CN112552246A

CN112552246A - Cyclopentapyrazine organic compound and application thereof

Info

Publication number: CN112552246A
Application number: CN202010944797.6A
Authority: CN
Inventors: 宋鑫龙; 杨曦; 宋晶尧; 李们在; 李先杰; 王煦; 张月
Original assignee: Guangzhou Chinaray Optoelectronic Materials Ltd; Wuhan China Star Optoelectronics Semiconductor Display Technology Co Ltd
Current assignee: Guangzhou Chinaray Optoelectronic Materials Ltd; Wuhan China Star Optoelectronics Semiconductor Display Technology Co Ltd
Priority date: 2019-09-26
Filing date: 2020-09-10
Publication date: 2021-03-26

Abstract

The invention relates to a cyclopentapyrazine organic compound and application thereof. The organic compound has a structure represented by general formula (1). 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 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.

Description

Cyclopentapyrazine organic compound and application thereof

Technical Field

The invention relates to the technical field of organic electroluminescence, in particular to a cyclopentapyrazine organic 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 their advantages of being versatile, low cost to manufacture, and good in optical and electrical performance.

The organic light emitting diode consists of three parts, namely an anode, a cathode and an organic layer between the anode and the cathode. In order to improve the efficiency and lifetime of the organic light emitting diode, the organic layer generally has a multi-layer structure, and each layer contains different organic substances. Specifically, the organic layer may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. The basic principle of the light emission of the organic light emitting diode is as follows: when a voltage is applied between the two electrodes, the positive electrode injects holes into the organic layer, the negative electrode injects electrons into the organic layer, and the injected holes and electrons meet to form excitons, which emit light when they transition back to the ground state. The organic light emitting diode has the advantages of self-luminescence, high brightness, high efficiency, low driving voltage, wide viewing angle, high contrast, high responsiveness and the like. In order to improve the recombination efficiency of the injected holes and electrons, further improvement in the structure, material, and the like of the organic light emitting diode is required.

At present, merck company uses aromatic diamine derivative (patent CN104718636A) or aromatic condensed ring diamine derivative (patent CN107922312A) as hole transport material of organic light emitting diode to improve the efficiency of injecting holes, but at this time, the use voltage needs to be increased to make the organic light emitting diode fully emit light, which results in the problems of reduced lifetime and increased power consumption of the organic light emitting diode.

Such problems have recently been solved by doping the hole transport layer of organic light emitting diodes with electron acceptors, such as Tetracyanoquinodimethane (TCNQ) or 2,3,5, 6-tetrafluoro-tetracyano-1, 4-benzoquinodimethane (F4TCNQ) (Chemical Science2018,9(19), 4468-: the operation is unstable in the manufacturing process of the organic light emitting diode, the stability is insufficient when the organic light emitting diode is driven, the life is reduced, or the above compound is diffused in the device to contaminate the device when the organic light emitting diode is manufactured by vacuum deposition.

Therefore, there is a need for further improvement of an electron acceptor, i.e., a P-dopant, doped in the hole transport layer, and particularly for providing a dopant that can realize a low voltage and a long lifetime of the organic light emitting diode.

Disclosure of Invention

In view of the defects of the prior art, the invention aims to provide a cyclopentadiene pyrazine organic compound 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 represented by the general formula (1)

Wherein:

each occurrence of X is independently selected from N, SiR₃Or PR₃；

Each occurrence of Y is independently selected from N, CR₄、SiR₄Or PR₄；

M is selected from CR₅R₆、NR₅、SiR₅R₆、PR₅Substituted or unsubstituted aromatic groups containing 6 to 60C atoms, substituted or unsubstituted heteroaromatic groups containing 5 to 60 ring atoms or non-aromatic ring system groups containing 3 to 30 ring atoms;

R₁-R₆independently selected from H, D, straight chain alkyl having 1 to 20C atoms, alkoxy or thioalkoxy having 1 to 20C atoms, branched or cyclic alkyl having 3 to 20C atoms, alkoxy or thioalkoxy having 3 to 20C atoms, silyl, keto having 1 to 20C atoms, alkoxycarbonyl having 2 to 20C atoms, aryloxycarbonyl having 7 to 20C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanic acid, at each occurrenceEster group, isothiocyanate group, hydroxyl group, nitro group, nitroso group, CF₃、C₂F₅、C₃F₇Cl, Br, F, I, a crosslinkable group, a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 60 ring atoms, an aryloxy or heteroaryloxy group having 5 to 60 ring atoms, or a combination of these systems; r₁And R₂May combine with each other to form a substituted or unsubstituted ring.

A mixture comprising a cyclopentapyrazine-based organic compound as described above, 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 a cyclopentapyrazine-based organic compound or mixture as described above, and at least one organic solvent.

An organic electronic device, comprising at least a cyclopentapyrazine-based organic compound or mixture as described above or prepared from a composition as described above.

Has the advantages that:

the cyclopentapyrazine 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 doped in a hole injection layer or a hole transport layer as a dopant, so that the cyclopentapyrazine organic compound can be driven by low voltage, the electroluminescent efficiency can be improved, and the service life of a device can be prolonged.

Drawings

Fig. 1 is a structural diagram of an organic light emitting device according to an embodiment, in which 101 is a substrate, 102 is an anode, 103 is a Hole Injection Layer (HIL), 104 is a Hole Transport Layer (HTL), 105 is a light emitting layer, 106 is an Electron Injection Layer (EIL) or an Electron Transport Layer (ETL), and 107 is a cathode.

Detailed Description

The invention provides a cyclopentapyrazine organic compound and application thereof. 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, for example, systems such as pyridine, thiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, pyrazine, pyridazine, pyrimidine, triazine, carbene, and the like, are also considered aromatic or heterocyclic aromatic groups for the purposes of this invention. For the purposes of the present invention, fused-ring aromatic or fused-heterocyclic aromatic ring systems include not only systems of aromatic or heteroaromatic groups, but also systems in which a plurality of aromatic or heterocyclic aromatic groups may also be interrupted by short non-aromatic units (< 10% of non-H atoms, preferably less than 5% of non-H atoms, such as C, N or O atoms). Thus, for example, systems such as 9, 9' -spirobifluorene, 9, 9-diarylfluorene, triarylamines, diaryl ethers, etc., are also considered fused aromatic ring systems for the purposes of this invention.

In the embodiment of the present invention, the energy level structure of the organic material, the triplet state energy level E_THOMO, LUMO play a key role. These energy levels are described below.

The HOMO and LUMO energy levels can be measured by the photoelectric effect, for example XPS (X-ray photoelectron spectroscopy) and UPS (ultraviolet photoelectron spectroscopy) or by cyclic voltammetry (hereinafter referred to as CV). Recently, quantum chemical methods, such as the density functional theory (hereinafter abbreviated as DFT), have become effective methods for calculating the molecular orbital level.

Triplet energy level E of organic material_T1Can be measured by low temperature Time resolved luminescence spectroscopy, or can be obtained by quantum simulation calculations (e.g., by Time-dependent DFT), such as by commercial software Gaussian 03W (Gaussian Inc.), specific simulation methods can be found in WO2011141110 or as described in the examples below.

Note that HOMO, LUMO, E_T1The absolute value of (c) depends on the measurement method or calculation method used, and even for the same method, different methods of evaluation, for example starting point and peak point on the CV curve, can give different HOMO/LUMO values. Thus, a reasonably meaningful comparison should be made with the same measurement method and the same evaluation method. In the description of the embodiments of the present invention, HOMO, LUMO, E_T1Is based on the simulation of the Time-dependent DFT but does not affect the application of other measurement or calculation methods.

In the present invention, (HOMO-1) is defined as the second highest occupied orbital level, (HOMO-2) is defined as the third highest occupied orbital level, and so on. (LUMO +1) is defined as the second lowest unoccupied orbital level, (LUMO +2) is the third lowest occupied orbital level, and so on.

A cyclopentapyrazine-based organic compound has a structure represented by general formula (1):

wherein:

each occurrence of X is independently selected from N, SiR₃Or PR₃；

R₁-R₆independently selected from H, D, straight chain alkyl having 1 to 20C atoms, alkoxy or thioalkoxy having 1 to 20C atoms, branched or cyclic alkyl having 3 to 20C atoms, alkoxy or thioalkoxy having 3 to 20C atoms, silyl, keto having 1 to 20C atoms, alkoxycarbonyl having 2 to 20C atoms, aryloxycarbonyl having 7 to 20C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, nitroso, CF, at each occurrence₃、C₂F₅、C₃F₇Cl, Br, F, I, a crosslinkable group, a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 60 ring atoms, an aryloxy or heteroaryloxy group having 5 to 60 ring atoms, or a combination of these systems; r₁And R₂May combine with each other to form a substituted or unsubstituted ring.

The substitution in the invention means that the substituent is substituted by R, and R has the same meaning as R₁。

In a preferred embodiment, R₁And R₂Combine with each other to form a substituted or unsubstituted ring; more preferably, said general formula (1) is selected from general formula (2):

wherein：Ar¹Selected from substituted or unsubstituted aromatic groups containing 6 to 60C atoms or heteroaromatic groups containing 5 to 60 ring atoms or non-aromatic ring system groups containing 3 to 30 ring atoms; preferably, Ar¹Selected from substituted or unsubstituted aromatic groups containing 6 to 30C atoms or heteroaromatic groups containing 5 to 30 ring atoms or non-aromatic ring system groups containing 3 to 30 ring atoms; more preferably, Ar¹Selected from substituted or unsubstituted fused ring aromatic groups containing 10 to 60C atoms or fused ring heteroaromatic groups containing 8 to 60 ring atoms.

In a preferred embodiment, said M is selected from one of the following groups:

wherein:

q, E are each independently selected from CR₇R₈、NR₇、O、S、SiR₇R₈、PR₇、P(＝O)R₇、S＝O、S(＝O)₂Or C ═ O;

R₇、R₈independently selected from H, D, straight chain alkyl having 1 to 20C atoms, alkoxy or thioalkoxy having 1 to 20C atoms, branched or cyclic alkyl having 3 to 20C atoms, alkoxy or thioalkoxy having 3 to 20C atoms, silyl, keto having 1 to 20C atoms, alkoxycarbonyl having 2 to 20C atoms, aryloxycarbonyl having 7 to 20C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, CF, and mixtures thereof₃Cl, Br, F, I, a crosslinkable group, a substituted or unsubstituted aryl or heteroaryl group having 5 to 60 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 60 ring atoms, or a combination of these systems;

n1 is selected from any integer from 0 to 4.

In one embodiment, M is selected from CR₅R₆Or NR₅；

At one endIn embodiments, M is selected from CR₅R₆。

In one embodiment, R₅And R₆Selected from cyano, nitro, nitroso, CF₃Cl, Br, I or F, or by cyano, nitro, nitroso, CF₃Cl, Br, I or F substituted aryl or heteroaryl having 5 to 60 ring atoms.

Preferably, R₅And R₆At least one of them is selected from cyano, nitro, nitroso, CF₃Cl, Br, I or F; more preferably, R₅And R₆Are all selected from cyano, nitroso, nitro, CF₃Cl, Br, I or F.

In certain preferred embodiments, the M is selected from one of the following groups:

in certain preferred embodiments, formula (1) is selected from the following formulae:

in certain embodiments, each occurrence of Y is selected from CR₄(ii) a The general formula (1) is selected from any one of general formulae (3-1) and (3-2):

preferably, R₁、R₂Independently selected from cyano, nitro, nitroso, CF₃、C₂F₅、C₃F₇Cl, Br, F or I.

In certain preferred embodiments, formula (1) is selected from any one of formulae (4-1) and (4-2):

preferably, R₁、R₂、R₅、R₆Independently selected from H, cyano, nitro, nitroso, CF₃、C₂F₅、C₃F₇Cl, Br, F, I, and R₅、R₆At least one of them is selected from cyano, nitroso, nitro, CF₃Cl, Br, F or I.

In certain preferred embodiments, Ar¹One selected from the following groups:

wherein:

w is independently selected from CR at each occurrence₉R₁₀、NR₉、O、S、SiR₉R₁₀、PR₉、P(＝O)R₉、S＝O、S(＝O)₂Or C ═ O;

each occurrence of Z is independently selected from CR₉N or P;

R₉and R₁₀Independently selected from H, D, straight chain alkyl having 1 to 20C atoms, alkoxy or thioalkoxy having 1 to 20C atoms, branched or cyclic alkyl having 3 to 20C atoms, alkoxy or thioalkoxy having 3 to 20C atoms, silyl, keto having 1 to 20C atoms, alkoxycarbonyl having 2 to 20C atoms, aryloxycarbonyl having 7 to 20C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, CF, and mixtures thereof₃Cl, Br, F, I, a crosslinkable group, a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 60 ring atoms, an aryloxy or heteroaryloxy group having 5 to 60 ring atoms, or a combination of these systems.

In one embodiment, Ar¹One selected from the following groups:

more preferably, Ar¹One selected from the following groups:

wherein: the above groups may be further substituted by R, which has the same meaning as R₄。

In certain preferred embodiments, formula (2) is selected from one of the following formulae:

more preferably, the general formula (2) is selected from one of the following general formulae:

in certain preferred embodiments, Z is selected from CR in the above formula₉。

In one embodiment, R is as described above₄Selected from cyano, nitro, CF₃Cl, Br, F, I, a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 60 ring atoms, an aryloxy or heteroaryloxy group having 5 to 60 ring atoms, or a combination of these systems.

Preferably, R₄Selected from substituted or unsubstituted aromatic or heteroaromatic groups having from 5 to 60 ring atoms, aryloxy or heteroaryloxy groups having from 5 to 60 ring atoms, or combinations of these systems;

more preferably, R₄Selected from cyano, nitro, CF₃Cl, Br, F or I substituted aromatic or heteroaromatic groups having 5 to 60 ring atoms.

More preferably, R₄Selected from the group consisting of:

wherein: the above groups may further be substituted by R₁₁Substituted, R₁₁Has the same meaning as R₄(ii) a Preferably, R₁₁Selected from cyano, nitro, CF₃Cl, Br, F or I.

More preferably, R₄One selected from the following substituents:

R₁₁selected from cyano, nitro, CF₃Cl, Br, F or I.

In one embodiment, R₄And, when present, are selected from the same group.

Specific examples of the compounds according to the invention are given below by way of illustration and not of limitation:

the invention also relates to the composition as an organic ferromagnetic material, wherein the ferromagnetic organic compound is an organic material with ferromagnetism, also called an organic ferromagnetic material, the traditional ferromagnetic materials are inorganic materials such as alloys and oxides containing iron group or rare earth group metal elements, the ferromagnetism of the traditional ferromagnetic materials is derived from atomic magnetic moments and consists of two parts of electron orbit magnetic moments and electron spin magnetic moments, and the inorganic magnetic materials have the defects of large density, difficult processing and forming and the like, in the radical anion salt or the di-anion salt of the cyclopentapyrazine organic compound, the LUMO energy level is low, the ground state is stable, and a stable unfilled electron layer exists, so that a stable magnetic moment source can be provided, and the cyclopentapyrazine organic compound is expressed as magnetism and can be applied to the ferromagnetic materials (particularly, refer to documents Angew. chem. int. ed. Engl.1994, 33.385-415).

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, organic compounds according to the inventionObject of T₁More 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 invention also provides a mixture, which is characterized by comprising at least one organic compound 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 Hole Injection Material (HIM) or hole transport material and a dopant, the dopant being an organic compound as described above, 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.

It is another object of the present invention to provide a material solution for printing OLEDs.

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 compound or mixture as described above, and at least one organic solvent; the at least one organic solvent is selected from aromatic or heteroaromatic, ester, aromatic ketone or aromatic ether, aliphatic ketone or aliphatic ether, alicyclic or olefinic compound, or boric acid ester or phosphoric acid ester compound, or a mixture of two or more solvents.

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

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

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

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

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

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

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

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

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

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^1/2Example (A) ofEnclosing;

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

The invention further relates to an organic electronic device comprising at least one compound or mixture as described above. Furthermore, the organic electronic device comprises at least one functional layer comprising a compound or mixture as described above. The functional layer is selected from a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an emission layer (EML), an Electron Blocking Layer (EBL), an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), and a Hole Blocking Layer (HBL).

In a preferred embodiment, the organic electronic device according to the 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.

In the above-mentioned light emitting device, especially an OLED, it comprises a substrate, an anode, at least one light emitting layer, and a cathode.

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

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

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

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

The light-emitting device according to the present invention emits light at a wavelength of 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.

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.

EXAMPLE 1 Synthesis of Compound DPF-1

Synthesis of compound a 1:

the compounds diaminomaleonitrile (1.08g, 10mmol), oxalyl chloride (1.25g, 10mmol), 1, 4-dioxane (100 ml) were stirred at 50 ℃ for 5 hours, the reaction product was cooled to room temperature, then the precipitate formed was filtered under reduced pressure, and anhydrous magnesium sulfate was added thereto to remove water, then the solvent was removed under reduced pressure, the residue was subjected to silica gel column using dichloromethane as an eluent to give a product, then the solvent was removed under reduced pressure and the product was dried in vacuo to give the desired solid compound A1(1.10g, 68%), MS: [ M + H ], (M + H)]⁺＝163。

Synthesis of compound a 2:

the compound pentafluorophenylnitrile (3.84g, 20mmol), n-butyllithium (20 ml), acetone (100 ml) were reacted at-78 ℃ for 8 hours, the reaction product was allowed to stand at room temperature, 200ml of distilled water was added, then the precipitate formed was filtered under reduced pressure, the filtrate was extracted with dichloromethane, and anhydrous magnesium sulfate was added thereto to remove water, then the solvent was removed under reduced pressure, the residue was passed through a silica gel column using dichloromethane as an eluent to obtain a product, then the solvent was removed under reduced pressure and the product was dried under vacuum to prepare the desired solid compound A2(2.18g, 54%), MS: [ M + H ] (M + H)]⁺＝405。

Synthesis of compound a 3:

compound A1(1.63g, 10mmol), A2(4.04g, 10mmol) and 10ml acetic acid were heated overnight, the reaction mixture was cooled to room temperature, the resulting solid was filtered, and A3(4.28g, 81%) was obtained under washing with ethanol and water, MS: [ M + H ]]⁺＝529.

Synthesis of Compound DPF-1:

titanium tetrachloride (4.67g, 25mmol), A3(5.29g, 10mmol), A4(1.32g, 20mmol) was stirred at reflux for 24 hours in a nitrogen-dried pyridine/dichloromethane solvent, then quenched with cold concentrated hydrochloric acid,dichloromethane was concentrated, then dried over anhydrous sodium sulfate, distilled under reduced pressure, and the residue was recrystallized with DCM/MeOH to give DPF-1(1.20g, 21%), MS: [ M + H ]]⁺＝577。

EXAMPLE 2 Synthesis of Compound DPF-2

Synthesis of Compound DPF-2:

titanium tetrachloride (4.67g, 25mmol), A3(5.29g, 10mmol), A5(0.84g, 20mmol) in nitrogen dried pyridine/dichloromethane solvent was stirred at reflux for 24 hours, then quenched with cold concentrated hydrochloric acid, dichloromethane concentrated, then dried over anhydrous sodium sulfate, distilled under reduced pressure, and the residue recrystallized with DCM/MeOH to give DPF-2(0.49g, 9%), MS: [ M + H ])]⁺＝553。

EXAMPLE 3 Synthesis of Compound DPF-3

Synthesis of Compound DPF-3:

titanium tetrachloride (4.67g, 25mmol), A3(5.29g, 10mmol), A6(3.04g, 20mmol) in nitrogen dried pyridine/dichloromethane solvent was stirred at reflux for 24 hours, then quenched with cold concentrated hydrochloric acid, dichloromethane concentrated, then dried over anhydrous sodium sulfate, distilled under reduced pressure, and the residue recrystallized with DCM/MeOH to give DPF-3(1.91g, 29%), MS: [ M + H ])]⁺＝662。

EXAMPLE 4 Synthesis of Compound DPF-4

Synthesis of Compound DPF-4:

titanium tetrachloride (4.67g, 25mmol), A3(5.29g, 10mmol), A7(2,.18g, 20mmol) was stirred at reflux for 24 hours in nitrogen dried pyridine/dichloromethane solvent, after which it was quenched with cold concentrated hydrochloric acidThe dichloromethane was concentrated, then dried over anhydrous sodium sulfate, distilled under reduced pressure, and the residue was recrystallized with DCM/MeOH to give DPF-4(1.11g, 18%), MS: [ M + H ]]⁺＝620。

EXAMPLE 5 Synthesis of Compound DPF-5

Synthesis of Compound DPF-5:

titanium tetrachloride (4.67g, 25mmol), A3(5.29g, 10mmol), A8(1.70g, 20mmol) in nitrogen dried pyridine/dichloromethane solvent was stirred at reflux for 24 hours, then quenched with cold concentrated hydrochloric acid, dichloromethane concentrated, then dried over anhydrous sodium sulfate, distilled under reduced pressure, and the residue recrystallized with DCM/MeOH to give DPF-5(0.65g, 11%), MS: [ M + H ])]⁺＝596。

EXAMPLE 6 Synthesis of Compound DPF-6

Synthesis of Compound DPF-6:

titanium tetrachloride (4.67g, 25mmol), A3(5.29g, 10mmol), A9(1.74g, 20mmol) in nitrogen dried pyridine/dichloromethane solvent was stirred at reflux for 24 hours, then quenched with cold concentrated hydrochloric acid, dichloromethane concentrated, then dried over anhydrous sodium sulfate, distilled under reduced pressure, and the residue recrystallized with DCM/MeOH to give DPF-6(1.91g, 32%), MS: [ M + H ])]⁺＝597。

EXAMPLE 7 Synthesis of Compound DPF-7

Synthesis of Compound DPF-7:

titanium tetrachloride (4.67g, 25mmol), A3(5.29g, 10mmol), A10(2.58g, 20mmol) was stirred at reflux for 24 hours in nitrogen dried pyridine/dichloromethane solvent, then quenched with cold concentrated hydrochloric acid,dichloromethane was concentrated, then dried over anhydrous sodium sulfate, distilled under reduced pressure, and the residue was recrystallized with DCM/MeOH to give DPF-7(1.46g, 23%), MS: [ M + H ]]⁺＝639。

Example 8 Synthesis of the Compound DPF-69:

synthesis of compound a 11:

reacting the compound octafluoronaphthalene (5.42g, 20mmol), n-butyllithium (20 ml), acetone (100 ml) at-78 deg.C for 8 hours, allowing the reaction product to stand at room temperature, adding 200ml of distilled water, then filtering the resulting precipitate under reduced pressure, extracting the filtrate with dichloromethane, and adding anhydrous magnesium sulfate thereto to remove water, then removing the solvent under reduced pressure, passing the residue through a silica gel column using dichloromethane as an eluent to obtain a product, then removing the solvent under reduced pressure and drying the product in vacuo to give the desired solid compound A11(1.68g, 30%), MS: [ M + H ] (M + H) ([ M + H ])]⁺＝568。

Synthesis of compound a 12:

compound A1(1.63g, 10mmol), A11(5.68g, 10mmol) and 10ml acetic acid were heated overnight, the reaction mixture was cooled to room temperature, the resulting solid was filtered, and A12(1.84g, 27%) was obtained under washing with ethanol and water, MS: [ M + H ]]⁺＝685.

Synthesis of Compound DPF-69:

titanium tetrachloride (4.67g, 25mmol), A12(6.85g, 10mmol), A4(1.32g, 20mmol) in nitrogen dried pyridine/dichloromethane solvent was stirred at reflux for 24 hours, then quenched with cold concentrated hydrochloric acid, dichloromethane concentrated, then dried over anhydrous sodium sulfate, distilled under reduced pressure, and the residue recrystallized with DCM/MeOH to give DPF-69(1.02g, 14%), MS: [ M + H ], (M + H)]⁺＝734。

Example 9 Synthesis of the Compound DPF-101:

synthesis of compound a 13:

the compounds o-pyrenediamine (2.32g, 10mmol), oxalyl chloride (1.25g, 10mmol), 1, 4-dioxane (100 ml) were stirred at 50 ℃ for 5 hours, the reaction product was cooled to room temperature, then the precipitate formed was filtered under reduced pressure, and anhydrous magnesium sulfate was added thereto to remove water, then the solvent was removed under reduced pressure, the residue was subjected to silica gel column using dichloromethane as an eluent to give a product, then the solvent was removed under reduced pressure and the product was dried in vacuo to prepare the desired solid compound A13(1.60g, 56%), MS: [ M + H ] (M + H)]⁺＝287。

Synthesis of compound a 14:

compound A13(2.86g, 10mmol), A2(4.04g, 10mmol) and 10ml acetic acid were heated overnight, the reaction mixture was cooled to room temperature, the resulting solid was filtered, and A14(2.67g, 41%) was obtained under washing with ethanol and water, MS: [ M + H ]]⁺＝652.

Synthesis of Compound DPF-101:

titanium tetrachloride (4.67g, 25mmol), A14(6.52g, 10mmol), A8(1.70g, 20mmol) in nitrogen dried pyridine/dichloromethane solvent was stirred at reflux for 24 hours, then quenched with cold concentrated hydrochloric acid, dichloromethane concentrated, then dried over anhydrous sodium sulfate, distilled under reduced pressure, and the residue recrystallized with DCM/MeOH to give DPF-101(2.23g, 31%), MS: [ M + H ])]⁺＝720。

Example 10 synthesis of compound DPF-108:

synthesis of compound a 16:

compound A15(2.10g, 10mmol), oxalyl chloride (1.25g, 10mmol), 1, 4-dioxane 100ml was stirred at 50 ℃ for 5 hours, the reaction product was cooled to room temperature, then the precipitate formed was filtered under reduced pressure, and anhydrous magnesium sulfate was added thereto to remove water, then the solvent was removed under reduced pressure, the residue was subjected to silica gel column using dichloromethane as eluent to give the product, then the solvent was removed under reduced pressure andthe product was dried in vacuo to give the desired solid compound A16(1.29g, 49%), MS: [ M + H ]]⁺＝263。

Synthesis of compound a 18:

compound A17(3.52g, 20mmol), n-butyllithium 20ml, acetone 100ml were reacted at-78 ℃ for 8 hours, the reaction product was allowed to stand at room temperature, 200ml of distilled water was added, then the precipitate formed was filtered under reduced pressure, the filtrate was extracted with dichloromethane, and anhydrous magnesium sulfate was added thereto to remove water, then the solvent was removed under reduced pressure, the residue was passed through a silica gel column using dichloromethane as an eluent to give a product, then the solvent was removed under reduced pressure and the product was dried in vacuo to give desired solid compound A18(1.37g, 37%), MS: [ M + H ] (M + H) ([ M + H ])]⁺＝372。

Synthesis of compound a 19:

compound A16(2.64g, 10mmol), A18(3.71g, 10mmol) and 10ml acetic acid were heated overnight, the reaction mixture was cooled to room temperature, the resulting solid was filtered, and A19(4.85g, 81%) was obtained under washing with ethanol and water MS: [ M + H ]]⁺＝597.

Synthesis of Compound DPF-108:

titanium tetrachloride (4.67g, 25mmol), A19(5.98g, 10mmol), malononitrile (1.32g, 20mmol) in nitrogen dried pyridine/dichloromethane solvent was stirred at reflux for 24 hours, then quenched with cold concentrated hydrochloric acid, dichloromethane concentrated, then dried over anhydrous sodium sulfate, distilled under reduced pressure, and the residue recrystallized with DCM/MeOH to give DPF-108(3.68g, 57%), MS: [ M + H ]]⁺＝645。

Example 11 Synthesis of the Compound DPF-130:

synthesis of compound a 21:

compound A20(3.08g, 20mmol), 20ml of n-butyllithium, 100ml of acetone were reacted at-78 ℃ for 8 hours, the reaction product was allowed to stand at room temperature, 200ml of distilled water was added, then the precipitate formed was filtered under reduced pressure, the filtrate was extracted with dichloromethane,and anhydrous magnesium sulfate was added thereto to remove water, the solvent was then removed under reduced pressure, the residue was subjected to a silica gel column using methylene chloride as an eluent to give a product, the solvent was then removed under reduced pressure and the product was dried in vacuo to give the desired solid compound A21(2.15g, 66%), MS: [ M + H ])]⁺＝327。

Synthesis of compound a 23:

compound A22(1.09g, 10mmol), oxalyl chloride (1.25g, 10mmol), 1, 4-dioxane 100ml was stirred at 50 ℃ for 5 hours, the reaction product was cooled to room temperature, then the precipitate formed was filtered under reduced pressure, and anhydrous magnesium sulfate was added thereto to remove water, then the solvent was removed under reduced pressure, the residue was subjected to silica gel column using dichloromethane as an eluent to give a product, then the solvent was removed under reduced pressure and the product was dried in vacuo to give the desired solid compound A23(0.93g, 57%), MS: [ M + H ]]⁺＝164。

Synthesis of compound a 24:

compound A21(3.26g, 10mmol), A23(1.64g, 10mmol) and 10ml acetic acid were heated overnight, the reaction mixture was cooled to room temperature, the resulting solid was filtered, and A24(3.79g, 84%) was obtained under washing with ethanol and water MS: [ M + H ]]⁺＝452.

Synthesis of Compound DPF-130:

titanium tetrachloride (4.67g, 25mmol), A24(4.52g, 10mmol), malononitrile (1.32g, 20mmol) in nitrogen dried pyridine/dichloromethane solvent was stirred at reflux for 24 hours, then quenched with cold concentrated hydrochloric acid, dichloromethane concentrated, then dried over anhydrous sodium sulfate, distilled under reduced pressure, and the residue recrystallized with DCM/MeOH to give DPF-130(1.34g, 27%), MS: [ M + H ], []⁺＝499。

Example 12 Synthesis of the Compound DPF-149:

synthesis of compound a 26:

a mixture of compound A25(2.86g, 20mmol), n-butyllithium (20 ml) and acetone (100 ml) was stirred at-78 ℃The reaction was carried out for 8 hours, the reaction product was allowed to stand at room temperature, and 200ml of distilled water was added, then the precipitate formed was filtered under reduced pressure, the filtrate was extracted with methylene chloride, and anhydrous magnesium sulfate was added thereto to remove water, then the solvent was removed under reduced pressure, the residue was subjected to silica gel column using methylene chloride as an eluent to give a product, which was then removed under reduced pressure and dried in vacuo to give the desired solid compound A26(4.35g, 76%), MS: [ M + H ]]⁺＝573。

Synthesis of compound a 28:

compound A27(2.00g, 10mmol), oxalyl chloride (1.25g, 10mmol), 1, 4-dioxane 100ml was stirred at 50 ℃ for 5 hours, the reaction product was cooled to room temperature, then the precipitate formed was filtered under reduced pressure, and anhydrous magnesium sulfate was added thereto to remove water, then the solvent was removed under reduced pressure, the residue was subjected to silica gel column using dichloromethane as an eluent to give a product, then the solvent was removed under reduced pressure and the product was dried in vacuo to give the desired solid compound A28(1.34g, 53%), MS: [ M + H ]]⁺＝254。

Synthesis of compound a 29:

compound A26(5.73g, 10mmol), A28(2.54g, 10mmol) and 10ml acetic acid were heated overnight, the reaction mixture was cooled to room temperature, the resulting solid was filtered, and A29(6.11g, 81%) was obtained under washing with ethanol and water, MS: [ M + H ]]⁺＝755.

Synthesis of Compound DPF-149:

titanium tetrachloride (4.67g, 25mmol), A29(7.55g, 10mmol), A5(0.84g, 20mmol) in nitrogen dried pyridine/dichloromethane solvent was stirred at reflux for 24 hours, then quenched with cold concentrated hydrochloric acid, dichloromethane concentrated, then dried over anhydrous sodium sulfate, distilled under reduced pressure, and the residue recrystallized with DCM/MeOH to give DPF-149(1.48g, 19%), MS: [ M + H ])]⁺＝779。

Example 13 synthesis of compound DPF-185:

synthesis of compound a 31:

compound A30(1.92g, 20mmol), n-butyllithium 20ml, acetone 100ml were reacted at-78 ℃ for 8 hours, the reaction product was allowed to stand at room temperature, 200ml of distilled water was added, then the precipitate formed was filtered under reduced pressure, the filtrate was extracted with dichloromethane, and anhydrous magnesium sulfate was added thereto to remove water, then the solvent was removed under reduced pressure, the residue was passed through a silica gel column using dichloromethane as an eluent to give a product, then the solvent was removed under reduced pressure and the product was dried in vacuo to give desired solid compound A31(1.94g, 92%), MS: [ M + H ] (M + H): (1.94g, 92%)]⁺＝211。

Synthesis of compound a 33:

compound A32(1.82g, 10mmol), oxalyl chloride (1.25g, 10mmol), 1, 4-dioxane 100ml was stirred at 50 ℃ for 5 hours, the reaction product was cooled to room temperature, then the precipitate formed was filtered under reduced pressure, and anhydrous magnesium sulfate was added thereto to remove water, then the solvent was removed under reduced pressure, the residue was subjected to silica gel column using dichloromethane as an eluent to give a product, then the solvent was removed under reduced pressure and the product was dried in vacuo to give the desired solid compound A33(1.95g, 82%), MS: [ M + H ]]⁺＝238。

Synthesis of compound a 34:

compound A31(2.11g, 10mmol), A33(2.38g, 10mmol) and 10ml acetic acid were heated overnight, the reaction mixture was cooled to room temperature, the resulting solid was filtered, and A34(3.51g, 86%) was obtained under washing with ethanol and water, MS: [ M + H ]]⁺＝409.

Synthesis of Compound DPF-185:

titanium tetrachloride (4.67g, 25mmol), A34(4.08g, 10mmol), malononitrile (1.32g, 20mmol) in nitrogen dried pyridine/dichloromethane solvent was stirred at reflux for 24 hours, then quenched with cold concentrated hydrochloric acid, dichloromethane concentrated, then dried over anhydrous sodium sulfate, distilled under reduced pressure, and the residue recrystallized with DCM/MeOH to give DPF-185(3.29g, 72%), MS: [ M + H ]]⁺＝457。

Preparation and characterization of OLED device

The energy level of the organic compound material can be obtained by quantum calculation, for example, by Gaussian 09W (Gaussian Inc.) by using TD-DFT (including time density functional theory), and a specific simulation method can be found 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 were calculated according to the following calibration formula, S1, T1 and resonance factor f (S1) 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, LUMO, T1, and S1 are direct calculations of Gaussian 09W, in Hartree. The results are shown in table 1 below:

TABLE 1

Material	HOMO[eV]	LUMO[eV]	T1[eV]	S1[eV]
					Compound DPF-1	-7.21	-5.54	0.68	2.13
Compound DPF-2	-6.56	-5.21	0.83	1.81
					Compound DPF-3	-6.32	-5.45	0.81	2.19
Compound DPF-4	-7.17	-5.68	0.72	2.06
					Compound DPF-5	-6.53	-5.44	0.79	1.74
Compound DPF-6	-7.24	-5.36	0.61	2.01
					Compound DPF-7	-6.67	-5.29	0.80	1.92
Compound DPF-69	-6.81	-5.41	0.71	2.03
					Compound DPF-101	-7.04	-5.42	0.70	2.06
Compound DPF-108	-6.68	-5.21	0.79	1.84
					Compound DPF-130	-7.25	-5.32	0.61	2.07
Compound DPF-149	-6.69	-5.31	0.76	1.71
					Compound DPF-185	-6.54	-5.31	0.72	2.16
Comparative Compound 1(F4TCNQ)	-7.84	-5.30	0.48	2.59

The device structure is as follows: ITO/HIL (10nm)/HT-1(120nm)/HT-2(10nm)/BH: BD (25nm)/ET: Liq30nm)/Liq (1nm)/Al (100nm),

materials used for the layers of the OLED device:

the preparation method comprises the following specific steps:

a. cleaning of the conductive glass substrate, the conductive glass substrate can be cleaned by using various solvents such as chloroform, ketone and isopropanol when being used for the first time, and then ultraviolet ozone plasma treatment is carried out.

b. HIL (10nm), HT-1(120nm), HT-2(10nm), EML (20nm), ETL (30 nm): the ITO substrate was transferred into a vacuum vapor deposition apparatus and evaporated under high vacuum (1X 10-6 mbar) using resistive heating, HT-1 and DPF-1 were heated at a rate of 98: 2 to form a10 nm HIL (hole injection layer), and then successively evaporated to form 120nm HT-1 and 10nm HT-2 layers. Then BH and BD were measured at 97: 3 to form a25 nm light-emitting layer. Then ET and Liq were put in different evaporation units and co-deposited at a ratio of 50 wt% respectively to form an electron transport layer of 30nm on the light emitting layer, and subsequently Liq of 1nm was deposited as an electron injection layer on the electron transport layer, and finally an Al cathode having a thickness of 100nm was deposited on the electron injection layer.

c. Encapsulation the devices were encapsulated with uv curable resin in a nitrogen glove box.

All devices have the same embodiment except that the HIL uses different compounds as dopants (P-dopants). The current-voltage (J-V) characteristics of each OLED device were characterized by a characterization apparatus, while recording important parameters such as efficiency, lifetime, and external quantum efficiency, as shown in table 2.

TABLE 2

According to detection, the efficiency and the service life of the device are better than those of the conventional commonly used P-dock material F4TCNQ by adopting the compound, particularly when the P-dock material is selected from DPF-1 and DPF-6, DPF-69 and DPF-130, the service life is improved by about 20%, and the efficiency of the device is improved by about 10%. From the above, it can be seen that the compounds of the present application as dopants in HTL layers result in devices with far better efficiency and lifetime than F4 TCNQ.

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. A cyclopentapyrazine-based organic compound having a structure represented by general formula (1):

wherein:

each occurrence of X is independently selected from N, SiR₃Or PR₃；

2. The cyclopentapyrazine-based organic compound according to claim 1, wherein: the general formula (1) is selected from general formula (2):

wherein: ar (Ar)¹Selected from substituted or unsubstituted aromatic groups containing 6 to 60C atoms, substituted or unsubstituted heteroaromatic groups containing 5 to 60 ring atoms, or non-aromatic ring system groups containing 3 to 30 ring atoms.

3. The cyclopentapyrazine-based organic compound according to claim 1 or 2, wherein: the M is selected from one of the following groups:

wherein:

n1 is selected from any integer from 0 to 4.

4. The cyclopentapyrazine-based organic compound according to claim 1 or 2, wherein: m is selected from CR₅R₆Or NR₅。

5. The cyclopentapyrazine-based organic compound according to claim 1 or 2, wherein: the M is selected from one of the following groups:

6. the cyclopentapyrazine-based organic compound according to claim 1 or 2, wherein: each occurrence of Y is selected from CR₄；

R₄Selected from cyano, nitro, CF₃Cl, Br, F, I, a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 60 ring atoms, an aryloxy or heteroaryloxy group having 5 to 60 ring atoms, or a combination of these systems.

7. The cyclopentapyrazine-based organic compound according to claim 1 or 2, wherein: the general formula (1) is selected from any one of general formulas (3-1) and (3-2):

8. the cyclopentapyrazine-based organic compound according to claim 2, wherein: ar is¹One selected from the following groups:

each occurrence of Z is independently selected from CR₉N or P;

R₉and R₁₀Each occurrence is independently selected from H, D, a straight chain alkyl group having 1 to 20C atoms, an alkoxy or thioalkoxy group having 1 to 20C atoms, a branched or cyclic alkyl group having 3 to 20C atoms, an alkoxy group having 3 to 20C atomsOr thioalkoxy, silyl, keto with 1 to 20C atoms, alkoxycarbonyl with 2 to 20C atoms, aryloxycarbonyl with 7 to 20C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, CF₃Cl, Br, F, I, a crosslinkable group, a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 60 ring atoms, an aryloxy or heteroaryloxy group having 5 to 60 ring atoms, or a combination of these systems.

9. The cyclopentapyrazine-based organic compound of claim 8, wherein: the general formula (2) is selected from one of the following general formulae:

10. the cyclopentapyrazine-based organic compound of claim 6, wherein: the R is₄One selected from the following substituents:

wherein: r₁₁Selected from cyano, nitro, CF₃Cl, Br, F or I.

11. A mixture, characterized by: comprising a cyclopentapyrazine-based organic compound according to any one of claims 1 to 10, 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.

12. A composition comprising a cyclopentapyrazine-based organic compound according to any one of claims 1 to 10 or a mixture according to claim 11, and at least one organic solvent.

13. An organic electronic device, characterized in that it comprises at least a cyclopentapyrazine-based organic compound according to any one of claims 1 to 10 or a mixture according to claim 11 or prepared from a composition according to claim 12.