetate for 3 times, washing with water for three times, drying with anhydrous magnesium sulfate, and carrying out column chromatography separation on ethyl acetate/petroleum ether to obtain a PD-1 solid product 63mg with the yield of 68%.

Example 2: synthesis of Compound PD-2

Synthesis of intermediate 4

To a dry autoclave, under nitrogen, was added anhydrous tetrahydrofuran (230mL) and lithium hydride (0.88 g). Cooling to 10-15 ℃, dissolving the compound 3(4mmol) in anhydrous tetrahydrofuran (30mL), slowly dropwise adding into a reaction kettle (keeping the temperature below 15 ℃), stirring for 45min after dropwise adding, and cooling to 0-5 ℃; dissolving pentachlorocyclopropane (1mmol) in anhydrous tetrahydrofuran (11mL), slowly dropwise adding into the reaction kettle, and naturally heating to room temperature after dropwise adding is finished, and reacting for 44 h. After the completion of the TLC and MS monitoring reactions, water (30mL) was slowly added to the reaction vessel, the reaction solution was acidified with concentrated hydrochloric acid, ethyl acetate (30mL) was added, the mixture was stirred for 30min, and then the mixture was allowed to stand for liquid separation, the aqueous phase was extracted with ethyl acetate, the organic phases were combined, washed with saturated brine and saturated sodium bicarbonate solution in this order, dried, and rotary-evaporated. Dissolving the obtained solid in acetic acid (13mL), slowly dropwise adding the solid into a mixed acid of concentrated nitric acid (65%, 1mL) and concentrated bromic acid (3mL) (keeping the temperature below 40 ℃), cooling the mixed solution to below 20 ℃, and slowly adding water (the temperature is controlled to be 20-30 ℃). After the product was precipitated, it was stirred for 30min, filtered off with suction and dried under nitrogen protection to yield 187mg of intermediate 4 in 47% yield.

Synthesis of Compound PD-2

60% hydrogen peroxide (0.3mL) was added to a 100mL three-necked flask, trifluoroacetic anhydride (0.6 mL) was added dropwise under ice-cooling, and stirred for 30min, followed by addition of 15mL of a dichloromethane solution of intermediate 4(0.18mmol) and reaction overnight. Slowly pouring the reaction liquid into ice water, adjusting the pH value of sodium bicarbonate to 9, extracting with ethyl acetate for 3 times, washing with water for three times, drying with anhydrous magnesium sulfate, and carrying out column chromatography separation on ethyl acetate/petroleum ether to obtain a PD-2 solid product 49mg with the yield of 55%.

Example 3: synthesis of Compound PD-3

Synthesis of Compound PD-3

A100 mL three-necked flask was charged with 60% hydrogen peroxide (0.3mL), and trifluoroacetic anhydride (0.6 mL) was added dropwise under ice-cooling, followed by stirring for 30min, followed by addition of 15mL of a dichloromethane solution of intermediate 2(0.18mmol) and reaction overnight. Slowly pouring the reaction liquid into ice water, adjusting the pH value of sodium bicarbonate to 9, extracting with ethyl acetate for 3 times, washing with water for three times, drying with anhydrous magnesium sulfate, and carrying out column chromatography separation on ethyl acetate/petroleum ether to obtain a PD-3 solid product 63mg with the yield of 62%.

Example 4: synthesis of Compound PD-4

Synthesis of Compound PD-4

To a dry autoclave, under nitrogen, was added anhydrous tetrahydrofuran (230mL) and lithium hydride (0.88 g). Cooling to 10-15 ℃, dissolving the compound 5(4mmol) in anhydrous tetrahydrofuran (30mL), slowly dropwise adding the mixture into a reaction kettle (keeping the temperature below 15 ℃), stirring for 45min after dropwise adding, and cooling to 0-5 ℃; dissolving pentachlorocyclopropane (1mmol) in anhydrous tetrahydrofuran (11mL), slowly dropwise adding into the reaction kettle, and naturally heating to room temperature after dropwise adding is finished, and reacting for 44 h. After the completion of the TLC and MS monitoring reactions, water (30mL) was slowly added to the reaction vessel, the reaction solution was acidified with concentrated hydrochloric acid, ethyl acetate (30mL) was added, the mixture was stirred for 30min, and then the mixture was allowed to stand for liquid separation, the aqueous phase was extracted with ethyl acetate, the organic phases were combined, washed with saturated brine and saturated sodium bicarbonate solution in this order, dried, and rotary-evaporated. Dissolving the obtained solid in acetic acid (13mL), slowly dropwise adding the solid into a mixed acid of concentrated nitric acid (65%, 1mL) and concentrated bromic acid (3mL) (keeping the temperature below 40 ℃), cooling the mixed solution to below 20 ℃, and slowly adding water (the temperature is controlled to be 20-30 ℃). After the product is precipitated, the mixture is stirred for 30min, filtered and dried under the protection of nitrogen, and 285mg of product PD-4 is obtained, and the yield is 49%.

Example 5: synthesis of Compound PD-5

Synthesis of Compound PD-5

To a dry autoclave, under nitrogen, was added anhydrous tetrahydrofuran (230mL) and lithium hydride (0.88 g). Cooling to 10-15 ℃, dissolving the compound 6(4mmol) in anhydrous tetrahydrofuran (30mL), slowly dropwise adding into a reaction kettle (keeping the temperature below 15 ℃), stirring for 45min after dropwise adding, and cooling to 0-5 ℃; dissolving pentachlorocyclopropane (1mmol) in anhydrous tetrahydrofuran (11mL), slowly dropwise adding into the reaction kettle, and naturally heating to room temperature after dropwise adding is finished, and reacting for 44 h. After the completion of the TLC and MS monitoring reactions, water (30mL) was slowly added to the reaction vessel, the reaction solution was acidified with concentrated hydrochloric acid, ethyl acetate (30mL) was added, the mixture was stirred for 30min, and then the mixture was allowed to stand for liquid separation, the aqueous phase was extracted with ethyl acetate, the organic phases were combined, washed with saturated brine and saturated sodium bicarbonate solution in this order, dried, and rotary-evaporated. Dissolving the obtained solid in acetic acid (13mL), slowly dropwise adding the solid into a mixed acid of concentrated nitric acid (65%, 1mL) and concentrated bromic acid (3mL) (keeping the temperature below 40 ℃), cooling the mixed solution to below 20 ℃, and slowly adding water (the temperature is controlled to be 20-30 ℃). After the product is precipitated, the mixture is stirred for 30min, filtered and dried under the protection of nitrogen, 375mg of product PD-5 is obtained, and the yield is 68%.

Example 6: synthesis of Compound PD-6

Synthesis of Compound PD-6

To a dry autoclave, under nitrogen, was added anhydrous tetrahydrofuran (230mL) and lithium hydride (0.88 g). Cooling to 10-15 ℃, dissolving the compound 7(4mmol) in anhydrous tetrahydrofuran (30mL), slowly dropwise adding into a reaction kettle (keeping the temperature below 15 ℃), stirring for 45min after dropwise adding, and cooling to 0-5 ℃; dissolving pentachlorocyclopropane (1mmol) in anhydrous tetrahydrofuran (11mL), slowly dropwise adding into the reaction kettle, and naturally heating to room temperature after dropwise adding is finished, and reacting for 44 h. After the completion of the TLC and MS monitoring reactions, water (30mL) was slowly added to the reaction vessel, the reaction solution was acidified with concentrated hydrochloric acid, ethyl acetate (30mL) was added, the mixture was stirred for 30min, and then the mixture was allowed to stand for liquid separation, the aqueous phase was extracted with ethyl acetate, the organic phases were combined, washed with saturated brine and saturated sodium bicarbonate solution in this order, dried, and rotary-evaporated. Dissolving the obtained solid in acetic acid (13mL), slowly dropwise adding the solid into a mixed acid of concentrated nitric acid (65%, 1mL) and concentrated bromic acid (3mL) (keeping the temperature below 40 ℃), cooling the mixed solution to below 20 ℃, and slowly adding water (the temperature is controlled to be 20-30 ℃). After the product is precipitated, the mixture is stirred for 30min, filtered and dried under the protection of nitrogen, and 227mg of product PD-6 is obtained, and the yield is 36%.

Example 7: synthesis of Compound PD-7

Synthesis of Compound PD-7

To a dry autoclave, under nitrogen, was added anhydrous tetrahydrofuran (230mL) and lithium hydride (0.88 g). Cooling to 10-15 ℃, dissolving the compound 8(4mmol) in anhydrous tetrahydrofuran (30mL), slowly dropwise adding into a reaction kettle (keeping the temperature below 15 ℃), stirring for 45min after dropwise adding, and cooling to 0-5 ℃; dissolving pentachlorocyclopropane (1mmol) in anhydrous tetrahydrofuran (11mL), slowly dropwise adding into the reaction kettle, and naturally heating to room temperature after dropwise adding is finished, and reacting for 44 h. After the completion of the TLC and MS monitoring reactions, water (30mL) was slowly added to the reaction vessel, the reaction solution was acidified with concentrated hydrochloric acid, ethyl acetate (30mL) was added, the mixture was stirred for 30min, and then the mixture was allowed to stand for liquid separation, the aqueous phase was extracted with ethyl acetate, the organic phases were combined, washed with saturated brine and saturated sodium bicarbonate solution in this order, dried, and rotary-evaporated. Dissolving the obtained solid in acetic acid (13mL), slowly dropwise adding the solid into a mixed acid of concentrated nitric acid (65%, 1mL) and concentrated bromic acid (3mL) (keeping the temperature below 40 ℃), cooling the mixed solution to below 20 ℃, and slowly adding water (the temperature is controlled to be 20-30 ℃). After the product is precipitated, the mixture is stirred for 30min, filtered and dried under the protection of nitrogen, and 479mg of product PD-7 is obtained, and the yield is 72 percent.

Example 8: synthesis of Compound PD-8

Synthesis of Compound PD-8

To a dry autoclave, under nitrogen, was added anhydrous tetrahydrofuran (230mL) and lithium hydride (0.88 g). Cooling to 10-15 ℃, dissolving the compound 9(4mmol) in anhydrous tetrahydrofuran (30mL), slowly dropwise adding into a reaction kettle (keeping the temperature below 15 ℃), stirring for 45min after dropwise adding, and cooling to 0-5 ℃; dissolving pentachlorocyclopropane (1mmol) in anhydrous tetrahydrofuran (11mL), slowly dropwise adding into the reaction kettle, and naturally heating to room temperature after dropwise adding is finished, and reacting for 44 h. After the completion of the TLC and MS monitoring reactions, water (30mL) was slowly added to the reaction vessel, the reaction solution was acidified with concentrated hydrochloric acid, ethyl acetate (30mL) was added, the mixture was stirred for 30min, and then the mixture was allowed to stand for liquid separation, the aqueous phase was extracted with ethyl acetate, the organic phases were combined, washed with saturated brine and saturated sodium bicarbonate solution in this order, dried, and rotary-evaporated. Dissolving the obtained solid in acetic acid (13mL), slowly dropwise adding the solid into a mixed acid of concentrated nitric acid (65%, 1mL) and concentrated bromic acid (3mL) (keeping the temperature below 40 ℃), cooling the mixed solution to below 20 ℃, and slowly adding water (the temperature is controlled to be 20-30 ℃). After the product is precipitated, the mixture is stirred for 30min, filtered and dried under the protection of nitrogen, and 238mg of product PD-8 is obtained, and the yield is 34%.

Example 9: synthesis of Compound PD-9

Synthesis of intermediate 11

To a dry autoclave, under nitrogen, was added anhydrous tetrahydrofuran (230mL) and lithium hydride (0.88 g). Cooling to 10-15 ℃, dissolving the compound 10(4mmol) in anhydrous tetrahydrofuran (30mL), slowly dropwise adding into a reaction kettle (keeping the temperature below 15 ℃), stirring for 45min after dropwise adding, and cooling to 0-5 ℃; dissolving pentachlorocyclopropane (1mmol) in anhydrous tetrahydrofuran (11mL), slowly dropwise adding into the reaction kettle, and naturally heating to room temperature after dropwise adding is finished, and reacting for 44 h. After the completion of the TLC and MS monitoring reactions, water (30mL) was slowly added to the reaction vessel, the reaction solution was acidified with concentrated hydrochloric acid, ethyl acetate (30mL) was added, the mixture was stirred for 30min, and then the mixture was allowed to stand for liquid separation, the aqueous phase was extracted with ethyl acetate, the organic phases were combined, washed with saturated brine and saturated sodium bicarbonate solution in this order, dried, and rotary-evaporated. Dissolving the obtained solid in acetic acid (13mL), slowly dropwise adding the solid into a mixed acid of concentrated nitric acid (65%, 1mL) and concentrated bromic acid (3mL) (keeping the temperature below 40 ℃), cooling the mixed solution to below 20 ℃, and slowly adding water (the temperature is controlled to be 20-30 ℃). After the product is precipitated, the mixture is stirred for 30min, filtered and dried under the protection of nitrogen, 596mg of intermediate 11 is obtained, and the yield is 66%.

Synthesis of Compound PD-9

A100 mL three-necked flask was charged with 60% hydrogen peroxide (0.3mL), and trifluoroacetic anhydride (0.6 mL) was added dropwise under ice-cooling, followed by stirring for 30min, followed by addition of 15mL of a dichloromethane solution of intermediate 11(0.18mmol) and reaction overnight. Slowly pouring the reaction liquid into ice water, adjusting the pH value of sodium bicarbonate to 9, extracting with ethyl acetate for 3 times, washing with water for three times, drying with anhydrous magnesium sulfate, and carrying out column chromatography separation on ethyl acetate/petroleum ether to obtain a PD-9 solid product 52mg with the yield of 28%.

Example 10: synthesis of Compound PD-10

Synthesis of intermediate 13

To a dry autoclave, under nitrogen, was added anhydrous tetrahydrofuran (230mL) and lithium hydride (0.88 g). Cooling to 10-15 ℃, dissolving the compound 12(4mmol) in anhydrous tetrahydrofuran (30mL), slowly dropwise adding into a reaction kettle (keeping the temperature below 15 ℃), stirring for 45min after dropwise adding, and cooling to 0-5 ℃; dissolving pentachlorocyclopropane (1mmol) in anhydrous tetrahydrofuran (11mL), slowly dropwise adding into the reaction kettle, and naturally heating to room temperature after dropwise adding is finished, and reacting for 44 h. After the completion of the TLC and MS monitoring reactions, water (30mL) was slowly added to the reaction vessel, the reaction solution was acidified with concentrated hydrochloric acid, ethyl acetate (30mL) was added, the mixture was stirred for 30min, and then the mixture was allowed to stand for liquid separation, the aqueous phase was extracted with ethyl acetate, the organic phases were combined, washed with saturated brine and saturated sodium bicarbonate solution in this order, dried, and rotary-evaporated. Dissolving the obtained solid in acetic acid (13mL), slowly dropwise adding the solid into a mixed acid of concentrated nitric acid (65%, 1mL) and concentrated bromic acid (3mL) (keeping the temperature below 40 ℃), cooling the mixed solution to below 20 ℃, and slowly adding water (the temperature is controlled to be 20-30 ℃). After the product is precipitated, the mixture is stirred for 30min, filtered, and dried under the protection of nitrogen, so that 496mg of intermediate 13 is obtained, and the yield is 58%.

Synthesis of Compound PD-10

A100 mL three-necked flask was charged with 60% hydrogen peroxide (0.3mL), and trifluoroacetic anhydride (0.6 mL) was added dropwise under ice-cooling, followed by stirring for 30min, followed by addition of 15mL of a dichloromethane solution of intermediate 13(0.18mmol) and reaction overnight. Slowly pouring the reaction liquid into ice water, adjusting the pH value of sodium bicarbonate to 9, extracting with ethyl acetate for 3 times, washing with water for three times, drying with anhydrous magnesium sulfate, and carrying out column chromatography separation on ethyl acetate/petroleum ether to obtain a PD-10 solid product 32mg with the yield of 19%.

Example 11: synthesis of Compound PD-11

Synthesis of Compound PD-11

To a dry autoclave, under nitrogen, was added anhydrous tetrahydrofuran (230mL) and lithium hydride (0.88 g). Cooling to 10-15 ℃, dissolving the compound 14(4mmol) in anhydrous tetrahydrofuran (30mL), slowly dropwise adding into a reaction kettle (keeping the temperature below 15 ℃), stirring for 45min after dropwise adding, and cooling to 0-5 ℃; dissolving pentachlorocyclopropane (1mmol) in anhydrous tetrahydrofuran (11mL), slowly dropwise adding into the reaction kettle, and naturally heating to room temperature after dropwise adding is finished, and reacting for 44 h. After the completion of the TLC and MS monitoring reactions, water (30mL) was slowly added to the reaction vessel, the reaction solution was acidified with concentrated hydrochloric acid, ethyl acetate (30mL) was added, the mixture was stirred for 30min, and then the mixture was allowed to stand for liquid separation, the aqueous phase was extracted with ethyl acetate, the organic phases were combined, washed with saturated brine and saturated sodium bicarbonate solution in this order, dried, and rotary-evaporated. Dissolving the obtained solid in acetic acid (13mL), slowly dropwise adding the solid into a mixed acid of concentrated nitric acid (65%, 1mL) and concentrated bromic acid (3mL) (keeping the temperature below 40 ℃), cooling the mixed solution to below 20 ℃, and slowly adding water (the temperature is controlled to be 20-30 ℃). After the product is precipitated, the mixture is stirred for 30min, filtered and dried under the protection of nitrogen, so that 494mg of product PD-11 is obtained, and the yield is 70%.

Example 12: synthesis of Compound PD-12

Synthesis of intermediate 16

To a dry autoclave, under nitrogen, was added anhydrous tetrahydrofuran (230mL) and lithium hydride (0.88 g). Cooling to 10-15 ℃, dissolving the compound 15(4mmol) in anhydrous tetrahydrofuran (30mL), slowly dropwise adding into a reaction kettle (keeping the temperature below 15 ℃), stirring for 45min after dropwise adding, and cooling to 0-5 ℃; dissolving pentachlorocyclopropane (1mmol) in anhydrous tetrahydrofuran (11mL), slowly dropwise adding into the reaction kettle, and naturally heating to room temperature after dropwise adding is finished, and reacting for 44 h. After the completion of the TLC and MS monitoring reactions, water (30mL) was slowly added to the reaction vessel, the reaction solution was acidified with concentrated hydrochloric acid, ethyl acetate (30mL) was added, the mixture was stirred for 30min, and then the mixture was allowed to stand for liquid separation, the aqueous phase was extracted with ethyl acetate, the organic phases were combined, washed with saturated brine and saturated sodium bicarbonate solution in this order, dried, and rotary-evaporated. Dissolving the obtained solid in acetic acid (13mL), slowly dropwise adding the solid into a mixed acid of concentrated nitric acid (65%, 1mL) and concentrated bromic acid (3mL) (keeping the temperature below 40 ℃), cooling the mixed solution to below 20 ℃, and slowly adding water (the temperature is controlled to be 20-30 ℃). After the product is precipitated, the mixture is stirred for 30min, filtered and dried under the protection of nitrogen to obtain 511mg of intermediate 16 with the yield of 66 percent

Synthesis of Compound PD-12

60% hydrogen peroxide (0.3mL) was added to a 100mL three-necked flask, trifluoroacetic anhydride (0.6 mL) was added dropwise under ice-cooling, and stirred for 30min, followed by addition of 15mL of a dichloromethane solution of intermediate 16(0.18mmol) and reaction overnight. Slowly pouring the reaction liquid into ice water, adjusting the pH value of sodium bicarbonate to 9, extracting with ethyl acetate for 3 times, washing with water for three times, drying with anhydrous magnesium sulfate, and carrying out column chromatography separation on ethyl acetate/petroleum ether to obtain a PD-12 solid product 34mg with the yield of 22%.

Example 13: synthesis of Compound PD-13

Synthesis of intermediate 18

To a dry autoclave, under nitrogen, was added anhydrous tetrahydrofuran (230mL) and lithium hydride (0.88 g). Cooling to 10-15 ℃, dissolving the compound 17(4mmol) in anhydrous tetrahydrofuran (30mL), slowly dropwise adding into a reaction kettle (keeping the temperature below 15 ℃), stirring for 45min after dropwise adding, and cooling to 0-5 ℃; dissolving pentachlorocyclopropane (1mmol) in anhydrous tetrahydrofuran (11mL), slowly dropwise adding into the reaction kettle, and naturally heating to room temperature after dropwise adding is finished, and reacting for 44 h. After the completion of the TLC and MS monitoring reactions, water (30mL) was slowly added to the reaction vessel, the reaction solution was acidified with concentrated hydrochloric acid, ethyl acetate (30mL) was added, the mixture was stirred for 30min, and then the mixture was allowed to stand for liquid separation, the aqueous phase was extracted with ethyl acetate, the organic phases were combined, washed with saturated brine and saturated sodium bicarbonate solution in this order, dried, and rotary-evaporated. Dissolving the obtained solid in acetic acid (13mL), slowly dropwise adding the solid into a mixed acid of concentrated nitric acid (65%, 1mL) and concentrated bromic acid (3mL) (keeping the temperature below 40 ℃), cooling the mixed solution to below 20 ℃, and slowly adding water (the temperature is controlled to be 20-30 ℃). After the product is precipitated, the mixture is stirred for 30min, filtered and dried under the protection of nitrogen to obtain 418mg of intermediate 18 with the yield of 51 percent

Synthesis of Compound PD-13

60% hydrogen peroxide (0.3mL) was added to a 100mL three-necked flask, trifluoroacetic anhydride (0.6 mL) was added dropwise under ice-cooling, and stirred for 30min, followed by addition of 15mL of a dichloromethane solution of intermediate 18(0.18mmol) and reaction overnight. Slowly pouring the reaction liquid into ice water, adjusting the pH value of sodium bicarbonate to 9, extracting with ethyl acetate for 3 times, washing with water for three times, drying with anhydrous magnesium sulfate, and carrying out column chromatography separation on ethyl acetate/petroleum ether to obtain a PD-13 solid product 33mg with the yield of 20%.

2. Energy level structure of compound

The organic small molecule energy structure can be obtained by quantum calculation, for example, by using TD-DFT (including time density functional theory) through Gaussian03W (Gaussian Inc.), and a specific simulation method can be seen in WO 2011141110. Firstly, a Semi-empirical method of 'group State/Semi-empirical/Default Spin/AM 1' (Charge 0/Spin Singlet) is used for optimizing the molecular geometrical structure, and then the energy structure of the organic molecules is calculated by a TD-DFT (including time density functional theory) method to obtain 'TD-SCF/DFT/Default Spin/B3PW 91' and a base group of '6-31G (d)' (Charge 0/Spin Singlet).

The HOMO and LUMO energy levels calculated above were calculated according to the following calibration formula, and S1 and T1 were used directly.

HOMO(eV)＝((HOMO(G)×27.212)-0.9899)/1.1206

LUMO(eV)＝((LUMO(G)×27.212)-2.0041)/1.385

Where HOMO (G) and LUMO (G) are direct calculations of Gaussian 09W in eV. The results are shown in table one, where Δ HOMO ═ HOMO- (HOMO-1):

3. preparation method of OLED device

The device structure of the OLED device (OLED-Ref) is as follows: the ITO/HIL (10nm)/HT-1(120nm)/HT-2(10nm)/BH BD (25nm)/ET LiQ (30nm)/LiQ (1nm)/Al (100nm) specifically comprises the following preparation steps:

1) cleaning of an ITO transparent electrode (anode) glass substrate: carrying out ultrasonic treatment for 30 minutes by using an aqueous solution of 5% Decon90 cleaning solution, then carrying out ultrasonic cleaning for several times by using deionized water, then carrying out ultrasonic cleaning by using isopropanol, and carrying out nitrogen blow-drying; processing for 5 minutes under oxygen plasma to clean the ITO surface and improve the work function of an ITO electrode;

2) preparation of HIL (10nm) layer: the ITO substrate was transferred into a vacuum vapor deposition apparatus under high vacuum (1X 10)^-6Millibar), adopting resistance heating evaporation, and forming a 10nm injection layer by HT-1 evaporation;

3) HT-1(120nm), HT-2(10nm), EML (20nm), ETL (30nm), EIL and cathode layer preparation: then, evaporation is sequentially carried out to obtain 120nm HT-1 and 10nm HT-2 layers. Then BH and BD were measured at 97: 3 to form a 25nm light-emitting layer. Then, placing ET and LiQ in different evaporation units, carrying out co-deposition on the ET and the LiQ respectively according to the proportion of 50 weight percent, forming an electron transport layer with the thickness of 30nm on the luminescent layer, then depositing LiQ with the thickness of 1nm on the electron transport layer to be used as an electron injection layer, and finally depositing an Al cathode with the thickness of 100nm on the electron injection layer;

4) all devices were encapsulated in a nitrogen glove box with uv cured resin plus glass cover plate.

The OLED devices (OLED-1 to OLED-13) were prepared as above, but in the case of the HIL layer, with PD-1 to PD-11 and comparative compound 1 and comparative compound 2, respectively, at a ratio of 2: the proportion of 98 was doped with HT-1 to replace the pure HT-1 of OLED-Ref.

The current-voltage (J-V) characteristics of each OLED device were characterized by a characterization device, while recording important parameters such as efficiency, lifetime, and external quantum efficiency.

The sulfur-containing heterocycle-substituted cyclopropane compound according to the present invention, when used for doping HIL, is improved in both efficiency and lifetime compared to undoped device performance, and also exceeds or approaches device performance compared to comparative compound 1(F4 TCNQ). This is probably because the compound according to the present invention has a similar electron orbital level, especially a lower LUMO level, as compared with compound 1, thereby providing some assistance in hole injection. Device performance, both efficiency and lifetime, are improved compared to comparative compound 2, which is likely to be a stronger electron-withdrawing group in the chemical structure of compound 2, making the LUMO of the compound lower and thus hole injection easier.

It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.

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

1. An organic compound characterized by: has a structure represented by the general formula (1):

wherein:

n is independently selected from 0 or 1 or 2 at each occurrence;

R₁、R₂、R₃、R₄each occurrence is independently selected from H, D, F, Cl, Br, I, CF₃Cyano group, isocyano group, hydroxyl group, nitro group, formyl group, carbamoyl group, haloformyl group, isocyanate group, thiocyanate, isothiocyanate, silyl group, straight-chain alkyl group or alkoxy group or thioalkoxy group having 1 to 20 carbon atoms, the compound having 3 to 20 carbon atomsA branched alkyl group or an alkoxy group or a thioalkoxy group, a cyclic alkyl group or an alkoxy group or a thioalkoxy group having 3 to 20 carbon atoms, a ketone group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, a crosslinkable group, a substituted or unsubstituted aromatic group or heteroaromatic group having 5 to 60 ring atoms, an aryloxy group or a heteroaromatic group having 5 to 60 ring atoms, or a combination of these groups;

2. An organic compound according to claim 1, characterized in that: r₂When occurring for multiple times, at least one is independently selected from cyano, nitro and CF₃Cl, Br, F, I, or by cyano, nitro, CF₃Aryl substituted by Cl, Br, F, I, or by cyano, nitro, CF₃Cl, Br, F, I substituted heteroaromatic groups.

3. An organic compound according to claim 1, characterized in that:

(A-1) is selected from the following groups:

(A-2) is selected from the following groups:

(A-3) is selected from the following groups:

(A-4) is selected from the following groups:

and (A-5) is selected from the group consisting of:

4. an organic compound according to claim 1, characterized in that: n is selected from 1 or 2.

5. An organic compound according to claim 1, characterized in that: when Ar occurs multiple times, Ar is selected from groups of the same structure.

6. An organic compound according to claim 1, characterized in that: the general formula (1) is selected from any one of the following structures:

7. Organic compound according to any one of claims 1 to 6An article, characterized in that: r₁When occurring for multiple times, at least one is independently selected from cyano, nitro and CF₃Cl, Br, F, I, or by cyano, nitro, CF₃Aryl substituted by Cl, Br, F, I, or by cyano, nitro, CF₃Cl, Br, F, I substituted heteroaromatic groups.

8. The organic compound according to any one of claims 1 to 6, wherein: r₁Selected from cyano groups.

9. An organic compound according to claim 1, characterized in that: the general formula (1) is selected from any one of the following structures:

10. a mixture, characterized by: comprising an organic compound according to any one of claims 1 to 9, and at least one organic functional material selected from hole injection materials, hole transport materials, electron injection materials, electron blocking materials, hole blocking materials, light emitters, host materials or organic dyes.

11. A composition characterized by: comprising an 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, characterized by: 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.