WO2021135841A1 - 有机电致发光器件和含稠环的芳香族化合物 - Google Patents

有机电致发光器件和含稠环的芳香族化合物 Download PDF

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WO2021135841A1
WO2021135841A1 PCT/CN2020/134314 CN2020134314W WO2021135841A1 WO 2021135841 A1 WO2021135841 A1 WO 2021135841A1 CN 2020134314 W CN2020134314 W CN 2020134314W WO 2021135841 A1 WO2021135841 A1 WO 2021135841A1
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organic electronic
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杨曦
陈佳
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广州华睿光电材料有限公司
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Priority to CN202080060029.2A priority Critical patent/CN114616233B/zh
Priority to EP20910838.0A priority patent/EP4086263A4/en
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Definitions

  • the present invention relates to the field of organic electroluminescence technology, in particular to a compound, mixture, composition and organic electronic device for organic electronic devices, especially applications in the field of electroluminescence devices.
  • OLEDs organic light-emitting diodes
  • Organic light-emitting diodes are composed of three parts: anode and cathode, and an organic layer between them.
  • the organic layer generally has a multilayer structure, and each layer contains different organic substances. Specifically, it 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 this kind of organic light-emitting diodes is that when a voltage is applied between two electrodes, the positive electrode injects holes into the organic layer, and the negative electrode injects electrons into the organic layer. When the injected holes and electrons meet, they will become excitons.
  • organic light-emitting diodes have 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 injected holes and electrons, it is necessary to further improve the structure and materials of organic light emitting diodes.
  • hole injection and high-efficiency transport are the key.
  • triarylamine derivatives or carbazole derivatives are generally used as hole injection materials.
  • the purpose of the present invention is to provide a compound, mixture, composition and organic electronic device for organic electronic devices, aiming to provide a new type of organic optoelectronic functional materials to improve the efficiency and efficiency of the device. life.
  • a compound used in organic electronic devices having a structure as the general formula (1):
  • Ar 1 is selected from structural formula (A-1) or (A-2):
  • M is selected from CR 2 R 3 , NR 2 , SiR 2 R 3 , PR 2 , or substituted or unsubstituted aromatic groups containing 6-60 C atoms, substituted or unsubstituted heteroaromatic groups containing 5-60 ring atoms Group, or a non-aromatic ring system group with 3-30 ring atoms;
  • n is selected from any integer from 0-4;
  • R 1 -R 5 is independently selected from H, D, or linear alkyl, alkoxy or thioalkoxy having 1 to 20 C atoms, or 3 to 20 C atoms A branched or cyclic alkyl, alkoxy or thioalkoxy group, or a silyl group, or a keto group having 1 to 20 C atoms, or an alkoxycarbonyl group having 2 to 20 C atoms , Or aryloxycarbonyl, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl with 7 to 20 C atoms , Nitro, nitroso, CF 3 , Cl, Br, F, I, cross-linkable groups, or substituted or unsubstituted aromatic groups with 5 to 60 ring atoms, heteroaromatic groups, or 5 Up to 60 ring atoms of aryloxy, heteroaryl
  • the present invention further relates to a mixture comprising a compound for use in organic electronic devices as described above, and at least one organic functional material selected from the group consisting of hole injection materials, hole transport materials, electron transport Materials, electron injection materials, electron blocking materials, hole blocking materials, luminous bodies, host materials, or organic dyes.
  • the present invention further relates to a composition
  • a composition comprising a compound for organic electronic devices as described above or a mixture as described above, and at least one organic solvent.
  • the present invention further relates to an organic electronic device comprising at least one functional layer, and the material of the functional layer comprises a compound for organic electronic devices as described above or a mixture as described above, or a combination as described above ⁇ Prepared from.
  • the functional layer is selected from hole injection layers.
  • the compound used in the organic electronic device of the present invention is an indolocarbazole organic compound, which is easy to synthesize. When it is used as a P-dopant in the hole injection layer of an organic electronic device, it can effectively improve the life and the life of the device. Efficiency, while reducing the operating voltage.
  • FIG. 1 is a structural diagram of an organic light-emitting device according to an embodiment.
  • 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 The electron injection layer (EIL) or electron transport layer (ETL)
  • 107 is the cathode.
  • the invention provides a compound mixture and composition of an organic electronic device and an organic electronic device.
  • an organic electronic device and an organic electronic device.
  • substituted means that the hydrogen atom in the substituted group is replaced by the substituent.
  • the number of ring atoms means the number of structural compounds (for example, monocyclic compounds, condensed ring compounds, cross-linked compounds, carbocyclic compounds, heterocyclic compounds) obtained by synthesizing a cyclic atom bond to form the ring itself The number of atoms among atoms.
  • the ring is substituted by a substituent, the atoms contained in the substituent are not included in the ring-forming atoms.
  • the number of ring atoms of the benzene ring is 6
  • the number of ring atoms of the naphthalene ring is 10
  • the number of ring atoms of the thienyl group is 5.
  • the aromatic group refers to a hydrocarbon group containing at least one aromatic ring.
  • a heteroaromatic group refers to an aromatic hydrocarbon group containing at least one heteroatom.
  • the heteroatoms are preferably selected from Si, N, P, O, S and/or Ge, particularly preferably selected from Si, N, P, O and/or S.
  • a fused-ring aromatic group means that the ring of an aromatic group can have two or more rings, in which two carbon atoms are shared by two adjacent rings, that is, a fused ring.
  • the fused heterocyclic aromatic group refers to a fused ring aromatic hydrocarbon group containing at least one heteroatom.
  • aromatic groups or heteroaromatic groups include not only aromatic ring systems but also non-aromatic ring systems.
  • systems such as pyridine, thiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, pyrazine, pyridazine, pyrimidine, triazine, carbene, etc., are also considered for the purpose of this invention Is an aromatic group or a heterocyclic aromatic group.
  • the fused-ring aromatic or fused heterocyclic aromatic ring system not only includes the system of aromatic groups or heteroaromatic groups, but also multiple aromatic groups or heterocyclic aromatic groups can be shortened
  • Non-aromatic units are discontinuous ( ⁇ 10% of non-H atoms, preferably less than 5% of non-H atoms, such as C, N or O atoms). Therefore, systems such as 9,9'-spirobifluorene, 9,9-diaryl fluorene, triarylamine, diaryl ether, etc., are also considered to be fused-ring aromatic ring systems for the purpose of this invention.
  • the present invention relates to a compound for organic electronic devices, which has a structure as the general formula (1):
  • Ar 1 is selected from structural formula (A-1) or (A-2):
  • M is selected from CR 2 R 3 , NR 2 , SiR 2 R 3 , PR 2 , or substituted or unsubstituted aromatic groups containing 6-60 C atoms, substituted or unsubstituted heteroaromatic groups containing 5-60 ring atoms Group, or a non-aromatic ring system group with 3-30 ring atoms;
  • n is selected from any integer from 0-4;
  • R 1 -R 5 is independently selected from H, D, or linear alkyl, alkoxy or thioalkoxy having 1 to 20 C atoms, or 3 to 20 C atoms A branched or cyclic alkyl, alkoxy or thioalkoxy group, or a silyl group, or a keto group having 1 to 20 C atoms, or an alkoxycarbonyl group having 2 to 20 C atoms , Or aryloxycarbonyl, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl with 7 to 20 C atoms , Nitro, nitroso, CF 3 , Cl, Br, F, I, cross-linkable groups, or substituted or unsubstituted aromatic groups with 5 to 60 ring atoms, heteroaromatic groups, or 5 Up to 60 ring atoms of aryloxy, heteroaryl
  • Ar 1 is selected from structural formula (A-1), and general formula (1) is selected from the following general formulas:
  • n in the general formula (I-1) or the general formula (2-1) or the general formula (2-2) is selected from any integer of 1-4.
  • Ar 1 is selected from structural formula (A-2), and general formula (1) is selected from the following general formulas:
  • n is selected from 0 in general formula (I-2) or general formula (2-3) or general formula (2-4).
  • n in the general formula (I-2) or the general formula (2-3) or the general formula (2-4) is selected from any integer of 1-4.
  • each time R 1 appears is independently selected from D, or a linear alkyl group having 1 to 20 C atoms, or a branched or cyclic alkyl group having 3 to 20 C atoms, Cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, CF 3 , Cl, Br, F, I, Or a substituted or unsubstituted aromatic group, heteroaromatic group with 5 to 60 ring atoms, or a combination of these systems; adjacent R 1 can be combined with each other to form a substituted or unsubstituted ring.
  • each time R 1 appears is independently selected from cyano, nitro, nitroso, CF 3 , Cl, B, I, F, or cyano, nitro, nitroso, CF 3.
  • R 1 when R 1 occurs multiple times, it is selected from the same group.
  • R 1 is selected from an aromatic group or a heteroaromatic group substituted by a cyano group, a nitro group, a nitroso group, CF 3 , Cl, B, I, or F.
  • R 1 in general formula (I-1) or general formula (2-1) or general formula (2-2) is selected from the group consisting of cyano, nitro, nitroso, CF 3 , Cl, B, I, F-substituted aromatic group or heteroaromatic group; further, R 1 in general formula (I-1) or general formula (2-1) or general formula (2-2) is selected from cyano, nitro, nitroso Group, CF 3 , Cl, B, I, F substituted aromatic group or heteroaromatic group with 6 ring atoms.
  • each occurrence of Y 1 -Y 4 is independently selected from a single bond, CR 4 R 5 , O or S.
  • Y 1 and Y 4 are selected from the same group, more preferably, Y 1 and Y 4 are selected from O or S or CR 4 R 5 at the same time.
  • Y 1 and Y 3 are selected from the same group, more preferably, Y 1 and Y 3 are selected from O or S or CR 4 R 5 at the same time.
  • Y 1 and Y 3 in the general formula (2-4) are selected from S at the same time.
  • M when M appears multiple times, it is independently selected from CR 2 R 3 or NR 2 ;
  • R 2 and R 3 are selected from cyano, nitro, nitroso, CF 3 , Cl, B, I, F, or cyano, nitro, nitroso, CF 3 , Cl, B, I, F-substituted aromatic or heteroaromatic group.
  • M is selected from one of the following groups:
  • each time R 6 appears it is independently selected from cyano, nitro, nitroso, CF 3 , Cl, B, I or F;
  • n is selected from any integer of 0-5; preferably, m is selected from any integer of 1-5.
  • M is selected from one of the following groups:
  • M when M appears multiple times, it is selected from the same group; further, M is selected from
  • the aromatic group or heteroaromatic group substituted by cyano, nitro, nitroso, CF 3 , Cl, B, I, F as described above is preferably selected from one of the following groups Species:
  • X is independently selected from CR 7 or N;
  • Each occurrence of R 7 -R 9 is independently selected from H, D, or a linear alkyl group having 1 to 20 C atoms, or a branched or cyclic alkyl group having 3 to 20 C atoms, or Keto groups having 1 to 20 C atoms, or alkoxycarbonyl groups having 2 to 20 C atoms, or aryloxycarbonyl groups having 7 to 20 C atoms, cyano, carbamoyl, cyano, nitro Group, nitroso group, CF 3 , Cl, B, I, F, or substituted or unsubstituted aryl group having 5 to 60 ring atoms, heteroaryl group, or aryloxy group having 5 to 60 ring atoms , Heteroaryloxy, or a combination of these systems; and at least one R 7 is selected from cyano, nitro, nitroso, CF 3 , Cl, B, I, or F.
  • each time R 1 appears is independently selected from Preferably, R 7 is independently selected from H, D, cyano, nitro, nitroso, CF 3 , Cl, B, I or F, and at least one R 7 is selected from cyano, nitro, nitroso, CF 3 , Cl, B, I, or F.
  • aromatic group or heteroaromatic group substituted by cyano, nitro, nitroso, CF 3 , Cl, B, I, F is preferably selected from one of the following groups:
  • the general formula (1) is preferably the general formula (I-3) or (I-4):
  • R 1 in (I-3) or (I-4) is selected from aromatic groups or heteroaromatic groups substituted by cyano, nitro, nitroso, CF 3 , Cl, B, I, F .
  • the general formula (1) is preferably the general formula (I-5) or (I-6):
  • R 7 has the same meaning as described above; preferably, when R 7 occurs multiple times, all are independently selected from cyano, nitro, nitroso, CF 3 , Cl, B, I or F.
  • the compound used for the organic electronic device as described above is further defined as a material used for the hole injection layer of the organic electronic device or a p-dopant material used for the hole transport layer of the organic electronic device.
  • Organic functional layers include, but are not limited to, hole injection layer (HIL), hole transport layer (HTL), electron transport layer (ETL), electron injection layer (EIL), electron blocking layer (EBL), hole blocking layer (HBL), the light-emitting layer (EML).
  • HIL hole injection layer
  • HTL hole transport layer
  • ETL electron transport layer
  • EIL electron injection layer
  • EBL electron blocking layer
  • HBL hole blocking layer
  • EML light-emitting layer
  • the organic compound according to the invention is used in the hole injection layer or P-dopant.
  • the present invention also provides a mixture comprising at least one of the above-mentioned compounds for use in organic electronic devices, and at least another organic functional material, and the at least another organic functional material is optional for hole injection Materials (HIM), hole transport materials (HTM), electron transport materials (ETM), electron injection materials (EIM), electron blocking materials (EBM), hole blocking materials (HBM), luminescent materials (Emitter), host materials (Host) and organic dyes.
  • HIM hole injection Materials
  • HTM hole transport materials
  • ETM electron transport materials
  • EIM electron injection materials
  • EBM electron blocking materials
  • Emitter hole blocking materials
  • host materials Hos
  • organic dyes organic dyes.
  • various organic functional materials are described in detail in WO2010135519A1, US20090134784A1 and WO2011110277A1, and the entire contents of these 3 patent documents are hereby incorporated by reference.
  • 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).
  • HIM hole injection material
  • HTM hole transport material
  • Host host material
  • the mixture includes at least one hole injection material (HIM) or hole transport material and one dopant, and the dopant is the above-mentioned compound for organic electronic devices.
  • HIM hole injection material
  • the molar ratio of dopant to host is 1:1 to 1:100,000.
  • Another object of the present invention is to provide a material solution for printed OLEDs.
  • the compound according to the present invention has a molecular weight of ⁇ 800 g/mol, preferably ⁇ 900 g/mol, very preferably ⁇ 1000 g/mol, more preferably ⁇ 1100 g/mol, and most preferably ⁇ 1200 g/mol.
  • the compound according to the present invention has a solubility in toluene at 25°C of ⁇ 2mg/ml, preferably ⁇ 3mg/ml, more preferably ⁇ 4mg/ml, most preferably ⁇ 5mg/ml.
  • the present invention also relates to a composition
  • a composition comprising at least one compound for organic electronic devices as described above or a 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 olefin compound, or borate or phosphate compound, or two or more solvents mixture.
  • a composition according to the present invention is characterized in that the at least one organic solvent is selected from aromatic or heteroaromatic-based solvents.
  • aromatic or heteroaromatic solvents suitable for the present invention include, but are not limited to: p-diisopropylbenzene, pentylbenzene, tetralin, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene , 3-isopropylbiphenyl, p-cymene, 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 , Cyclohexylbenzen
  • aromatic ketone-based solvents suitable for the present invention include, but are not limited to: 1-tetralone, 2-tetralone, 2-(phenylepoxy)tetralone, 6-(methoxy) Base) tetralone, acetophenone, phenylacetone, benzophenone, and their derivatives, such as 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylpropiophenone, 3-methylpropiophenone, 2-methylpropiophenone, etc.;
  • aromatic ether-based solvents suitable for the present invention include, but are not limited to: 3-phenoxytoluene, butoxybenzene, p-anisaldehyde dimethyl acetal, tetrahydro-2-phenoxy-2H -Pyran, 1,2-dimethoxy-4-(1-propenyl)benzene, 1,4-benzodioxane, 1,3-dipropylbenzene, 2,5-dimethoxy Toluene, 4-ethyl ethyl ether, 1,3-dipropoxybenzene, 1,2,4-trimethoxybenzene, 4-(1-propenyl)-1,2-dimethoxybenzene, 1, 3-Dimethoxybenzene, glycidyl phenyl ether, dibenzyl ether, 4-tert-butyl anisole, trans-p-propenyl anisole, 1,2-dimethoxybenzene, 1-methyl Oxynaphthalene,
  • the at least one solvent may be selected from: aliphatic ketones, for example, 2-nonanone, 3-nonanone, 5-nonanone, 2 -Decanone, 2,5-hexanedione, 2,6,8-trimethyl-4-nonanone, fenchone, phorone, isophorone, di-n-amyl ketone, etc.; or aliphatic ether , For example, 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, etc.
  • aliphatic ketones for example, 2-nonanone
  • the at least one solvent may be selected from ester-based solvents: alkyl octanoate, alkyl sebacate, alkyl stearate, benzene Alkyl formate, alkyl phenylacetate, alkyl cinnamate, alkyl oxalate, alkyl maleate, alkyl lactone, alkyl oleate, etc.
  • ester-based solvents alkyl octanoate, alkyl sebacate, alkyl stearate, benzene Alkyl formate, alkyl phenylacetate, alkyl cinnamate, alkyl oxalate, alkyl maleate, alkyl lactone, alkyl oleate, etc.
  • Particularly preferred are octyl octanoate, diethyl sebacate, diallyl phthalate, and isononyl isononanoate.
  • the solvent can be used alone or as a mixture of two or more organic solvents.
  • a composition according to the present invention is characterized in that it contains at least one organic compound or polymer or mixture as described above and at least one organic solvent, and may further contain another An organic solvent.
  • another organic solvent include (but are not limited to): methanol, ethanol, 2-methoxyethanol, dichloromethane, 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-phenoxy toluene, 1,1 ,1-Trichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethylsulfoxide, tetral
  • the solvent particularly suitable for the present invention is a solvent whose Hansen solubility parameter is within the following range:
  • ⁇ d (dispersion force) is in the range of 17.0-23.2MPa 1/2 , especially in the range of 18.5-21.0MPa 1/2;
  • ⁇ p polar forces in the range of 0.2 ⁇ 12.5MPa 1/2, especially in the 2.0 ⁇ 6.0MPa 1/2;
  • the boiling point parameter of the organic solvent needs to be considered when selecting the organic solvent.
  • the boiling point of the organic solvent is ⁇ 150°C; preferably ⁇ 180°C; more preferably ⁇ 200°C; more preferably ⁇ 250°C; most preferably ⁇ 275°C or ⁇ 300°C. Boiling points in these ranges are beneficial to prevent nozzle clogging of inkjet print heads.
  • the organic solvent can be evaporated from the solvent system to form a film containing functional materials.
  • the composition according to the invention is a solution.
  • composition according to the invention is a suspension.
  • composition in the embodiment of the present invention may include 0.01 to 10 wt% of the compound or mixture for organic electronic devices according to the present invention, preferably 0.1 to 15 wt%, more preferably 0.2 to 5 wt%, most preferably Is 0.25 to 3wt%.
  • the present invention also relates to the use of the composition as a coating or printing ink in the preparation of organic electronic devices, and the preparation method by printing or coating is particularly preferred.
  • suitable printing or coating technologies include (but are not limited to) inkjet printing, nozzle printing, letterpress printing, screen printing, dip coating, spin coating, doctor blade coating, roller printing, and twisting roller Printing, offset printing, flexographic printing, rotary printing, spraying, brushing or pad printing, slit-type extrusion coating, etc.
  • the first choice is gravure printing, jet printing and inkjet printing.
  • the solution or suspension may additionally include one or more components such as surface active compounds, lubricants, wetting agents, dispersants, hydrophobic agents, adhesives, etc., for adjusting viscosity, film-forming properties, and improving adhesion. Relevant printing technology and related requirements for related solutions, such as solvent and concentration, viscosity, etc.
  • the present invention also provides an application of the compound, mixture or composition as described above in an organic electronic device.
  • the organic electronic device can be selected from, but not limited to, organic light-emitting diodes (OLED), organic photovoltaic cells (OPV) ), Organic Light Emitting Battery (OLEEC), Organic Field Effect Tube (OFET), Organic Light Emitting Field Effect Tube, Organic Laser, Organic Spintronic Device, Organic Sensor and Organic Plasmon Emitting Diode (Organic Plasmon Emitting Diode), etc., Particularly preferred is OLED.
  • OLED organic light-emitting diodes
  • OLED organic photovoltaic cells
  • OFET Organic Field Effect Tube
  • OLED Organic Light Emitting Field Effect Tube
  • Organic Laser Organic Spintronic Device
  • Organic Sensor and Organic Plasmon Emitting Diode Organic Plasmon Emitting Diode
  • Organic Plasmon Emitting Diode Organic Plasmon Emitting Diode
  • the present invention further relates to an organic electronic device, which comprises at least one compound or mixture for organic electronic devices as described above, or is prepared from the above-mentioned composition.
  • the organic electronic device includes at least one functional layer, and the functional layer includes a compound or mixture or high polymer for an organic electronic device as described above, or is prepared from the above-mentioned composition.
  • the functional layer is selected from a hole injection layer, a hole transport layer, a light emitting layer, an electron blocking layer, an electron injection layer, an electron transport layer, and a hole blocking layer.
  • the organic electronic device according to the present invention includes at least one hole injection layer or hole transport layer, and the hole injection layer or hole transport layer includes an organic material as described above. Compound.
  • the organic electronic device of the present invention includes at least a cathode, an anode, and a functional layer located between the cathode and the anode, wherein the functional layer includes at least one of the above-mentioned organic electronic devices.
  • the organic electronic devices can be selected from, but not limited to, organic light-emitting diodes, organic photovoltaic cells, organic light-emitting batteries, organic field effect tubes, organic light-emitting field effect tubes, organic lasers, organic spintronic devices, organic sensors, and organic light emitting diodes.
  • Plasma emission diodes, etc. are particularly preferably organic electroluminescent devices, such as OLED, OLEEC, and organic light emitting field effect tubes.
  • the hole injection layer or the hole transport layer of the electroluminescent device includes a compound used in an organic electronic device as described above.
  • the above-mentioned light-emitting device especially OLED, includes a substrate, an anode, at least one light-emitting layer, and a cathode.
  • the substrate can be opaque or transparent.
  • a transparent substrate can be used to make a transparent light-emitting component.
  • the substrate can be rigid or elastic.
  • the substrate can be plastic, metal, semiconductor wafer or glass.
  • the substrate has a smooth surface.
  • a substrate without surface defects is a particularly ideal choice.
  • the substrate is flexible and can be selected from polymer films or plastics. Its glass transition temperature Tg is above 150°C, preferably more than 200°C, more preferably more than 250°C, most preferably Over 300°C. Examples of suitable flexible substrates are poly(ethylene terephthalate) (PET) and polyethylene glycol (2,6-naphthalene) (PEN).
  • the anode may include 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 a light emitting layer.
  • HIL hole injection layer
  • HTL hole transport layer
  • the absolute value of the difference between the work function of the anode and the luminous body in the light-emitting layer or the HOMO energy level or the valence band energy level of the p-type semiconductor material as HIL or HTL or electron blocking layer (EBL) is less than 0.5 eV, preferably less than 0.3 eV, most preferably less than 0.2 eV.
  • 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.
  • suitable anode materials are known, and those of ordinary skill in the art can easily select and use them.
  • the anode material can 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 anode is patterned and structured. Patterned ITO conductive substrates are commercially available and can be used to prepare devices according to the present invention.
  • the cathode may include a conductive metal or metal oxide.
  • the cathode can easily inject electrons into the EIL or ETL or directly into the light-emitting layer.
  • the work function of the cathode and the LUMO energy level of the luminous body in the light-emitting layer or the n-type semiconductor material as the electron injection layer (EIL) or electron transport layer (ETL) or hole blocking layer (HBL) or
  • the absolute value of the difference in conduction band energy level is less than 0.5 eV, preferably less than 0.3 eV, and most preferably less than 0.2 eV.
  • all materials that can be used as the cathode of an OLED can be used as the cathode material of the device of the invention.
  • cathode materials include, but are not limited to: Al, Au, Ag, Ca , Ba, Mg, LiF / Al, MgAg alloy, BaF 2 / Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO and the like.
  • the cathode material can 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.
  • OLED can also contain other functional layers, such as hole injection layer (HIL), hole transport layer (HTL), electron blocking layer (EBL), electron injection layer (EIL), electron transport layer (ETL), hole blocking layer (HBL).
  • HIL hole injection layer
  • HTL hole transport layer
  • EBL electron blocking layer
  • EIL electron injection layer
  • ETL electron transport layer
  • HBL hole blocking layer
  • the light-emitting device has a light-emitting wavelength between 300 and 1200 nm, preferably between 350 and 1000 nm, and more preferably between 400 and 900 nm.
  • the present invention also relates to the application of the electroluminescent device according to the present invention in various electronic equipment, including, but not limited to, display equipment, lighting equipment, light sources, sensors and the like.
  • the yield is about 40%.
  • the device structure is:
  • Dopant(40nm)/ETL: Liq(30nm)/Liq(1nm)/Al(100nm)/cathode are as follows: a, Cleaning of the conductive glass substrate: when used for the first time, it can be cleaned with a variety of solvents, such as chloroform, ketone, isopropanol, and then subjected to ultraviolet ozone plasma treatment;
  • HIL (10nm), HTL (50nm), EML (40nm), ETL (30nm): formed by thermal evaporation in high vacuum (1 ⁇ 10 -6 mbar, mbar).
  • Cathode Liq/Al (1nm/100nm) is thermally evaporated in high vacuum (1 ⁇ 10 -6 mbar);
  • Encapsulation The device is encapsulated with ultraviolet hardening resin in a nitrogen glove box.
  • EML material is selected from Host: 10% Dopant (40nm); ETL material is selected from ETL: Liq (30nm).
  • HIL is selected from compound 1-12 and comparative compound 1-2.
  • Comparative compound 1 is F4TCNQ.
  • Comparative compound 2 is HATCN.
  • the current and voltage (J-V) characteristics of each OLED device are characterized by the characterization equipment, and important parameters such as efficiency, lifetime and external quantum efficiency are recorded at the same time. After testing, the efficiency and lifetime of the device obtained by using compound 1 to compound 10 as the HIL are better than those of the comparative example, and the details are as described in Table 1.
  • the compound according to the present invention has greatly improved efficiency and lifetime compared with comparative compounds 1 and 2.
  • the device example 11 is compared with the comparative implementation.
  • the life span is increased by about 2 times, and the efficiency is increased by nearly 33%.

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Abstract

一种用于有机电子器件的化合物、混合物、组合物及有机电子器件。所述用于有机电子器件的化合物具有如通式(1)所式的结构，并具有优异的空穴传输性能和稳定性，可作为有机电致发光器件的空穴注入材料，也可作为掺杂剂掺杂在空穴注入层或空穴传输层中，这样既可低压驱动，也可提高电致发光效率，延长器件寿命。

Description

[根据细则37.2由ISA制定的发明名称]　有机电致发光器件和含稠环的芳香族化合物 技术领域
本发明涉及有机电致发光技术领域，特别是涉及一种用于有机电子器件的化合物、混合物、组合物及有机电子器件，特别是电致发光器件领域的应用。
背景技术
由于有机发光二极管(OLED)具有种类多、制造成本低和光学与电学性能良好等优点，其在光电器件(例如平板显示器和照明)的应用方面具有很大的潜力。
有机发光二极管是由正极与负极以及在它们中间的有机物层三部分组成。为了提高有机发光二极管的效率与寿命，有机物层一般具有多层结构，每一层包含有不同的有机物质。具体可以包括空穴注入层、空穴传输层、发光层、电子传输层、电子注入层等。这种有机发光二极管发光的基本原理为：当在两个电极之间施加电压时，正极向有机层注入空穴，负极向有机层注入电子，注入的空穴与电子相遇时会成激子，该激子跃迁回基态时发光。这种有机发光二极管具有自发光、高亮度、高效率、低驱动电压、广视角、高对比度、高响应性等优点。为了提高注入的空穴和电子的复合效率，需要进一步对有机发光二极管的结构和材料等方面进行改良。
要获得高性能的有机发光二极管，空穴的注入和高效传输是关键。目前OLED发光器件中，一般采用三芳胺衍生物或咔唑衍生物作为空穴注入材料，然而，此处仍需要对寿命、效率及工作电压进一步改进。
因此，仍需要进一步开发能够提高有机发光二极管效率及寿命的空穴注入材料。
发明内容
鉴于上述现有技术的不足，本发明的目的在于提供一种用于有机电子器件的化合物、混合物、组合物及有机电子器件，旨在提供一类新型的有机光电功能材料，提高器件的效率和寿命。
本发明的技术方案如下：
一种用于有机电子器件的化合物，具有如通式(1)所式的结构：
Figure PCTCN2020134314-appb-000001
其中：
Ar 1选自结构式(A-1)或(A-2)：
Figure PCTCN2020134314-appb-000002
M选自CR 2R 3、NR 2、SiR 2R 3、PR 2、或取代或未取代含有6-60个C原子的芳香基团、取代或未取代含有5-60个环原子的杂芳香基团、或3-30个环原子的非芳香环系基团；
Y 1-Y 4每次出现，分别独立选自单键、CR 4R 5、NR 4、O、S、SiR 4R 5、PR 4、P(＝O)R 4、S＝O、S(＝O) 2或C＝O；且Y 1和Y 2不同时为单键，Y 3和Y 4不同时为单键；
n选自0-4的任一整数；
R 1-R 5每次出现时，分别独立选自H，D，或具有1至20个C原子的直链烷基、烷氧基或硫代烷氧基，或具有3至20个C原子的支链或环状的烷基、烷氧基或硫代烷氧基，或甲硅烷基，或具有1至20个C原子的酮基，或具有2至20个C原子的烷氧基羰基，或具有7至20个C原子的芳氧基羰基，氰基，氨基甲酰基，卤甲酰基，甲酰基，异氰基，异氰酸酯基，硫氰酸酯基，异硫氰酸酯基，羟基，硝基，亚硝基，CF 3，Cl，Br，F，I，可交联的基团，或具有5至60个环原子的取代或未取代的芳香基、杂芳香基，或具有5至60个环原子的芳氧基、杂芳氧基，或这些体系的组合；相邻的R 1可以彼此结合形成取代或未取代的环；
*表示连接位点。
本发明进一步涉及一种混合物，包含一种如上所述的用于有机电子器件的化合物，及至少一种有机 功能材料，所述有机功能材料选自空穴注入材料、空穴传输材料、电子传输材料、电子注入材料、电子阻挡材料、空穴阻挡材料、发光体、主体材料或有机染料。
本发明进一步涉及一种组合物，包括一种如上所述的用于有机电子器件的化合物或如上所述的混合物，及至少一种有机溶剂。
本发明进一步涉及一种有机电子器件，包含至少一功能层，所述功能层的材料包含一种如上所述的用于有机电子器件的化合物或如上所述的混合物，或由如上所述的组合物制备而成。优选地，所述功能层选自空穴注入层。
有益效果：
本发明所述用于有机电子器件的化合物为吲哚咔唑类有机化合物，其易合成，当其被用于有机电子器件的空穴注入层作为P-dopant时，可有效提高器件的寿命和效率，同时降低工作电压。
附图说明
图1是一实施例的有机发光器件结构图，图中101是基板，102是阳极，103是空穴注入层(HIL)，104是空穴传输层(HTL)，105是发光层，106是电子注入层(EIL)或电子传输层(ETL)，107是阴极。
具体实施方式
本发明提供一种有机电子器件的化合物混合物、组合物及有机电子器件。为使本发明的目的、技术方案及效果更加清楚、明确，以下对本发明进一步详细说明。应当理解，此处所描述的具体实施例仅用以解释本发明，并不用于限定本发明。
在本发明中，“取代”表示被取代基中的氢原子被取代基所取代。
在本发明中，同一取代基多次出现时，可独立选自不同基团。如通式含有多个M，则M可独立选自不同基团。
在本发明中，“环原子数”表示原子键合成环状而得到的结构化合物(例如，单环化合物、稠环化合物、交联化合物、碳环化合物、杂环化合物)的构成该环自身的原子之中的原子数。该环被取代基所取代时，取代基所包含的原子不包括在成环原子内。关于以下所述的“环原子数”，在没有特别说明的条件下也是同样的。例如，苯环的环原子数为6，萘环的环原子数为10，噻吩基的环原子数为5。
芳香基团指至少包含一个芳环的烃基。杂芳香基团指包含至少一个杂原子的芳香烃基。杂原子优选选自Si、N、P、O、S和/或Ge，特别优选选自Si、N、P、O和/或S。稠环芳香基团指芳香基团的环可以具有两个或多个环，其中两个碳原子被两个相邻的环共用，即稠环。稠杂环芳香基团指包含至少一个杂原子的稠环芳香烃基。对于本发明的目的，芳香基团或杂芳香基团不仅包括芳香环的体系，而且包含非芳香族的环系。因此，比如吡啶、噻吩、吡咯、吡唑、三唑、咪唑、噁唑、噁二唑、噻唑、四唑、吡嗪、哒嗪、嘧啶、三嗪、卡宾等体系，对于该发明目的同样认为是芳香基团或杂环芳香基团。对于本发明的目的，稠环芳香族或稠杂环芳香族环系不仅包括芳香基团或杂芳香基团的体系，而且，其中多个芳香基团或杂环芳香基团也可以被短的非芳族单元间断(<10％的非H原子，优选小于5％的非H原子，比如C、N或O原子)。因此，比如9，9'-螺二芴，9，9-二芳基芴，三芳胺，二芳基醚等体系，对于该发明目的同样认为是稠环芳香族环系。
本发明涉及一种用于有机电子器件的化合物，具有如通式(1)所式的结构：
Figure PCTCN2020134314-appb-000003
其中：
Ar 1选自结构式(A-1)或(A-2)：
Figure PCTCN2020134314-appb-000004
M选自CR 2R 3、NR 2、SiR 2R 3、PR 2、或取代或未取代含有6-60个C原子的芳香基团、取代或未取代含有5-60个环原子的杂芳香基团、或3-30个环原子的非芳香环系基团；
Y 1-Y 4每次出现，分别独立选自单键、CR 4R 5、NR 4、O、S、SiR 4R 5、PR 4、P(＝O)R 4、S＝O、S(＝O) 2或C＝O；且Y 1和Y 2不同时为单键，Y 3和Y 4不同时为单键；
n选自0-4的任一整数；
R 1-R 5每次出现时，分别独立选自H，D，或具有1至20个C原子的直链烷基、烷氧基或硫代烷氧基，或具有3至20个C原子的支链或环状的烷基、烷氧基或硫代烷氧基，或甲硅烷基，或具有1至20个C原子的酮基，或具有2至20个C原子的烷氧基羰基，或具有7至20个C原子的芳氧基羰基，氰基，氨基甲酰基，卤甲酰基，甲酰基，异氰基，异氰酸酯基，硫氰酸酯基，异硫氰酸酯基，羟基，硝基，亚硝基，CF 3，Cl，Br，F，I，可交联的基团，或具有5至60个环原子的取代或未取代的芳香基、杂芳香基，或具有5至60个环原子的芳氧基、杂芳氧基，或这些体系的组合；相邻的R 1可以彼此结合形成取代或未取代的环；
*表示连接位点。
在一实施例中，Ar 1选自结构式(A-1)，通式(1)选自如下通式：
Figure PCTCN2020134314-appb-000005
进一步，通式(I-1)选自如下通式：
Figure PCTCN2020134314-appb-000006
在一实施例中，通式(I-1)或通式(2-1)或通式(2-2)中n选自1-4的任一整数。
在一实施例中，Ar 1选自结构式(A-2)，通式(1)选自如下通式：
Figure PCTCN2020134314-appb-000007
进一步，通式(2-1)选自如下通式：
Figure PCTCN2020134314-appb-000008
在一实施例中，通式(I-2)或通式(2-3)或通式(2-4)中n选自0。
在一实施例中，通式(I-2)或通式(2-3)或通式(2-4)中n选自1-4的任一整数。
在一实施例中，R 1每次出现时，独立选自D，或具有1至20个C原子的直链烷基，或具有3至20个C原子的支链或环状的烷基，氰基，氨基甲酰基，卤甲酰基，甲酰基，异氰基，异氰酸酯基，硫氰酸酯基，异硫氰酸酯基，羟基，硝基，CF 3，Cl，Br，F，I，或具有5至60个环原子的取代或未取代的芳香基、杂芳香基，或这些体系的组合；相邻的R 1可以彼此结合形成取代或未取代的环。
在一实施例中，R 1每次出现时，独立选自氰基，硝基，亚硝基，CF 3，Cl，B，I，F，或被氰基、硝基、亚硝基、CF 3、Cl、B、I、F取代的芳香基或杂芳香基。
在一实施例中，R 1多次出现时，选自相同的基团。
在一实施例中，R 1选自被氰基、硝基、亚硝基、CF 3、Cl、B、I、F取代的芳香基或杂芳香基。
进一步，通式(I-1)或通式(2-1)或通式(2-2)中R 1选自被氰基、硝基、亚硝基、CF 3、Cl、B、I、F取代的芳香基或杂芳香基；更进一步，通式(I-1)或通式(2-1)或通式(2-2)中R 1选自被氰基、硝基、亚硝基、CF 3、Cl、B、I、F取代的环原子数为6的芳香基或杂芳香基。
在一实施例中，Y 1-Y 4每次出现，分别独立选自单键、CR 4R 5、O或S。
在一实施例中，Y 1和Y 4选自相同的基团，更优选地，Y 1和Y 4同时选自O或S或CR 4R 5。
在一实施例中，Y 1和Y 3选自相同的基团，更优选地，Y 1和Y 3同时选自O或S或CR 4R 5。
在一实施例中，通式(2-4)中Y 1和Y 3同时选自S。
在一优选地实施例中，按照本发明所述的用于有机电子器件的化合物，M多次出现时，独立选自CR 2R 3或NR 2；
在一实施例中，按照本发明所述的用于有机电子器件的化合物，M多次出现时，独立选自CR 2R 3。优选地，R 2和R 3选自氰基，硝基，亚硝基，CF 3，Cl，B，I，F，或被氰基、硝基、亚硝基、CF 3、Cl、B、I、F取代的芳香基或杂芳香基。
在一优选地实施例中，M选自以下基团中的一种：
Figure PCTCN2020134314-appb-000009
其中：R 6每次出现时，独立选自氰基、硝基、亚硝基、CF 3、Cl、B、I或F；
m选自0-5的任一整数；优选地，m选自1-5的任一整数。
进一步地，M选自以下基团中的一种：
Figure PCTCN2020134314-appb-000010
在一实施例中，M多次出现时，选自相同的基团；进一步，M均选自
Figure PCTCN2020134314-appb-000011
Figure PCTCN2020134314-appb-000012
在一实施例中，按照上述所述的被氰基、硝基、亚硝基、CF 3、Cl、B、I、F取代的芳香基或杂芳香基优选地选自如下基团中的一种：
Figure PCTCN2020134314-appb-000013
其中：
X每次出现时，独立选自CR 7或N；
W每次出现时，独立选自CR 8R 9、NR 8、O、S、SiR 8R 9、PR 8、P(＝O)R 8、S＝O、S(＝O) 2或C＝O；
R 7-R 9每次出现时，独立选自H，D，或具有1至20个C原子的直链烷基，或具有3至20个C原子的支链或环状的烷基，或具有1至20个C原子的酮基，或具有2至20个C原子的烷氧基羰基，或具有7至20个C原子的芳氧基羰基，氰基，氨基甲酰基，氰基，硝基，亚硝基，CF 3，Cl，B，I，F，或具有5至60个环原子的取代或未取代的芳香基、杂芳香基，或具有5至60个环原子的芳氧基、杂芳氧基，或这些体系的组合；且至少一个R 7选自氰基、硝基、亚硝基、CF 3、Cl、B、I或F。
在一实施例中，R 1每次出现时，独立选自
Figure PCTCN2020134314-appb-000014
优选地，R 7独立选自H，D，氰基、硝基、亚硝基、CF 3、Cl、B、I或F，且至少一个R 7选自氰基、硝基、亚硝基、CF 3、Cl、B、I或F。
进一步地，被氰基、硝基、亚硝基、CF 3、Cl、B、I、F取代的芳香基或杂芳香基优选自如下基团中的一种：
Figure PCTCN2020134314-appb-000015
在一优选地实施例中，按照本发明所述的用于有机电子器件的化合物，通式(1)优选地通式(I-3)或(I-4)：
Figure PCTCN2020134314-appb-000016
进一步地，(I-3)或(I-4)中R 1选自被氰基、硝基、亚硝基、CF 3、Cl、B、I、F取代的芳香基团或杂芳香基团。
更进一步地，通式(1)优选地通式(I-5)或(I-6)：
Figure PCTCN2020134314-appb-000017
其中：R 7含义同上所述；优选地，R 7多次出现时，均独立选自氰基、硝基、亚硝基、CF 3、Cl、B、I或F。
在一实施例中，按照如上所述用于有机电子器件的化合物，进一步限定为用于有机电子器件空穴注入层的材料或用于有机电子器件空穴传输层p-dopant材料。
下面列出按照本发明所述的用于有机电子器件的化合物的结构，但不限于此：
Figure PCTCN2020134314-appb-000018
Figure PCTCN2020134314-appb-000019
Figure PCTCN2020134314-appb-000020
Figure PCTCN2020134314-appb-000021
Figure PCTCN2020134314-appb-000022
按照发明的所述的用于有机电子器件的化合物，可以作为功能材料用于有机电子器件的功能层中。有机功能层包括，但不限于，空穴注入层(HIL),空穴传输层(HTL),电子传输层(ETL),电子注入层(EIL),电子阻挡层(EBL),空穴阻挡层(HBL),发光层(EML)。
在一个特别优选的实施例中，按照本发明的有机化合物用于空穴注入层或P-dopant。
本发明还提供一种混合物，包含有至少一种以上所述的用于有机电子器件的化合物，及至少另一种有机功能材料，所述至少另一种的有机功能材料可选于空穴注入材料(HIM)，空穴传输材料(HTM)，电子传输材料(ETM)，电子注入材料(EIM)，电子阻挡材料(EBM)，空穴阻挡材料(HBM)，发光材料(Emitter)，主体材料(Host)和有机染料。例如在WO2010135519A1,US20090134784A1和WO2011110277A1中对各种有机功能材料有详细的描述，特此将此3专利文件中的全部内容并入本文作为参考。
在一些优选的实施例中，所述混合物，其中所述的另一种有机功能材料选于空穴注入材料(HIM)，空穴传输材料(HTM)，和主体材料(Host)。
在其中一个实施例中，所述混合物包括至少一种空穴注入材料(HIM)或空穴传输材料和一种掺杂剂，所述掺杂剂是上述用于有机电子器件的化合物，所述掺杂剂与主体的摩尔比是1:1至1:100000。
其中关于HIM/HTM/EBM，和Host(主体材料/基质材料)的详细描述详见专利WO2018095395A1。
本发明的另一个目的是为印刷OLED提供材料解决方案。
在某些实施例中，按照本发明的化合物，其分子量≥800g/mol，优选≥900g/mol，很优选≥1000g/mol，更优选≥1100g/mol，最优选≥1200g/mol。
在另一些实施例中，按照本发明的化合物，在25℃时，在甲苯中的溶解度≥2mg/ml，优选≥3mg/ml，更优选≥4mg/ml，最优选≥5mg/ml。
本发明还涉及一种组合物，包含至少一种如上所述的用于有机电子器件的化合物或如上所述混合物，及至少一种有机溶剂；所述的至少一种的有机溶剂选自芳族或杂芳族、酯、芳族酮或芳族醚、脂肪族酮或脂肪族醚、脂环族或烯烃类化合物，或硼酸酯或磷酸酯类化合物，或两种及两种以上溶剂的混合物。
在一个优选的实施例中，按照本发明的一种组合物，其特征在于，所述的至少的一种有机溶剂选自基于芳族或杂芳族的溶剂。
适合本发明的基于芳族或杂芳族溶剂的例子有，但不限制于：对二异丙基苯、戊苯、四氢萘、环己基苯、氯萘、1,4-二甲基萘、3-异丙基联苯、对甲基异丙苯、二戊苯、三戊苯、戊基甲苯、邻二乙苯、间二乙苯、对二乙苯、1,2,3,4-四甲苯、1,2,3,5-四甲苯、1,2,4,5-四甲苯、丁苯、十二烷基苯、二己基苯、二丁基苯、对二异丙基苯、环己基苯、苄基丁基苯、二甲基萘、3-异丙基联苯、对甲基异丙苯、1-甲基萘、1,2,4-三氯苯、4,4-二氟二苯甲烷、1,2-二甲氧基-4-(1-丙烯基)苯、二苯甲烷、2-苯基吡啶、3-苯基吡啶、N-甲基二苯胺、4-异丙基联苯、α，α-二氯二苯甲烷、4-(3-苯基丙基)吡啶、苯甲酸苄酯、1,1-双(3,4-二甲基苯基)乙烷、2-异丙基萘、喹啉、异喹啉、2-呋喃甲酸甲酯、2-呋喃甲酸乙酯等；
适合本发明的基于芳族酮溶剂的例子有，但不限制于：1-四氢萘酮，2-四氢萘酮，2-(苯基环氧)四氢萘酮，6-(甲氧基)四氢萘酮，苯乙酮、苯丙酮、二苯甲酮、及它们的衍生物，如4-甲基苯乙酮、3-甲基苯乙酮、2-甲基苯乙酮、4-甲基苯丙酮、3-甲基苯丙酮、2-甲基苯丙酮等；
适合本发明的基于芳族醚溶剂的例子有，但不限制于：3-苯氧基甲苯、丁氧基苯、对茴香醛二甲 基乙缩醛、四氢-2-苯氧基-2H-吡喃、1,2-二甲氧基-4-(1-丙烯基)苯、1,4-苯并二噁烷、1,3-二丙基苯、2,5-二甲氧基甲苯、4-乙基本乙醚、1,3-二丙氧基苯、1,2,4-三甲氧基苯、4-(1-丙烯基)-1,2-二甲氧基苯、1,3-二甲氧基苯、缩水甘油基苯基醚、二苄基醚、4-叔丁基茴香醚、反式-对丙烯基茴香醚、1,2-二甲氧基苯、1-甲氧基萘、二苯醚、2-苯氧基甲醚、2-苯氧基四氢呋喃、乙基-2-萘基醚；
在一些优选的实施例中，按照本发明的组合物，所述的至少一种的有溶剂可选自：脂肪族酮，例如，2-壬酮、3-壬酮、5-壬酮、2-癸酮、2,5-己二酮、2,6,8-三甲基-4-壬酮、葑酮、佛尔酮、异佛尔酮、二正戊基酮等；或脂肪族醚，例如，戊醚、己醚、二辛醚、乙二醇二丁醚、二乙二醇二乙醚、二乙二醇丁基甲醚、二乙二醇二丁醚、三乙二醇二甲醚、三乙二醇乙基甲醚、三乙二醇丁基甲醚、三丙二醇二甲醚、四乙二醇二甲醚等。
在另一些优选的实施例中，按照本发明的组合物，所述的至少一种的有溶剂可选自基于酯的溶剂：辛酸烷酯、癸二酸烷酯、硬脂酸烷酯、苯甲酸烷酯、苯乙酸烷酯、肉桂酸烷酯、草酸烷酯、马来酸烷酯、烷内酯、油酸烷酯等。特别优选辛酸辛酯、癸二酸二乙酯、邻苯二甲酸二烯丙酯、异壬酸异壬酯。
所述的溶剂可以是单独使用，也可以是作为两种或多种有机溶剂的混合物使用。
在某些优选的实施例中，按照本发明的一种组合物，其特征在于，包含至少一种如上所述的有机化合物或高聚物或混合物及至少一种有机溶剂，还可进一步包含另一种有机溶剂。另一种有机溶剂的例子包括(但不限于)：甲醇、乙醇、2-甲氧基乙醇、二氯甲烷、三氯甲烷、氯苯、邻二氯苯、四氢呋喃、苯甲醚、吗啉、甲苯、邻二甲苯、间二甲苯、对二甲苯、1,4二氧杂环己烷、丙酮、甲基乙基酮、1,2二氯乙烷、3-苯氧基甲苯、1,1,1-三氯乙烷、1,1,2,2-四氯乙烷、醋酸乙酯、醋酸丁酯、二甲基甲酰胺、二甲基乙酰胺、二甲基亚砜、四氢萘、萘烷、茚和/或它们的混合物。
一些优选的实施例中，特别适合本发明的溶剂是汉森(Hansen)溶解度参数在以下范围内的溶剂：
δ d(色散力)在17.0～23.2MPa 1/2的范围，尤其是在18.5～21.0MPa 1/2的范围；
δ p(极性力)在0.2～12.5MPa 1/2的范围，尤其是在2.0～6.0MPa 1/2的范围；
δ h(氢键力)在0.9～14.2MPa 1/2的范围，尤其是在2.0～6.0MPa 1/2的范围。
按照本发明的组合物，其中有机溶剂在选取时需考虑其沸点参数。本发明中，所述的有机溶剂的沸点≥150℃；优选为≥180℃；较优选为≥200℃；更优为≥250℃；最优为≥275℃或≥300℃。这些范围内的沸点对防止喷墨印刷头的喷嘴堵塞是有益的。所述的有机溶剂可从溶剂体系中蒸发，以形成包含功能材料薄膜。
在一个优选的实施方案中，按照本发明的组合物是一溶液。
在另一个优选的实施方案中，按照本发明的组合物是一悬浮液。
本发明实施例中的组合物中可以包括0.01至10wt％的按照本发明的用于有机电子器件的化合物或混合物，较好的是0.1至15wt％，更好的是0.2至5wt％，最好的是0.25至3wt％。
本发明还涉及所述组合物作为涂料或印刷油墨在制备有机电子器件时的用途，特别优选的是通过打印或涂布的制备方法。
其中，适合的打印或涂布技术包括(但不限于)喷墨打印，喷印(Nozzle Printing)，活版印刷，丝网印刷，浸涂，旋转涂布，刮刀涂布，辊筒印花，扭转辊印刷，平版印刷，柔版印刷，轮转印刷，喷涂，刷涂或移印，狭缝型挤压式涂布等。首选的是凹版印刷，喷印及喷墨印刷。溶液或悬浮液可以另外包括一个或多个组份例如表面活性化合物，润滑剂，润湿剂，分散剂，疏水剂，粘接剂等，用于调节粘度，成膜性能，提高附着性等。有关打印技术，及其对有关溶液的相关要求，如溶剂及浓度，粘度等。
本发明还提供一种如上所述的化合物、混合物或组合物在有机电子器件中的应用，所述的有机电子器件可选于，但不限于，有机发光二极管(OLED)，有机光伏电池(OPV)，有机发光电池(OLEEC)，有机场效应管(OFET)，有机发光场效应管，有机激光器，有机自旋电子器件，有机传感器及有机等离激元发射二极管(Organic Plasmon Emitting Diode)等，特别优选为OLED。本发明实施例中，优选将所述有机化合物或混合物用于OLED器件的空穴注入层。
本发明进一步涉及一种有机电子器件，至少包含一种如上所述的用于有机电子器件的化合物或混合物，或由上述组合物制备而成。更进一步地，所述有机电子器件至少包含一功能层，所述功能层包含一种如上所述的用于有机电子器件的化合物或混合物或高聚物，或由上述组合物制备而成。所述功能层选自空穴注入层、空穴传输层、发光层、电子阻挡层、电子注入层、电子传输层、空穴阻挡层。
在某个优选地实施例中，按照本发明所述的有机电子器件，至少包含一空穴注入层或空穴传输层，所述空穴注入层或空穴传输层包含一种如上所述的有机化合物。
一般地，本发明所述有机电子器件至少包含一个阴极，一个阳极及位于阴极和阳极之间的一个功能层，其中所述的功能层中至少包含一种如上所述的用于有机电子器件的化合物。所述的有机电子器件可选于，但不限于，有机发光二极管，有机光伏电池，有机发光电池，有机场效应管，有机发光场效应管，有机激光器，有机自旋电子器件，有机传感器及有机等离激元发射二极管等，特别优选的是有机电致发 光器件，如OLED，OLEEC，有机发光场效应管。
在某些优先的实施例中，所述的电致发光器件，其空穴注入层或空穴传输层包含一种如上所述的用于有机电子器件的化合物。
在以上所述的发光器件，特别是OLED中，包括一基片，一阳极，至少一发光层，一阴极。
基片可以是不透明或透明。一个透明的基板可以用来制造一个透明的发光元器件。例如可参见，Bulovic等Nature 1996,380,p29，和Gu等，Appl.Phys.Lett.1996,68,p2606。基片可以是刚性的或弹性的。基片可以是塑料，金属，半导体晶片或玻璃。最好是基片有一个平滑的表面。无表面缺陷的基板是特别理想的选择。在一个优选的实施例中，基片是柔性的，可选于聚合物薄膜或塑料，其玻璃化温度Tg为150℃以上，较好是超过200℃，更好是超过250℃，最好是超过300℃。合适的柔性基板的例子有聚(对苯二甲酸乙二醇酯)(PET)和聚乙二醇(2,6-萘)(PEN)。
阳极可包括一导电金属或金属氧化物，或导电聚合物。阳极可以容易地注入空穴到空穴注入层(HIL)或空穴传输层(HTL)或发光层中。在一个的实施例中，阳极的功函数和发光层中的发光体或作为HIL或HTL或电子阻挡层(EBL)的p型半导体材料的HOMO能级或价带能级的差的绝对值小于0.5eV，较好是小于0.3eV，最好是小于0.2eV。阳极材料的例子包括但不限于：Al、Cu、Au、Ag、Mg、Fe、Co、Ni、Mn、Pd、Pt、ITO、铝掺杂氧化锌(AZO)等。其他合适的阳极材料是已知的，本领域普通技术人员可容易地选择使用。阳极材料可以使用任何合适的技术沉积，如一合适的物理气相沉积法，包括射频磁控溅射，真空热蒸发，电子束(e-beam)等。在某些实施例中，阳极是图案结构化的。图案化的ITO导电基板可在市场上买到，并且可以用来制备根据本发明的器件。
阴极可包括一导电金属或金属氧化物。阴极可以容易地注入电子到EIL或ETL或直接到发光层中。在一个的实施例中，阴极的功函数和发光层中发光体或作为电子注入层(EIL)或电子传输层(ETL)或空穴阻挡层(HBL)的n型半导体材料的LUMO能级或导带能级的差的绝对值小于0.5eV，较好是小于0.3eV，最好是小于0.2eV。原则上，所有可用作OLED的阴极的材料都可能作为本发明器件的阴极材料。阴极材料的例子包括但不限于：Al、Au、Ag、Ca、Ba、Mg、LiF/Al、MgAg合金、BaF 2/Al、Cu、Fe、Co、Ni、Mn、Pd、Pt、ITO等。阴极材料可以使用任何合适的技术沉积，如一合适的物理气相沉积法，包括射频磁控溅射，真空热蒸发，电子束(e-beam)等。
OLED还可以包含其他功能层，如空穴注入层(HIL)、空穴传输层(HTL)、电子阻挡层(EBL)、电子注入层(EIL)、电子传输层(ETL)、空穴阻挡层(HBL)。适合用于这些功能层中的材料在上面及在WO2010135519A1、US20090134784A1和WO2011110277A1中有详细的描述，特此将此3篇专利文件中的全部内容并入本文作为参考。
按照本发明的发光器件，其发光波长在300到1200nm之间，较好的是在350到1000nm之间，更好的是在400到900nm之间。
本发明还涉及按照本发明的电致发光器件在各种电子设备中的应用，包含，但不限于，显示设备，照明设备，光源，传感器等等。
下面将结合优选实施例对本发明进行了说明，但本发明并不局限于下述实施例，应当理解，所附权利要求概括了本发明的范围在本发明构思的引导下本领域的技术人员应意识到，对本发明的各实施例进行的一定的改变，都将被本发明的权利要求书的精神和范围所覆盖。
具体实施例
1、按照本发明的化合物的合成方法举例，但本发明并不局限于下述实施例。
合成例1：化合物1的合成
Figure PCTCN2020134314-appb-000023
1)中间体1-3的合成：氮气环境下，将(6.3g,20mmol)的化合物1-1和(5.5g,40mmol)的化合物1-2，(1.4g,1.2mmol)四(三苯基磷)钯，2.00mol/L的碳酸钠(8.48g，80mmol)和(50mL)甲 苯加入250mL的三口瓶中，加热90℃搅拌反应12小时，结束反应，TLC和MS显示反应完全，主要为目标产物,冷却，将反应液用150ml的饱和食盐水洗涤三次，无水硫酸钠干燥，然后蒸发除去溶剂，残余物用DCM/PE过柱子纯化，得到化合物1-3,产率约60％。
2)中间体1-4的合成：氮气环境下，将(6.8g,20mmol)的化合物1-3和过氧化苯甲酸叔丁酯20ml,3-硝基吡啶30ml,乙二醇二甲醚100ml加入到250mL的三口瓶中，150℃反应0.5小时，将反应液用150ml的饱和食盐水洗涤三次，无水硫酸钠干燥，然后减压蒸馏除去溶剂，残余物用DCM/PE过柱子纯化，得到化合物1-4,产率约50％。
3)化合物1的合成：将原料1-4(6.7g,20mmol),四氯化钛(0.228g,1.2mmol),氮气保护下加入三氯甲烷100ml溶解，冰浴下加入丙二腈(3.9g,60mmol)，升至室温搅拌过夜。水洗，干燥，柱色谱纯化得到化合物1，MS:[M+H] +＝434.0，产率约40％。
合成例2：化合物2的合成
Figure PCTCN2020134314-appb-000024
1)中间体2-3的合成：氮气环境下，将(6.3g,20mmol)的化合物2-1和(6.0g,40mmol)的化合物2-2，(1.4g,1.2mmol)四(三苯基磷)钯，2.00mol/L的碳酸钠(8.48g，80mmol)和(50mL)甲苯加入250mL的三口瓶中，加热90℃搅拌反应12小时，结束反应，TLC和MS显示反应完全，主要为目标产物,冷却，将反应液用150ml的饱和食盐水洗涤三次，无水硫酸钠干燥，然后蒸发除去溶剂，残余物用DCM/PE过柱子纯化，得到化合物2-3,产率约60％。
2)中间体2-4的合成：氮气环境下，将(7.4g,20mmol)的化合物2-3放入250ml两口瓶中，加入50m四氢呋喃溶解，液氮降温至-78度，加入1M甲基溴化镁(100ml,100mmol至反应液中，后升至室温，反应12小时，将反应液倒入水中淬灭，用150ml的饱和食盐水洗涤三次，无水硫酸钠干燥，然后蒸发除去溶剂，加入30ml醋酸，30磷酸，搅拌12小时，将混合液倒入冰水中，加入碳酸钾中和至中性，用二氯甲烷萃取，旋干，残余物用DCM/PE过柱子纯化得到化合物2-4,产率约40％。
3)化合物2的合成：将原料2-4(7.8g,20mmol),四氯化钛(0.228g,1.2mmol),氮气保护下加入三氯甲烷100ml溶解，冰浴下加入丙二腈(3.9g,60mmol)，升至室温搅拌过夜。水洗，干燥，柱色谱纯化得到化合物2，MS:[M+H] +＝486.3，产率约40％。
合成例3：化合物3的合成
Figure PCTCN2020134314-appb-000025
1)中间体3-2的合成：将化合物3-1(7.3,20mmol)放入100ml两口瓶中，加入40ml四氢呋喃溶解，加入N-溴代丁二酰亚胺(7.2g,40mmol),搅拌12小时，旋干，用二氯甲烷，甲醇重结晶得到中间体3-2，产率约45％。
2)中间体3-4的合成：氮气环境下，将(8.9g,20mmol)的化合物3-2和(10.2g,40mmol)的化合物3-3，(1.4g,1.2mmol)四(三苯基磷)钯，2.00mol/L的碳酸钠(8.48g，80mmol)和(50 mL)甲苯加入250mL的三口瓶中，加热90℃搅拌反应12小时，结束反应，TLC和MS显示反应完全，主要为目标产物,冷却，将反应液用150ml的饱和食盐水洗涤三次，无水硫酸钠干燥，然后蒸发除去溶剂，残余物用DCM/PE过柱子纯化，得到化合物3-4,产率约60％。
3)化合物3的合成：将原料3-4(14.2g,20mmol),四氯化钛(0.228g,1.2mmol),氮气保护下加入三氯甲烷100ml溶解，冰浴下加入丙二腈(3.9g,60mmol)，升至室温搅拌过夜。水洗，干燥，柱色谱纯化得到化合物3，MS:[M+H] +＝808.6，产率约40％。
合成例4：化合物4的合成
Figure PCTCN2020134314-appb-000026
1)中间体4-2的合成：将化合物4-1(6.4,20mmol)放入100ml两口瓶中，加入40ml四氢呋喃溶解，加入N-溴代丁二酰亚胺(7.2g,40mmol),搅拌12小时，旋干，用二氯甲烷，甲醇重结晶得到中间体4-2，产率约45％。
2)中间体4-4的合成：氮气环境下，将(9.5g,20mmol)的化合物4-2和(6.3g,40mmol)的化合物4-3，(1.4g,1.2mmol)四(三苯基磷)钯，2.00mol/L的碳酸钠(8.48g，80mmol)和(50mL)甲苯加入250mL的三口瓶中，加热90℃搅拌反应12小时，结束反应，TLC和MS显示反应完全，主要为目标产物,冷却，将反应液用150ml的饱和食盐水洗涤三次，无水硫酸钠干燥，然后蒸发除去溶剂，残余物用DCM/PE过柱子纯化，得到化合物4-4,产率约60％。
3)化合物4的合成：将原料4-4(10.8g,20mmol),四氯化钛(0.228g,1.2mmol),氮气保护下加入三氯甲烷100ml溶解，冰浴下加入丙二腈(3.9g,60mmol)，升至室温搅拌过夜。水洗，干燥，柱色谱纯化得到化合物4，MS:[M+H] +＝640.5，产率约40％。
合成例5：化合物5的合成
Figure PCTCN2020134314-appb-000027
1)中间体5-1的合成:同化合物3-2的合成
2)中间体5-3的合成：氮气环境下，将(8.8g,20mmol)的化合物5-1和(8.7g,40mmol)的化合物5-2，(1.4g,1.2mmol)四(三苯基磷)钯，2.00mol/L的碳酸钠(8.48g，80mmol)和(50mL)甲苯加入250mL的三口瓶中，加热90℃搅拌反应12小时，结束反应，TLC和MS显示反应完全，主要为目标产物,冷却，将反应液用150ml的饱和食盐水洗涤三次，无水硫酸钠干燥，然后蒸发除去溶剂，残余物用DCM/PE过柱子纯化，得到化合物5-3,产率约60％。
3)化合物5的合成：将原料5-3(12.6g,20mmol),四氯化钛(0.228g,1.2mmol),氮气保护下加入三氯甲烷100ml溶解，冰浴下加入丙二腈(3.9g,60mmol)，升至室温搅拌过夜。水洗，干燥，柱色谱纯化得到化合物5，MS:[M+H] +＝740.1，产率约40％。
合成例6：化合物6的合成
Figure PCTCN2020134314-appb-000028
1)中间体6-2的合成：将化合物6-1(6.4,20mmol)放入100ml两口瓶中，加入40ml四氢呋喃溶解，加入N-溴代丁二酰亚胺(7.2g,40mmol),搅拌12小时，旋干，用二氯甲烷，甲醇重结晶得到中间体6-2，产率约45％。
2)中间体6-4的合成：氮气环境下，将(9.5g,20mmol)的化合物6-2和(10.2g,40mmol)的化合物6-3，(1.4g,1.2mmol)四(三苯基磷)钯，2.00mol/L的碳酸钠(8.48g，80mmol)和(50mL)甲苯加入250mL的三口瓶中，加热90℃搅拌反应12小时，结束反应，TLC和MS显示反应完全，主要为目标产物,冷却，将反应液用150ml的饱和食盐水洗涤三次，无水硫酸钠干燥，然后蒸发除去溶剂，残余物用DCM/PE过柱子纯化，得到化合物6-4,产率约60％。
3)化合物6的合成：将原料6-4(14.8g,20mmol),四氯化钛(0.228g,1.2mmol),氮气保护下加入三氯甲烷100ml溶解，冰浴下加入丙二腈(3.9g,60mmol)，升至室温搅拌过夜。水洗，干燥，柱色谱纯化得到化合物6，MS:[M+H] +＝840.6，产率约40％。
合成例7：化合物7的合成
Figure PCTCN2020134314-appb-000029
1)中间体7-1的合成:同化合物1-4的合成。
2)中间体7-2的合成：将化合物7-1(6.7,20mmol)放入100ml两口瓶中，加入40ml四氢呋喃溶解，加入N-溴代丁二酰亚胺(7.2g,40mmol),搅拌12小时，旋干，用二氯甲烷，甲醇重结晶得到中间体7-2，产率约45％。
3)中间体7-4的合成：氮气环境下，将(10.0g,20mmol)的化合物7-2和(10.2g,40mmol)的化合物7-3，(1.4g,1.2mmol)四(三苯基磷)钯，2.00mol/L的碳酸钠(8.48g，80mmol)和(50mL)甲苯加入250mL的三口瓶中，加热90℃搅拌反应12小时，结束反应，TLC和MS显示反应完全，主要为目标产物,冷却，将反应液用150ml的饱和食盐水洗涤三次，无水硫酸钠干燥，然后蒸发除去溶剂，残余物用DCM/PE过柱子纯化，得到化合物7-4,产率约60％。
4)化合物7的合成：将原料7-4(15.2g,20mmol),四氯化钛(0.228g,1.2mmol),氮气保护下加入三氯甲烷100ml溶解，冰浴下加入丙二腈(3.9g,60mmol)，升至室温搅拌过夜。水洗，干燥，柱色谱纯化得到化合物7，MS:[M+H] +＝858.4，产率约40％。
合成例8：化合物8的合成
Figure PCTCN2020134314-appb-000030
1)中间体8-3的合成：氮气环境下，将(6.3g,20mmol)的化合物8-1和(6.7g,40mmol)的化合物8-2，(1.4g,1.2mmol)四(三苯基磷)钯，2.00mol/L的碳酸钠(8.48g，80mmol)和(50mL)甲苯加入250mL的三口瓶中，加热90℃搅拌反应12小时，结束反应，TLC和MS显示反应完全，主要为目标产物,冷却，将反应液用150ml的饱和食盐水洗涤三次，无水硫酸钠干燥，然后蒸发除去溶剂，残余物用DCM/PE过柱子纯化，得到化合物8-3,产率约60％。
2)中间体8-4的合成：氮气环境下，将(8.0g,20mmol)的化合物8-3和过氧化苯甲酸叔丁酯20ml,3-硝基吡啶30ml,乙二醇二甲醚100ml加入到250mL的三口瓶中，150度反应0.5小时，将反应液用150ml的饱和食盐水洗涤三次，无水硫酸钠干燥，然后减压蒸馏除去溶剂，残余物用DCM/PE过柱子纯化，得到化合物8-4,产率约50％。
3)中间体8-5的合成：将化合物8-4(7.4g,20mmol)放入100ml两口瓶中，加入40ml四氢呋喃溶解，加入N-溴代丁二酰亚胺(7.2g,40mmol),搅拌12小时，旋干，用二氯甲烷，甲醇重结晶得到中间体8-5，产率约45％
4)中间体8-7的合成：氮气环境下，将(10.5g,20mmol)的化合物8-5和(8.7g,40mmol)的化合物8-6，(1.4g,1.2mmol)四(三苯基磷)钯，2.00mol/L的碳酸钠(8.48g，80mmol)和(50mL)甲苯加入250mL的三口瓶中，加热90℃搅拌反应12小时，结束反应，TLC和MS显示反应完全，主要为目标产物,冷却，将反应液用150ml的饱和食盐水洗涤三次，无水硫酸钠干燥，然后蒸发除去溶剂，残余物用DCM/PE过柱子纯化，得到化合物8-7,产率约60％。
5)化合物8的合成：将原料8-7(14.3g,20mmol),四氯化钛(0.228g,1.2mmol),氮气保护下加入三氯甲烷100ml溶解，冰浴下加入丙二腈(3.9g,60mmol)，升至室温搅拌过夜。水洗，干燥，柱色谱纯化得到化合物8，MS:[M+H] +＝812.6，产率约40％。
合成例9：化合物9的合成
Figure PCTCN2020134314-appb-000031
1)中间体9-1的合成:同化合物3-2的合成。
2)中间体9-3的合成：氮气环境下，将(9.0g,20mmol)的化合物9-1和(10.2g,40mmol)的化合物9-2，(1.4g,1.2mmol)四(三苯基磷)钯，2.00mol/L的碳酸钠(8.48g，80mmol)和(50mL)甲苯加入250mL的三口瓶中，加热90℃搅拌反应12小时，结束反应，TLC和MS显示反应完全，主要为目标产物,冷却，将反应液用150ml的饱和食盐水洗涤三次，无水硫酸钠干燥，然后 蒸发除去溶剂，残余物用DCM/PE过柱子纯化，得到化合物9-3,产率约60％。
3)化合物9的合成:将化合物9-3(14.2g,20mmol)、放入三口瓶中,加入乙醇200ml,50％氢氧化钠水溶液50ml,冰浴条件下加入9-4(10.7g,50mmol)，后升至室温，将反应液搅拌反应12小时，TLC和MS显示反应完全，将反应液150ml的饱和食盐水洗涤三次，二氯甲烷萃取，无水硫酸钠干燥，然后蒸发除去溶剂，残余物用DCM/PE(1:4)过柱子纯化，得到化合物9，MS:[M+H] +＝1104.8，产率约40％。
合成例10：化合物10的合成
Figure PCTCN2020134314-appb-000032
1)中间体10-1的合成:同化合物3-2的合成
2)中间体10-3的合成：氮气环境下，将(9.0g,20mmol)的化合物10-1和(6.3g,40mmol)的化合物10-2，(1.4g,1.2mmol)四(三苯基磷)钯，2.00mol/L的碳酸钠(8.48g，80mmol)和(50mL)甲苯加入250mL的三口瓶中，加热90℃搅拌反应12小时，结束反应，TLC和MS显示反应完全，主要为目标产物,冷却，将反应液用150ml的饱和食盐水洗涤三次，无水硫酸钠干燥，然后蒸发除去溶剂，残余物用DCM/PE过柱子纯化，得到化合物10-3,产率约60％。
3)化合物10的合成:将化合物10-3(11.2g,20mmol)、放入三口瓶中,加入乙醇200ml,50％氢氧化钠水溶液50ml,冰浴条件下加入10-4(10.7g,50mmol)，后升至室温，将反应液搅拌反应12小时，TLC和MS显示反应完全，将反应液150ml的饱和食盐水洗涤三次，二氯甲烷萃取，无水硫酸钠干燥，然后蒸发除去溶剂，残余物用DCM/PE(1:4)过柱子纯化，得到化合物10，MS:[M+H] +＝954.6，产率约40％。
合成例11：化合物11的合成
Figure PCTCN2020134314-appb-000033
1)中间体11-1的合成:同化合物8-5的合成。
2)中间体11-3的合成：氮气环境下，将(10.5g,20mmol)的化合物11-1和(10.2g,40mmol)的化合物11-2，(1.4g,1.2mmol)四(三苯基磷)钯，2.00mol/L的碳酸钠(8.48g，80mmol)和(50mL)甲苯加入250mL的三口瓶中，加热90℃搅拌反应12小时，结束反应，TLC和MS显示反应完全，主要为目标产物,冷却，将反应液用150ml的饱和食盐水洗涤三次，无水硫酸钠干燥，然后蒸发除去溶剂，残余物用DCM/PE过柱子纯化，得到化合物11-3,产率约60％。
3)化合物10的合成:将化合物11-3(13.2g,20mmol)、放入三口瓶中,加入乙醇200ml,50％氢氧化钠水溶液50ml,冰浴条件下加入11-4(10.7g,50mmol)，后升至室温，将反应液搅拌反应12小时，TLC和MS显示反应完全，将反应液150ml的饱和食盐水洗涤三次，二氯甲烷萃取，无水硫酸钠干燥，然后蒸发除去溶剂，残余物用DCM/PE(1:4)过柱子纯化，得到化合物11，MS:[M+H] +,1183.1，
产率约40％。
合成例12：化合物12的合成
Figure PCTCN2020134314-appb-000034
1)中间体12-3的合成：氮气环境下，将(8.9g,20mmol)的化合物12-1和(6.8g,40mmol)的化合物12-2，(1.4g,1.2mmol)四(三苯基磷)钯，2.00mol/L的碳酸钠(8.48g，80mmol)和(50mL)甲苯加入250mL的三口瓶中，加热90℃搅拌反应12小时，结束反应，TLC和MS显示反应完全，主要为目标产物,冷却，将反应液用150ml的饱和食盐水洗涤三次，无水硫酸钠干燥，然后蒸发除去溶剂，残余物用DCM/PE过柱子纯化，得到化合物12-3,产率约60％。
2)化合物10的合成:将原料12-3(10.8g,20mmol),四氯化钛(0.228g,1.2mmol),氮气保护下加入二氯甲烷100ml溶解，冰浴下加入二(三甲基硅基)碳酰二亚胺(11.2g,60mmol)，升至室温搅拌过夜。水洗，干燥，柱色谱纯化得到化合物12，MS:[M+H] +＝588.4，产率为57.1％。
2、OLED器件的制备与表征
器件结构为：
具有ITO/HIL(10nm)/HTL(50nm)/Host：10％Dopant(40nm)/ETL：Liq(30nm)/Liq(1nm)/Al(100nm)/阴极的OLED器件的制备步骤如下:a、导电玻璃基片的清洗:首次使用时，可用多种溶剂进行清洗，例如氯仿、酮、异丙醇进行清洗，然后进行紫外臭氧等离子处理；
b、HIL(10nm)，HTL(50nm)，EML(40nm)、ETL(30nm)：在高真空(1×10 -6毫巴，mbar)中热蒸镀而成。
c、阴极:Liq/Al(1nm/100nm)在高真空(1×10 -6毫巴)中热蒸镀而成；
d、封装:器件在氮气手套箱中用紫外线硬化树脂封装。
其中：EML材料选自Host：10％Dopant(40nm)；ETL材料选自ETL：Liq(30nm)。
其中：HIL选自化合物1-12及对比化合物1-2.
Figure PCTCN2020134314-appb-000035
对比化合物1为F4TCNQ。
对比化合物2为HATCN。
各OLED器件的电流电压(J-V)特性通过表征设备来表征，同时记录重要的参数如效率，寿命及外部量子效率。经检测，采用化合物1-化合物10作为HIL所得到器件的效率和寿命都优于对比实施例，具体如表1所述。
表1
Figure PCTCN2020134314-appb-000036
Figure PCTCN2020134314-appb-000037
由表1可知，按照本发明所述的化合物作为有机电子器件的空穴注入层材料，其效率和寿命相对于对比化合物1和2均有大幅提高，特别是器件实施例11，相对于对比实施例，寿命提高了2倍左右，且效率提高了近33％。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (17)

  1. 一种用于有机电子器件的化合物，其特征在于，具有如通式(1)所式的结构：
    Figure PCTCN2020134314-appb-100001
    其中：
    Ar 1选自结构式(A-1)或(A-2)：
    Figure PCTCN2020134314-appb-100002
    M选自CR 2R 3、NR 2、SiR 2R 3、PR 2、或取代或未取代含有6-60个C原子的芳香基团、取代或未取代含有5-60个环原子的杂芳香基团、或3-30个环原子的非芳香环系基团；
    Y 1-Y 4每次出现，分别独立选自单键、CR 4R 5、NR 4、O、S、SiR 4R 5、PR 4、P(＝O)R 4、S＝O、S(＝O) 2或C＝O；且Y 1和Y 2不同时为单键，Y 3和Y 4不同时为单键；
    n选自0-4的任一整数；
    R 1-R 5每次出现时，分别独立选自H，D，或具有1至20个C原子的直链烷基、烷氧基或硫代烷氧基，或具有3至20个C原子的支链或环状的烷基、烷氧基或硫代烷氧基，或甲硅烷基，或具有1至20个C原子的酮基，或具有2至20个C原子的烷氧基羰基，或具有7至20个C原子的芳氧基羰基，氰基，氨基甲酰基，卤甲酰基，甲酰基，异氰基，异氰酸酯基，硫氰酸酯基，异硫氰酸酯基，羟基，硝基，亚硝基，CF 3，Cl，Br，F，I，可交联的基团，或具有5至60个环原子的取代或未取代的芳香基、杂芳香基，或具有5至60个环原子的芳氧基、杂芳氧基，或这些体系的组合；相邻的R 1可以彼此结合形成取代或未取代的环；
    *表示连接位点。
  2. 根据权利要求1所述的用于有机电子器件的化合物，其特征在于：所述用于有机电子器件的化合物具有如通式(2-1)-(2-4)中的任一结构：
    Figure PCTCN2020134314-appb-100003
  3. 根据权利要求2所述的用于有机电子器件的化合物，其特征在于：所述R 1每次出现时，分别独立选自氰基，硝基，亚硝基，CF 3，Cl，B，I，F，或被氰基、硝基、亚硝基、CF 3、Cl、B、I、F取代的芳香基或杂芳香基。
  4. 根据权利要求2所述的用于有机电子器件的化合物，其特征在于：所述通式(2-1)和通式(2-2)中，n选自1-4的任一整数。
  5. 根据权利要求4所述的用于有机电子器件的化合物，其特征在于：所述R 1每次出现时，分别独立选自被氰基、硝基、亚硝基、CF 3、Cl、B、I、F取代的芳香基或杂芳香基。
  6. 根据权利要求2所述的用于有机电子器件的化合物，其特征在于：所述通式(2-4)中，Y 1和Y 3 同时选自S。
  7. 根据权利要求3或5所述的用于有机电子器件的化合物，其特征在于：所述被氰基、硝基、亚硝基、CF 3、Cl、B、I、F取代的芳香基或杂芳香基选自如下基团中的一种：
    Figure PCTCN2020134314-appb-100004
    其中：
    X每次出现时，独立选自CR 7或N；
    W每次出现时，独立选自CR 8R 9、NR 8、O、S、SiR 8R 9、PR 8、P(＝O)R 8、S＝O、S(＝O) 2或C＝O；
    R 7-R 9每次出现时，独立选自H，D，或具有1至20个C原子的直链烷基，或具有3至20个C原子的支链或环状的烷基，或具有1至20个C原子的酮基，或具有2至20个C原子的烷氧基羰基，或具有7至20个C原子的芳氧基羰基，氰基，氨基甲酰基，氰基，硝基，亚硝基，CF 3，Cl，B，I，F，或具有5至60个环原子的取代或未取代的芳香基、杂芳香基，或具有5至60个环原子的芳氧基、杂芳氧基，或这些体系的组合；且至少一个R 7选自氰基、硝基、亚硝基、CF 3、Cl、B、I或F。
  8. 根据权利要求7所述的用于有机电子器件的化合物，其特征在于：所述R 1每次出现时，分别独立选自
    Figure PCTCN2020134314-appb-100005
    其中：R 7每次出现时，独立选自H，D，氰基、硝基、亚硝基、CF 3、Cl、B、I或F，且至少一个R 7选自氰基、硝基、亚硝基、CF 3、Cl、B、I或F。
  9. 根据权利要求1所述的用于有机电子器件的化合物，其特征在于：Ar 1选自结构式(A-2)。
  10. 根据权利要求1所述的用于有机电子器件的化合物，其特征在于：所述M选自CR 2R 3或NR 2。
  11. 根据权利要求10所述的用于有机电子器件的化合物，其特征在于：所述M选自以下基团中的一种：
    Figure PCTCN2020134314-appb-100006
    其中：
    R 6每次出现时，独立选自氰基、硝基、亚硝基、CF 3、Cl、B、I或F；
    m选自0-5的任一整数。
  12. 根据权利要求11所述的用于有机电子器件的化合物，其特征在于：所述M选自以下基团中的一种：
    Figure PCTCN2020134314-appb-100007
  13. 一种混合物，其特征在于：包含如权利要求1-12任一项所述的用于有机电子器件的化合物，及至少一种有机功能材料，所述有机功能材料选自空穴注入材料、空穴传输材料、电子传输材料、电子注入材料、电子阻挡材料、空穴阻挡材料、发光体、主体材料或有机染料。
  14. 一种组合物，其特征在于，包括如权利要求1-12任一项所述的用于有机电子器件的化合物或权利要求13所述的混合物，及至少一种有机溶剂。
  15. 一种有机电子器件，其特征在于，包含至少一功能层，所述功能层的材料包含如权利要求1-12任一项所述的用于有机电子器件的化合物或如权利要求13所述的混合物，或由权利要求14所述的组合物制备而成。
  16. 根据权利要求15所述的有机电子器件，其特征在于，所述功能层选自空穴注入层。
  17. 根据权利要求15所述的有机电子器件，其特征在于，所述有机电子器件选自有机发光二极管，有机光伏电池，有机发光电池，有机场效应管，有机激光器，有机自旋电子器件，有机传感器及有机等离激元发射二极管。
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