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WO2019114611A1 - 芳香胺化合物，包含其的有机电子器件及应用 - Google Patents

芳香胺化合物，包含其的有机电子器件及应用 Download PDF

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Publication number
WO2019114611A1
WO2019114611A1 PCT/CN2018/119622 CN2018119622W WO2019114611A1 WO 2019114611 A1 WO2019114611 A1 WO 2019114611A1 CN 2018119622 W CN2018119622 W CN 2018119622W WO 2019114611 A1 WO2019114611 A1 WO 2019114611A1
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organic
aromatic amine
aromatic
amine compound
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PCT/CN2018/119622
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English (en)
French (fr)
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谭甲辉
张晨
潘君友
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广州华睿光电材料有限公司
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Priority to CN201880069460.6A priority Critical patent/CN111278834B/zh
Publication of WO2019114611A1 publication Critical patent/WO2019114611A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to an aromatic amine compound, including mixtures thereof, compositions, and organic electronic devices thereof, particularly in organic light emitting diodes.
  • OLEDs Organic light-emitting diodes
  • Organic electroluminescence refers to the phenomenon of converting electrical energy into light energy using organic matter.
  • An organic electroluminescence device utilizing an organic electroluminescence phenomenon generally has a structure in which a positive electrode and a negative electrode and an organic layer are contained therebetween.
  • the organic layer has a multilayer structure, and each layer contains a different organic substance. Specifically, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and the like may be included.
  • Such an organic electroluminescence device when a voltage is applied between the two electrodes, holes are injected from the positive electrode into the organic layer, electrons are injected from the negative electrode into the organic layer, and excitons are formed when the injected holes meet the electrons. The excitons emit light when they transition back to the ground state.
  • Such an organic electroluminescence device has characteristics such as self-luminescence, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, and high responsiveness.
  • the OLED device needs to be further improved in luminous efficiency and service life. Because OLED is used as a current-driven device, it is in a high current density state during operation, and the material is prone to Joule heat, resulting in device degradation, especially between the anode and the hole transport layer. .
  • the commonly used hole transporting materials have a low glass transition temperature, and the accumulation of Joule heat causes a change in the morphology of the film, and at the same time accelerates the decomposition of the material, thereby affecting the life of the device.
  • the hole mobility of the organic semiconductor material is generally higher than the electron mobility, resulting in a hole-electron transport imbalance that affects the device's luminous efficiency.
  • the devices of the above disclosed compounds have to be improved in power efficiency, luminous efficiency and working life, so new OLED materials still need to be proposed to improve the performance of the device.
  • an object of the present invention to provide a novel class of aromatic amine compounds having excellent current efficiency, mixtures and compositions thereof, and their use in organic electronic devices.
  • an aromatic amine group derivative of an anthracene heterocyclic skeleton can be used as an electroluminescent material, particularly as a hole transporting or hole injecting material, to obtain an OLED device having high luminous efficiency and long life.
  • Ea electron affinity
  • L 1 -L 3 is a linking group selected from a single bond, an aromatic group or a heteroaromatic group
  • Each occurrence of Ar 1 -Ar 6 may be independently selected from an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms. Or a combination of these systems, wherein Ar 1 and Ar 2 , Ar 3 and Ar 4 and Ar 5 and Ar 6 may be linked to each other to form a monocyclic or polycyclic aliphatic or aromatic ring system.
  • o, p, q each independently represent an integer of 0 to 1, and o + p + q ⁇ 1;
  • n and n each independently represent an integer of 0 to 3.
  • a high polymer characterized by comprising at least one repeating structural unit represented by the general formula (I).
  • a mixture comprising at least one aromatic amine compound or polymer as described above, and at least one other organic functional material, said another organic functional material being selected from the group consisting of hole injecting materials (HIM), hole transport material (HTM), p-dopant, electron transport material (ETM), electron injecting material (EIM), electron blocking material (EBM), hole blocking material (HBM), luminescent material (Emitter) , host material (Host) and organic dyes.
  • HIM hole injecting materials
  • HTM hole transport material
  • ETM electron transport material
  • EIM electron injecting material
  • EBM electron blocking material
  • Emitter hole blocking material
  • Hos host material
  • organic dyes organic dyes
  • a composition comprising at least one aromatic amine compound, polymer or mixture as described above, and at least one organic solvent.
  • An organic electronic device comprising at least one aromatic amine compound, polymer or mixture as described above.
  • An electroluminescent device characterized in that the luminescent layer comprises at least one aromatic amine compound, polymer, or mixture according to the above.
  • the aromatic amine compound of the present invention contains an anthracene heterocyclic skeleton, and when used as a hole transporting or hole injecting material, an OLED device having high luminous efficiency and long life can be obtained.
  • EA electron affinity
  • EA electron affinity
  • the present invention provides an aromatic amine compound, an organic electronic device comprising the same, and an application thereof.
  • an aromatic amine compound an organic electronic device comprising the same, and an application thereof.
  • the host material, the matrix material, the Host material, and the Matrix material have the same meaning and are interchangeable.
  • the singlet states and the singlet states have the same meaning and are interchangeable.
  • the triplet state and the triplet state have the same meaning and are interchangeable.
  • composition and the printing ink, or ink have the same meaning and are interchangeable.
  • the complex excited state, exciplex, and Exciplex have the same meaning and are interchangeable.
  • small molecule refers to a molecule that is not a polymer, oligomer, dendrimer, or blend. In particular, there are no repeating structures in small molecules.
  • the molecular weight of the small molecule is ⁇ 3000 g/mol, preferably ⁇ 2000 g/mol, preferably ⁇ 1500 g/mol.
  • the present invention relates to an aromatic amine compound of the formula (I):
  • L 1 -L 3 is a linking group selected from a single bond, an aromatic group or a heteroaromatic group
  • Each occurrence of Ar 1 -Ar 6 may be independently selected from an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms. Or a combination of these systems, wherein between Ar 1 and Ar 2 , between Ar 3 and Ar 4 , and between Ar 5 and Ar 6 may be linked to form a monocyclic or polycyclic aliphatic or aromatic ring system.
  • o, p, q each independently represent an integer of 0 to 1, and o + p + q ⁇ 1;
  • n and n each independently represent an integer of 0 to 3.
  • R 0 is selected from H, or D, or a substituted or unsubstituted aromatic or heteroaromatic ring system having from 5 to 20 ring atoms. In a most preferred embodiment, R 0 is selected from H, or D.
  • an aromatic amine compound according to the present invention is characterized in that the aromatic amine compound has a structure represented by the general formula (II-1)-(II-8):
  • Ar 1 -Ar 6 , o, p, q, m, n, R 0 , R 1 , R 2 , L 1 -L 3 have the same meaning as in claim 1.
  • each of Ar 1 -Ar 6 may be independently selected from an aromatic or heteroaromatic ring system having 5 to 30 ring atoms. Or an aryloxy or heteroaryloxy group having 5 to 30 ring atoms, or a combination of these systems, wherein one or more groups may form a single ring to each other and/or to the ring to which the group is bonded Or a polycyclic aliphatic or aromatic ring system;
  • each of Ar 1 -Ar 6 may be independently selected from an aromatic or heteroaromatic ring system having 5 to 20 ring atoms. Or an aryloxy or heteroaryloxy group having 5 to 20 ring atoms, or a combination of these systems, wherein between Ar 1 and Ar 2 , between Ar 3 and Ar 4 , and between Ar 5 and Ar 6 It may be linked to form a monocyclic or polycyclic aliphatic or aromatic ring system.
  • Ar 1 -Ar 6 may be independently selected from the following structures:
  • each occurrence of Z may be independently selected from N or CR 5 , and two adjacent Zs may not be N at the same time; when Z is connected to N in the general formula (I), Z is C;
  • R 3 , R 4 and R 5 have the same meanings as R 1 ;
  • P represents a saturated cycloalkane or heterocycloalkane having 3 to 10 ring atoms; preferably represents a saturated cycloalkane or heterocycloalkane having 3 to 8 ring atoms; more preferably represents a saturation having 3 to 5 ring atoms a cycloalkane or a heterocycloalkane;
  • the dotted line indicates a single bond in which the group is bonded to the N atom of the aromatic amine.
  • Ar 1 to Ar 6 are independently selected from the following structures:
  • L 1 -L 3 is a linking group selected from a single bond, an aromatic group or a heteroaromatic group
  • An aromatic group refers to a hydrocarbon group containing at least one aromatic ring, including a monocyclic group and a polycyclic ring system.
  • Heteroaromatic groups refer to hydrocarbyl groups (containing heteroatoms) comprising at least one heteroaromatic ring, including monocyclic groups and polycyclic ring systems. These polycyclic rings may have two or more rings in which two carbon atoms are shared by two adjacent rings, a fused ring. At least one of these heterocyclic rings is an aromatic or heteroaromatic group.
  • an aromatic group or a heteroaromatic group includes not only a system of an aromatic group or a heteroaryl group, but also a plurality of aryl or heteroaryl groups may also be interrupted by short non-aromatic units (for example, ⁇ 10). % of non-H atoms, 5% of non-H atoms, such as C, N or O atoms).
  • systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether and the like are also considered to be aromatic groups for the purposes of the present invention.
  • aromatic group preferred examples include: benzene, naphthalene, anthracene, phenanthrene, perylene, tetracene, anthracene, benzopyrene, triphenylene, anthracene, anthracene, and derivatives thereof.
  • heteroaromatic groups are: furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, hydrazine, hydrazine Oxazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrol, furanfuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, pyridine, pyrazine, Pyridazine, pyrimidine, triazine, quinoline, isoquinoline, o-diazine, quinoxaline, phenanthridine, carbaidine, quinazoline, quinazolinone, and derivatives thereof.
  • the L 1 -L 3 of the present invention is selected from an aromatic group having 6 to 40 carbon atoms or a heteroaromatic group having 3 to 40 carbon atoms. Further, L 1 -L 3 is selected from an aromatic group having 6 to 30 carbon atoms or a heteroaromatic group having 3 to 30 carbon atoms. Further, L 1 -L 3 is selected from an aromatic group having 6 to 20 carbon atoms or a heteroaromatic group having 3 to 20 carbon atoms.
  • Suitable aromatic or heteroaromatic groups which may be L 1 -L 3 are, but not limited to, benzene, naphthalene, anthracene, phenanthrene, anthracene, pyridine, pyrimidine, triazine, anthracene, sulfonium, silicon germanium. , carbazole, thiophene, furan, thiazole, triphenylamine, triphenylphosphine oxide, tetraphenyl silicon, snail, spirosilicone and the like.
  • linking group L 1 -L 3 of the present invention may comprise one or more combinations of the following structural formulas:
  • linking group L 1 -L 3 of the present invention may be selected from the following structural units, which may be further substituted:
  • the energy level structure of the organic compound the triplet energy level E T , the highest occupied orbital energy level HOMO, and the lowest occupied orbital energy level LUMO play an important role.
  • the following is an introduction to the determination of these energy levels.
  • the HOMO and LUMO levels can be measured by photoelectric effect, such as XPS (X-ray photoelectron spectroscopy) and UPS (UV photoelectron spectroscopy) or by cyclic voltammetry (hereinafter referred to as CV).
  • photoelectric effect such as XPS (X-ray photoelectron spectroscopy) and UPS (UV photoelectron spectroscopy) or by cyclic voltammetry (hereinafter referred to as CV).
  • quantum chemical methods such as density functional theory (hereinafter referred to as DFT) have also become effective methods for calculating molecular orbital energy levels.
  • the triplet energy level E T of organic materials can be measured by low temperature time-resolved luminescence spectroscopy, or by quantum simulation calculations (eg by Time-dependent DFT), as by commercial software Gaussian 03W (Gaussian Inc.), specific simulation methods. See WO2011141110 or as described below in the examples.
  • the absolute values of HOMO, LUMO, E T depend on the measurement method or calculation method used. Even for the same method, different evaluation methods, such as starting point and peak point on the CV curve, can give different HOMO/ LUMO value. Therefore, reasonable and meaningful comparisons should be made using the same measurement method and the same evaluation method.
  • the values of HOMO, LUMO, and E T are simulations based on Time-dependent DFT, but do not affect the application of other measurement or calculation methods. The energy level values determined by different methods should be calibrated against each other.
  • (HOMO-1) is defined as the second highest occupied orbital level
  • (HOMO-2) is the third highest occupied orbital level
  • (LUMO+1) is defined as the second lowest unoccupied orbital level
  • (LUMO+2) is the third lowest occupied orbital level, and so on.
  • the compound according to the invention is at least partially deuterated, preferably 10% of H is deuterated, more preferably 20% of H is deuterated, very preferably 30% H It is best to be replaced by 40% of H.
  • the compounds according to the invention can be used in various functional layers of organic electronic devices.
  • the compound according to the invention is used as a hole transporting material, a hole injecting material, and a host material.
  • the compound according to the invention has a HOMO ⁇ -5.5 eV, preferably ⁇ - 5.2 eV, more preferably ⁇ - 5.1 eV, most preferably ⁇ - 5.0 eV.
  • the compound according to the invention ((HOMO-(HOMO-1)) ⁇ 0.15 eV, preferably ⁇ 0.25 eV, more preferably ⁇ 0.3 eV, more preferably ⁇ 0.35 eV, very good is ⁇ 0.4eV, preferably ⁇ 0.5eV.
  • the compound according to the invention has a LUMO ⁇ -3.0 eV, preferably ⁇ -2.3 eV, more preferably ⁇ -2.2 eV, most preferably ⁇ - 2.0 eV.
  • the compound according to the invention has a triplet energy level E T ⁇ 2.4 eV, preferably ⁇ 2.6 eV, more preferably ⁇ 2.7 eV, most preferably ⁇ 2.8 eV.
  • hole mobility is sometimes a very important parameter.
  • the compounds according to the present invention has a high hole mobility, typically ⁇ 10 -5 cm 2 / Vs, Jiaoyou ⁇ 10 -4 cm 2 / Vs, and most ⁇ 10 -3 cm 2 /Vs.
  • the compound according to the invention has a glass transition temperature of ⁇ 100 ° C, preferably ⁇ 110 ° C, more preferably ⁇ 120 ° C, most preferably ⁇ 140 ° C.
  • a compound according to the invention is preferably, but not limited to, the following structure:
  • the aromatic amine compound according to the present invention also has luminescent properties with an emission wavelength of between 300 and 1000 nm, preferably between 350 and 900 nm, more preferably between 400 and 800 nm.
  • the luminescence referred to herein means photoluminescence or electroluminescence.
  • the aromatic amine compound according to the present invention has a photo or electroluminescence efficiency of ⁇ 30%, preferably ⁇ 40%, more preferably ⁇ 50%, most preferably ⁇ 60%.
  • the aromatic amine compound according to the present invention may also be a hole transport material or an electron injecting material.
  • the invention still further relates to a high polymer comprising at least one repeating unit comprising a structural unit represented by the general formula (I).
  • the method for synthesizing the high polymer is selected from the group consisting of SUZUKI-, YAMAMOTO-, STILLE-, NIGESHI-, KUMADA-, HECK-, SONOGASHIRA-, HIYAMA-, FUKUYAMA-, HARTWIG-BUCHWALD- and ULLMAN.
  • the polymer according to the invention has a glass transition temperature (Tg) ⁇ 100 ° C, preferably ⁇ 120 ° C, more preferably ⁇ 140 ° C, more preferably ⁇ 160 ° C, optimal. It is ⁇ 180 °C.
  • the polymer according to the present invention preferably has a molecular weight distribution (PDI) in the range of from 1 to 5; more preferably from 1 to 4; more preferably from 1 to 3, still more preferably 1 ⁇ 2 is most preferably 1 to 1.5.
  • PDI molecular weight distribution
  • the weight average molecular weight (Mw) of the high polymer according to the present invention preferably ranges from 10,000 to 1,000,000; more preferably from 50,000 to 500,000; more preferably from 100,000 to 40. More preferably, it is 150,000 to 300,000, and most preferably 200,000 to 250,000.
  • the present invention also provides a mixture comprising at least one of the above-described aromatic amine compounds or polymers, and at least one other organic functional material, said at least one other organic functional material being selectable In hole injection material (HIM), hole transport material (HTM), p-dopant, electron transport material (ETM), electron injecting material (EIM), electron blocking material (EBM), hole blocking material (HBM), Emitter, host material and organic dye.
  • HIM hole injection material
  • HTM hole transport material
  • ETM electron transport material
  • EIM electron injecting material
  • EBM electron blocking material
  • Emitter Emitter
  • host material and organic dye Emitter
  • organic functional materials are described in detail in, for example, WO2010135519A1, US20090134784A1, and WO 2011110277A1, the entire disclosure of which is hereby incorporated by reference.
  • the mixture of the ones comprises at least one aromatic amine compound or polymer according to the invention and a p-dopant, wherein the p-dopant weight percentage is ⁇ 10 wt%, preferably ⁇ 9 wt%, more preferably ⁇ 7 wt%, particularly preferably ⁇ 6 wt%, most preferably ⁇ 5 wt%.
  • the mixture comprises at least one aromatic amine compound or polymer according to the present invention, and a fluorescent host material.
  • a mixture may be used as a fluorescent host material, and may further comprise a fluorescent illuminant, wherein the fluorescent illuminant has a weight percentage of ⁇ 10% by weight, preferably ⁇ 9wt%, more preferably ⁇ 8wt%, particularly preferably ⁇ 7wt% Preferably, it is ⁇ 5 wt%.
  • the mixture of said one comprises at least one aromatic amine compound or polymer according to the invention and a phosphorescent host material.
  • a mixture may be used as a phosphorescent host material, and may further comprise a phosphorescent emitter, wherein the phosphorescent emitter has a weight percentage of ⁇ 25 wt%, preferably ⁇ 20 wt%, more preferably ⁇ 15 wt%.
  • the fluorescent host material singlet illuminant, phosphorescent host material, triplet illuminant and p-dopant material are described in detail below (but are not limited to):
  • Singlet emitters tend to have longer conjugated pi-electron systems.
  • styrylamine and its derivatives disclosed in JP 2913116 B and WO 2001021729 A1, indenoindoles and derivatives thereof disclosed in WO 2008/006449 and WO 2007/140847, and disclosed in US Pat. No. 7,233,019, KR2006-0006760 A quinone triarylamine derivative.
  • the singlet emitter can be selected from the group consisting of monostyrylamine, dibasic styrylamine, ternary styrylamine, quaternary styrylamine, styrene phosphine, styrene ether and aromatic amine.
  • a monostyrylamine refers to a compound comprising an unsubstituted or substituted styryl group and at least one amine, preferably an aromatic amine.
  • a dibasic styrylamine refers to a compound comprising two unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine.
  • a ternary styrylamine refers to a compound comprising three unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine.
  • a quaternary styrylamine refers to a compound comprising four unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine.
  • a preferred styrene is stilbene, which may be further substituted.
  • the corresponding phosphines and ethers are defined similarly to amines.
  • An arylamine or an aromatic amine refers to a compound comprising three unsubstituted or substituted aromatic ring or heterocyclic systems directly bonded to a nitrogen. At least one of these aromatic or heterocyclic ring systems is preferably selected from the fused ring system and preferably has at least 14 aromatic ring atoms.
  • Preferred examples thereof are aromatic decylamine, aromatic quinone diamine, aromatic decylamine, aromatic quinone diamine, aromatic thiamine and aromatic quinone diamine.
  • An aromatic amide refers to a compound in which a diaryl arylamine group is attached directly to the oxime, preferably at the position of 9.
  • An aromatic quinone diamine refers to a compound in which two diaryl arylamine groups are attached directly to the oxime, preferably at the 9,10 position.
  • the definitions of aromatic decylamine, aromatic quinone diamine, aromatic thiamine and aromatic quinone diamine are similar, wherein the diaryl aryl group is preferably bonded to the 1 or 1,6 position of hydrazine.
  • Examples of singlet emitters based on vinylamines and arylamines are also preferred examples and can be found in the following patent documents: WO 2006/000388, WO 2006/058737, WO 2006/000389, WO 2007/065549, WO 2007 /115610, US 7250532 B2, DE 102005058557 A1, CN 1583691 A, JP 08053397 A, US 6251531 B1, US 2006/210830 A, EP 1957606 A1 and US 2008/0113101 A1 are hereby incorporated by reference in their entirety. This article is incorporated herein by reference.
  • Further preferred singlet emitters can be selected from indenoindole-amines and indenofluorene-diamines, as disclosed in WO 2006/122630, benzoindoloindole-amines and benzoindenoindole-diamines , as disclosed in WO 2008/006449, dibenzoindolo-amine and dibenzoindeno-diamine, as disclosed in WO 2007/140847.
  • Further preferred singlet emitters are selected from the group consisting of ruthenium-based fused ring systems as disclosed in US2015333277A1, US2016099411A1, US2016204355A1.
  • More preferred singlet emitters may be selected from the derivatives of hydrazine, such as those disclosed in US2013175509A1; triarylamine derivatives of hydrazine, such as triarylamine derivatives of hydrazine containing dibenzofuran units disclosed in CN102232068B; A triarylamine derivative of hydrazine having a specific structure, as disclosed in CN105085334A, CN105037173A.
  • polycyclic aromatic hydrocarbon compounds in particular derivatives of the following compounds: for example, 9,10-bis(2-naphthoquinone), naphthalene, tetraphenyl, xanthene, phenanthrene , ⁇ (such as 2,5,8,11-tetra-t-butyl fluorene), anthracene, phenylene such as (4,4'-bis(9-ethyl-3-carbazolevinyl)-1 , 1 '-biphenyl), indenyl hydrazine, decacycloolefin, hexacene benzene, anthracene, spirobifluorene, aryl hydrazine (such as US20060222886), arylene vinyl (such as US5121029, US5130603), cyclopentane Alkene such as tetraphenylcyclopentadiene, rub
  • Triplet emitters are also known as phosphorescent emitters.
  • the triplet emitter is a metal complex of the formula M(L)n, wherein M is a metal atom, and each occurrence of L may be the same or different and is an organic ligand. It is bonded to the metal atom M by one or more positional bonding or coordination, and n is an integer greater than 1, preferably 1, 2, 3, 4, 5 or 6.
  • these metal complexes are coupled to a polymer by one or more positions, preferably by an organic ligand.
  • the metal atom M is selected from a transition metal element or a lanthanide or a lanthanide element, preferably Ir, Pt, Pd, Au, Rh, Ru, Os, Sm, Eu, Gd, Tb, Dy Re, Cu or Ag, with Os, Ir, Ru, Rh, Re, Pd, Au or Pt being particularly preferred.
  • the triplet emitter comprises a chelating ligand, ie a ligand, coordinated to the metal by at least two bonding sites, with particular preference being given to the triplet emitter comprising two or three identical or different pairs Tooth or multidentate ligand.
  • Chelating ligands are beneficial for increasing the stability of metal complexes.
  • Examples of the organic ligand may be selected from a phenylpyridine derivative, a 7,8-benzoquinoline derivative, a 2(2-thienyl)pyridine derivative, a 2(1-naphthyl)pyridine derivative, or a 2 benzene.
  • a quinolinol derivative All of these organic ligands may be substituted, for example by fluorine or trifluoromethyl.
  • the ancillary ligand may preferably be selected from the group consisting of acetone acetate or picric acid.
  • the metal complex that can be used as the triplet emitter has the following form:
  • M is a metal selected from a transition metal element or a lanthanide or actinide element, particularly preferably Ir, Pt, Au;
  • Ar 1 may be the same or different at each occurrence, and is a cyclic group containing at least one donor atom, that is, an atom having a lone pair of electrons, such as nitrogen or phosphorus, through which a cyclic group is coordinated to a metal.
  • Ar 2 may be the same or different each time it appears, is a cyclic group containing at least one C atom through which a cyclic group is attached to the metal; Ar 1 and Ar 2 are bonded by a covalent bond Together, each may carry one or more substituent groups, which may also be joined together by a substituent group; L' may be the same or different at each occurrence, and is a bidentate chelate auxiliary ligand, preferably Is a monoanionic bidentate chelate ligand; q1 can be 0, 1, 2 or 3, preferably 2 or 3; q2 can be 0, 1, 2 or 3, preferably 1 or 0.
  • triplet emitters Some examples of suitable triplet emitters are listed in the table below:
  • the fluorescent host material is also referred to as a singlet host material, and the example of the fluorescent host material is not particularly limited, and any organic compound may be used as a host as long as it has a singlet energy ratio illuminant, particularly a singlet illuminant. Or the fluorescent illuminant is higher.
  • Examples of the organic compound used as the fluorescent host material may be selected from the group consisting of a cyclic aromatic hydrocarbon compound such as benzene, biphenyl, triphenyl, benzo, naphthalene, anthracene, anthracene, phenanthrene, anthracene, anthracene, fluorene, fluorene, fluorene, fluorene, fluorene; Aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, carbazole, pyridinium , pyrrole dipyridine, pyrazole, imidazole, triazole, isoxazole, thiazole, oxadiazole, triazole, dioxazole, thiadiazole, pyridine, pyridazin
  • the fluorescent host material can be selected from compounds comprising at least one of the following groups:
  • R 1 may be independently of one another selected from the group consisting of hydrogen, deuterium, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl; n is a An integer from 0 to 20; X 1 -X 8 is selected from CH or N; X 9 and X 10 are selected from CR 1 R 2 or NR 1 . R 2 has the same meaning as R 1 .
  • the fluorescent host is selected from the group consisting of hydrazine derivatives, such as those disclosed in the patent documents CN102224614 B, CN 100471827 C, CN 1914293 B, WO2015033559A1, US2014246657A1, WO2016117848A1, WO2016117861A1, WO2016171429A2, CN102369256B, CN102428158B.
  • hydrazine derivatives such as those disclosed in the patent documents CN102224614 B, CN 100471827 C, CN 1914293 B, WO2015033559A1, US2014246657A1, WO2016117848A1, WO2016117861A1, WO2016171429A2, CN102369256B, CN102428158B.
  • fluorenyl-based fluorescent host materials are listed in the table below:
  • the fluorenyl-based fluorescent host material is deuterated, that is, the host material molecule contains at least one ruthenium atom, such as disclosed in the patent documents CN102369256B, CN102428158B, CN102639671B, US2015021586A1, and the like. Specific examples are:
  • the phosphorescent host material is also referred to as a triplet host material, and the example of the triplet host material is not particularly limited, and any metal complex or organic compound may be used as a host as long as its triplet level is higher than that of the illuminant, especially
  • the triplet emitter or phosphorescent emitter is higher, and examples of metal complexes that can be used as a triplet host include, but are not limited to, the following general structure:
  • M is a metal
  • (Y 3 -Y 4 ) is a bidentate ligand, Y 3 and Y 4 are independently selected from C, N, O, P, and S
  • L is an ancillary ligand
  • m is an integer The value is from 1 to the maximum coordination number of the metal; in a preferred embodiment, the metal complex that can be used as the triplet host has the following form:
  • (O-N) is a two-tooth ligand in which a metal is coordinated to an O and N atom.
  • m is an integer whose value ranges from 1 to the maximum coordination number of the metal;
  • M is optional for Ir and Pt.
  • Examples of the organic compound which can be used as the host of the triplet state are selected from compounds containing a cyclic aromatic hydrocarbon group such as benzene, biphenyl, triphenylbenzene, benzindene; compounds containing an aromatic heterocyclic group such as dibenzothiophene, Dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, oxazole, dibenzoxazole, carbazole, pyridinium, pyrrole dipyridine, Pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxazine , oxadiazin
  • each Ar may be further substituted, and the substituent may be hydrogen, hydrazine, cyano, halogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl. base.
  • the triplet host material can be selected from compounds comprising at least one of the following groups:
  • R 2 -R 7 have the same meaning as R 1
  • X 9 is selected from CR 1 R 2 or NR 1
  • Y is selected from CR 1 R 2 or NR 1 or O or S.
  • R 1 , n, X 1 -X 8 , and Ar 1 to Ar 3 have the same meanings as described above.
  • triplet host materials examples include:
  • Such an organic semiconductor material may be composed of a compound having good electron donating properties or good electron withdrawing properties.
  • strong electron acceptors such as tetracyanoquinone dimethane (TCNQ) or 2,3,5,6-tetrafluorotetracyano-1,4- Benzoyl dimethane (F4TCNQ) is well known. See article M. Pfeiffer, A. Beyer, T. Fritz, K. Leo, App. Phys. Lett., 73 (22), 3202-3204 (1998) and J. Blochwitz, M. Pfeiffer, T. Fritz, K. Leo, App. Phys. Lett., 73 (6), 729-731 (1998).
  • P-type dopants Due to defects in TCNQ and F4TCNQ in specific applications (molecular weight is too small, too volatile), a series of hydroquinone derivatives can be used as P-type dopants, the structure of which includes but is not limited to the following structure (patent TW200629362A):
  • R 8 to R 19 are independently F, Cl, CN, NO 2 , CF 3 , perfluoroalkyl, SO 3 R 20 , aryl or heteroaryl, wherein the aryl and heteroaryl are from one to the other F, Cl, CN, NO 2 , CF 3 , perfluoroalkyl, SO 3 R;
  • A, B, C, and D are independently selected from C(CN) 2 , (CF 3 )C(CN), (NO 2 )C(CN), C(halogen) 2 , C(CF 3 ) 2 , NCN , O, S, NR 20 and the following structure:
  • n2 is selected from a natural number from 1 to 4; each of X 1 , X 2 , and X 3 is independently selected from the group consisting of C(CN) 2 , (CF 3 )C(CN), (NO 2 )C(CN), C ( Halogen) 2 , C(CF 3 ) 2 , NCN, O, S, NR1 and the following structures:
  • the compounds according to the invention have a molecular weight of ⁇ 1100 g/mol, preferably ⁇ 1000 g/mol, very preferably ⁇ 950 g/mol, more preferably ⁇ 900 kg/mol, most preferably ⁇ 800 g/mol.
  • Another object of the invention is to provide a material solution for printing OLEDs.
  • the compounds according to the invention have a molecular weight of ⁇ 700 g/mol, preferably ⁇ 800 g/mol, very preferably ⁇ 900 g/mol, more preferably ⁇ 1000 g/mol, most preferably ⁇ 1100 g/mol.
  • the compound according to the invention has a solubility in toluene of > 2 mg/ml, preferably > 3 mg/ml, more preferably > 4 mg/ml, most preferably > 5 mg/ml at 25 °C.
  • Another object of the invention is a solution for providing materials for printing OLEDs.
  • the invention further relates to a composition or ink comprising the aromatic amine compound, polymer or mixture of any of the above, and at least one organic solvent.
  • the at least one organic solvent is selected from the group consisting of aromatic or heteroaromatic, ester, aromatic ketone or aromatic ether, aliphatic ketone or aliphatic ether, alicyclic or olefinic a compound, or a borate or phosphate compound, or a mixture of two or more solvents.
  • a composition according to the invention is characterized in that said at least one organic solvent is selected from solvents based on aromatic or heteroaromatic.
  • aromatic or heteroaromatic solvents suitable for the present invention are, but are not limited to, p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene.
  • aromatic ketone solvents suitable for the present invention are, but are not limited to, 1-tetralone, 2-tetralone, 2-(phenyl epoxy) tetralone, 6-(methoxy Tetrendanone, acetophenone, propiophenone, benzophenone, and derivatives thereof, such as 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylpropiophenone, 3-methylpropiophenone, 2-methylpropiophenone, etc.;
  • aromatic ether-based solvents suitable for the present invention are, but are not limited to, 3-phenoxytoluene, butoxybenzene, p-anisaldehyde dimethyl acetal, tetrahydro-2-phenoxy-2H -pyran, 1,2-dimethoxy-4-(1-propenyl)benzene, 1,4-benzodioxane, 1,3-dipropylbenzene, 2,5-dimethoxy Toluene, 4-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, diphenyl ether
  • the at least one organic solvent may be selected from the group consisting of: an aliphatic ketone, for example, 2-fluorenone, 3-fluorenone, 5-fluorenone, 2 - anthrone, 2,5-hexanedione, 2,6,8-trimethyl-4-indanone, anthrone, phorone, isophorone, di-n-pentyl ketone, etc.; or an aliphatic ether
  • the at least one organic 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, alkanolide, alkyl oleate, and the like. Particularly preferred are octyl octanoate, diethyl sebacate, diallyl phthalate, isodecyl isononanoate.
  • the solvent may be used singly or as a mixture of two or more organic solvents.
  • a composition according to the present invention comprising the organic compound or composition of any one of the above, and at least one organic solvent, may further comprise another organic solvent,
  • an organic solvent including but 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-phenoxytoluene, 1,1 , 1-trichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydronaphthalene ,
  • the invention further relates to the use of a composition as a printing ink for the preparation of organic electronic devices, particular preference being given to a preparation process by printing or coating.
  • suitable printing or coating techniques include, but are not limited to, inkjet printing, typography, screen printing, dip coating, spin coating, blade coating, roller printing, twist roll printing, lithography, flexography Printing, rotary printing, spraying, brushing or pad printing, slit-type extrusion coating, etc.
  • Preferred are gravure, screen printing and inkjet printing. Gravure printing, ink jet printing will be applied in embodiments of the invention.
  • the solution or suspension may additionally comprise one or more components such as surface active compounds, lubricants, wetting agents, dispersing agents, hydrophobic agents, binders and the like for adjusting viscosity, film forming properties, adhesion, and the like.
  • the invention further relates to the use of an aromatic amine compound, polymer, mixture or composition according to any of the preceding claims in an organic electronic device.
  • An organic electronic device characterized by comprising an aromatic amine compound, a polymer, or a mixture thereof according to any one of the above.
  • the organic electronic device may be selected from, but not limited to, an organic light emitting diode (OLED), an organic photovoltaic cell (OPV), an organic light emitting cell (OLEEC), an organic field effect transistor (OFET), an organic light emitting field effect transistor, and an organic Lasers, organic spintronic devices, organic sensors and organic plasmon emitting diodes (Organic Plasmon Emitting Diode), etc., particularly preferred are organic electroluminescent devices such as OLED, OLEEC, organic light-emitting field effect transistors.
  • the organic electronic device is an electroluminescent device comprising a hole injection layer or a hole transport layer, the hole injection layer or the hole transport layer comprising at least An aromatic amine compound, polymer, or mixture as described above.
  • a substrate an anode, at least one light-emitting layer, and a cathode are included.
  • the substrate can be opaque or transparent.
  • a transparent substrate can be used to make a transparent light-emitting component. See, for example, Bulovic et al. Nature 1996, 380, p29, and Gu et al, Appl. Phys. Lett. 1996, 68, p2606.
  • the substrate can be rigid or elastic.
  • the substrate can be plastic, metal, semiconductor wafer or glass.
  • the substrate has a smooth surface. Substrates without surface defects are a particularly desirable choice.
  • the substrate is flexible, optionally in the form of a polymer film or plastic, having a glass transition temperature Tg of 150 ° C or higher, preferably more than 200 ° C, more preferably more than 250 ° C, preferably More than 300 ° C. Examples of suitable flexible substrates are poly(ethylene terephthalate) (PET) and polyethylene glycol (2,6-naphthalene) (PEN).
  • PET poly(ethylene terephthalate)
  • PEN polyethylene glycol (2,6-na
  • the anode can 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 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 HOMO level or the valence band level of the illuminant in the luminescent layer or the p-type semiconductor material as the HIL or HTL or electron blocking layer (EBL) is less than 0.5 eV, preferably less than 0.3 eV, and most preferably less than 0.2 eV.
  • anode material examples 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 can be readily selected for use by one of ordinary skill in the art.
  • the anode material can be deposited using any suitable technique, such as a suitable physical vapor deposition process, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.
  • the anode is patterned. Patterned ITO conductive substrates are commercially available and can be used to prepare devices in accordance with the present invention.
  • the cathode can include a conductive metal or metal oxide.
  • the cathode can easily inject electrons into the EIL or ETL or directly into the luminescent layer.
  • the work function of the cathode and the LUMO level of the illuminant or the n-type semiconductor material as an electron injection layer (EIL) or electron transport layer (ETL) or hole blocking layer (HBL) in the luminescent layer or
  • EIL electron injection layer
  • ETL electron transport layer
  • HBL hole blocking layer
  • the absolute value of the difference in conduction band energy levels is less than 0.5 eV, preferably less than 0.3 eV, and most preferably less than 0.2 eV.
  • all materials which can be used as cathodes for OLEDs are possible as cathode materials for the devices of the invention.
  • cathode material examples 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 process, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.
  • the OLED may further include other 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), and a hole blocking layer.
  • 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 an emission wavelength of between 300 and 1000 nm, preferably between 350 and 900 nm, more preferably between 400 and 800 nm.
  • the invention further relates to the use of an electroluminescent device according to the invention in various electronic devices, including, but not limited to, display devices, illumination devices, light sources, sensors and the like.
  • the energy structure of the organic repeating structural unit can be obtained by quantum calculation, for example, by TD-DFT (time-dependent density functional theory) by Gaussian 03W (Gaussian Inc.), and the specific simulation method can be found in WO2011141110.
  • TD-DFT time-dependent density functional theory
  • Gaussian 03W Gaussian Inc.
  • the specific simulation method can be found in WO2011141110.
  • the semi-empirical method “Ground State/Semi-empirical/Default Spin/AM1” (Charge 0/Spin Singlet) is used to optimize the molecular geometry, and then the energy structure of the organic molecule is determined by TD-DFT (time-dependent density functional theory) method.
  • TD-SCF/DFT/Default Spin/B3PW91 and the base group "6-31G(d)” (Charge 0/Spin Singlet).
  • the HOMO and LUMO levels are calculated according to the following calibration formula, and S1 and T1 are used directly
  • HOMO(eV) ((HOMO(G) ⁇ 27.212)-0.9899)/1.1206
  • HOMO(G) and LUMO(G) are direct calculation results of Gaussian 09W, and the unit is eV.
  • Compound 1, Compound 4, Compound 5, Ref-1, NPB are used as hole transport materials
  • DNTPD is used as hole injection material
  • B3PYMPM is used as electron transport material
  • the device structure is ITO/HATCN/empty.
  • ITO indium tin oxide
  • a conductive glass substrate cleaning using a variety of solvents (such as one or several of chloroform, acetone or isopropanol) cleaning, and then UV ozone treatment;
  • DNTPD 60 nm
  • hole transport material 20 nm
  • BH: BD 95:5; 20 nm
  • B3PYMPM 30 nm
  • Al 100 nm
  • high vacuum (1 ⁇ 10 -6 m Ba
  • the device is encapsulated in a nitrogen glove box with an ultraviolet curable resin.
  • the current and voltage (IVL) characteristics of each OLED device are characterized by characterization equipment, as described in Table 2.

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Abstract

本发明公开了一种芳香胺化合物，及其在有机电子器件的应用，特别是在有机电致发光二极管中的应用。本发明还公开了包含有按照本发明的芳香胺化合物的有机电子器件，特别是有机电致发光二极管，及其在显示及照明技术中的应用。本发明还进一步公开了包含有按照本发明的芳香胺化合物的有机电子器件。

Description

芳香胺化合物，包含其的有机电子器件及应用
本申请要求于2017年12月14日提交中国专利局、申请号为201711341865.4发明名称为“芳香胺化合物，包含其的有机电子器件及应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及一种芳香胺化合物，包含其的混合物，组合物，及其有机电子器件，特别是在有机发光二极管中的应用。
背景技术
由于有机半导体材料在合成上具有多样性、制造成本相对较低和优良的光学与电学性能，有机发光二极管(OLED)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。
有机电致发光现象是指利用有机物质将电能转化为光能的现象。利用有机电致发光现象的有机电致发光元件通常具有正极与负极以及在它们中间包含有机物层的结构。为了提高有机电致发光元件的效率与寿命，有机物层具有多层结构，每一层包含有不同的有机物质。具体的，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。在这种有机电致发光元件中，在两个电极之间施加电压，则由正极向有机物层注入空穴，由负极向有机物层注入电子，当注入的空穴与电子相遇时形成激子，该激子跃迁回基态时发出光。这种有机电致发光元件具有自发光、高亮度、高效率、低驱动电压、广视角、高对比度、高响应性等特性。
然而OLED器件在发光效率及使用寿命还需要进一步改善，因为OLED作为电流驱动器件，工作时处于高电流密度状态，材料容易出现焦耳热，导致器件劣化，尤其是在阳极和空穴传输层之间。常用的空穴传输材料玻璃化转变温度较低，焦耳热的积累导致薄膜形貌发生变化，同时会加速材料分解，从而影响器件寿命。此外，有机半导体材料的空穴迁移率普遍高于电子迁移率，导致的空穴-电子传输不平衡从而影响器件发光效率。
基于此，现有研究工作希望能降低器件工作电压和提升效率(Synthetic Metals,2009,159,69；J.Phys.D:Appl.Phys.2007,40,5553)。专利文献US8021764B2中公开了3位咔唑取代的芳胺化合物用作空穴传输材料改善器件发光效率；专利文献WO2009148015A1公开了用于一类化合物，其中包括咔唑、二苯并呋喃和二苯并噻吩的杂芳环直接与多环化合物的主链碳原子相连，所述多环化合物通过芴、咔唑、二苯并呋喃和二苯并噻吩与包括茚、吲哚、苯并呋喃和苯并噻吩的杂芳基稠合形成；US2015105563 A1公开了一个或多个二芳胺基直接或经由芳基键合到与芳基或杂芳基稠合的螺[芴-9,9’-芴]主链的苯环的化合物。
不过上述公开的化合物的器件在功率效率，发光效率以及工作寿命上均有待提高，因此仍需提出新的OLED材料，来提高器件的性能。
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类具有极佳电流效率的新型芳香胺化合物，包含其的混合物和组合物、及其在有机电子器件中的应用。通过大量研究发现，将吲哚杂环骨架的芳香胺族衍生物作为电致发光材料，尤其用作空穴传输或空穴注入材料，可以得到高发光效率长寿命的OLED器件。进一步研究发现，基于本发明的化合物，Ea(电子亲和力)变弱从而具有阻挡来自电子传输层的相邻层电子的效果，同时具有较高的电化学稳定性，所以复合效率提高，发光效率提高，器件寿命延长。
本发明的技术方案如下：
一种如通式(I)所示的芳香胺化合物：
Figure PCTCN2018119622-appb-000001
其中：
R 0、R 1、R 2每次出现时，相同或不同地选自H、或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(-CN)，氨基甲酰基(-C(＝O)NH 2)，卤甲酰基(-C(＝O)-X其中X代表卤素原子),甲酰基(-C(＝O)-H)，异氰基，异氰酸酯，硫氰酸酯或异硫氰酸酯，羟基，硝基，CF 3，Cl，Br，F，可交联的基团，或者具有5至40个环原子的取代或未取代的芳族或杂芳族环系，或具有5至40个环原子的芳氧基或杂芳氧基基团，或这些体系的组合，其中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系；
L 1-L 3为连接基团，选自单键、芳香基团或杂芳香基团；
Ar 1-Ar 6每次出现时，可独立选自具有5至40个环原子的芳族或杂芳族环系，或具有5至40个环原子的芳氧基或杂芳氧基基团，或这些体系的组合，其中Ar 1与Ar 2、Ar 3与Ar 4和Ar 5与Ar 6彼此可以链接形成单环或多环的脂族或芳族环系。
o、p、q各自独立地表示0～1的整数，并且o+p+q≥1；
m、n各自独立地表示0～3的整数。
一种高聚物，其特征在于，包含至少一个如通式(I)表示的重复结构单元。
一种混合物，其特征在于，包含至少一种如上所述的芳香胺化合物或高聚物，及至少另一种的有机功能材料，所述另一种的有机功能材料可选自空穴注入材料(HIM)，空穴传输材料(HTM)，p-dopant，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。
一种组合物，其特征在于，包含至少一种如上所述所述的芳香胺化合物、高聚物或混合物，及至少一种有机溶剂。
一种根据如上所述的芳香胺化合物、高聚物、混合物或组合物在有机电子器件中的应用。
一种有机电子器件，其特征在于，至少包含一种如上所述的芳香胺化合物、高聚物或混合物。
一种根据如上所述电致发光器件，其特征在于，其发光层至少包含一种根据如上所述的芳香胺化合物、高聚物、或混合物。
有益效果：本发明的芳香胺化合物，包含有吲哚杂环骨架，当作为空穴传输或空穴注入材料时，可以得到高发光效率长寿命的OLED器件。同时基于本发明的化合物，EA(电子亲和力)变弱从而具有阻挡来自电子传输层的相邻层电子的效果，具有较高的电化学稳定性，所以复合效率提高，发光效率提高，器件寿命延长。
具体实施方式
本发明提供一种芳香胺化合物，包含其的有机电子器件及应用。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仅用以解释本发明，并不用于限定本发明。
在本发明实施例中，主体材料、基质材料、Host材料和Matrix材料具有相同的含义，可以互换。
在本发明实施例中，单线态，单重态具有相同的含义，可以互换。
在本发明实施例中，三线态，三重态具有相同的含义，可以互换。
在本发明中，组合物和印刷油墨，或油墨具有相同的含义，可以互换。
在本发明中，复合受激态，激基络合物，Exciplex具有相同的含义，可以互换。
本文中所定义的术语“小分子”是指不是聚合物，低聚物，树枝状聚合物，或共混物的分子。特别是，小分子中没有重复结构。小分子的分子量≤3000克/摩尔，较好是≤2000克/摩尔，最好是≤1500克/摩尔。
本发明涉及一种如通式(I)所示的芳香胺化合物：
Figure PCTCN2018119622-appb-000002
其中：
R 0、R 1、R 2每次出现时，相同或不同地选自H、或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(-CN)，氨基甲酰基(-C(＝O)NH 2)，卤甲酰基(-C(＝O)-X其中X代表卤素原子),甲酰基(-C(＝O)-H)，异氰基，异氰酸酯，硫氰酸酯或异硫氰酸酯，羟基，硝基，CF 3，Cl，Br，F，可交联的基团，或者具有5至40个环原子的取代或未取代的芳族或杂芳族环系，或具有5至40个环原子的芳氧基或杂芳氧基基团，或这些体系的组合，其中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系；
L 1-L 3为连接基团，选自单键、芳香基团或杂芳香基团；
Ar 1-Ar 6每次出现时，可独立选自具有5至40个环原子的芳族或杂芳族环系，或具有5至40个环原子的芳氧基或杂芳氧基基团，或这些体系的组合，其中Ar 1与Ar 2之间、Ar 3与Ar 4之间及Ar 5与Ar 6之间可以链接形成单环或多环的脂族或芳族环系。
o、p、q各自独立地表示0～1的整数，并且o+p+q≥1；
m、n各自独立地表示0～3的整数。
在一个优选的实施例中，R 0、R 1、R 2每次出现时，相同或不同地选自H、或D，或具有1至10个C原子的直链烷基、烷氧基或硫代烷氧基，或具有3至10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10个C原子的酮基，或具有2至10个C原子的烷氧基羰基，或具有7至10个C原子的芳氧基羰基，氰基(-CN)，氨基甲酰基 (-C(＝O)NH 2)，卤甲酰基(-C(＝O)-X其中X代表卤素原子),甲酰基(-C(＝O)-H)，异氰基，异氰酸酯，硫氰酸酯或异硫氰酸酯，羟基，硝基，CF 3，Cl，Br，F，可交联的基团，或者具有5至20个环原子的取代或未取代的芳族或杂芳族环系，或具有5至20个环原子的芳氧基或杂芳氧基基团，或这些体系的组合，其中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系；
在一个更为优选的实施例中，R 0选自H、或D，或者具有5至20个环原子的取代或未取代的芳族或杂芳族环系。在一个最为优选的实施例中，R 0选自H、或D。
在一个优选的实施例中，按照本发明所述的一种芳香胺化合物，其特征在于，所述的芳香胺化合物具有通式(II-1)-(II-8)所示的结构：
Figure PCTCN2018119622-appb-000003
其中Ar 1-Ar 6、o、p、q、m、n、R 0、R 1、R 2、L 1-L 3含义同权利要求1。
在一个优选的实施例中，按照本发明的芳香胺化合物，所述的Ar 1-Ar 6每次出现时，可独立选自具有5至30个环原子的芳族或杂芳族环系，或具有5至30个环原子的芳氧基或杂芳氧基基团，或这些体系的组合，其中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系；
在一个更优选的实施例中，按照本发明的芳香胺化合物，所述的Ar 1-Ar 6每次出现时，可独立选自具有5至20个环原子的芳族或杂芳族环系，或具有5至20个环原子的芳氧基或杂芳氧基基团，或这些体系的组合，其中Ar 1与Ar 2之间、Ar 3与Ar 4之间及Ar 5与Ar 6之间可以链接形成单环或多环的脂族或芳族环系。
具体的，所述的Ar 1-Ar 6可独立的选自如下结构：
Figure PCTCN2018119622-appb-000004
其中Z每次出现时，可独立的选自N或CR 5，而且两个相邻的Z不能同时为N；当Z为与通式(I)中N相连时，Z为C；
R 3、R 4、R 5含义同R 1；
P表示具有3-10个环原子的饱和环烷烃或杂环烷烃；优选的表示具有3-8个环原子的饱和环烷烃或杂环烷烃；更优选的表示具有3-5个环原子的饱和环烷烃或杂环烷烃；
虚线表示所述基团与芳香胺的N原子连接的单键。
在一个更加优先的实施例中，其中Ar 1～Ar 6可相独立的选自以下结构：
Figure PCTCN2018119622-appb-000005
Figure PCTCN2018119622-appb-000006
在一个优选的实施例中，L 1-L 3为连接基团，选自单键、芳香基团或杂芳香基团；
芳香基团指至少包含一个芳环的烃基，包括单环基团和多环的环系统。杂芳香基团指包含至少一个杂芳环的烃基(含有杂原子)，包括单环基团和多环的环系统。这些多环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。多环的这些环种，至少一个是芳香的或杂芳香基团。对于本发明的目的，芳香基团或杂芳香基团不仅包括芳香基或杂芳香基的体系，而且，其中多个芳基或杂芳基也可以被短的非芳族单元间断(例如<10％的非H原子，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芳香基团。
具体地，芳香基团优选的例子有：苯、萘、蒽、菲、二萘嵌苯、并四苯、芘、苯并芘、三亚苯、苊、芴、及其衍生物。
具体地，杂芳香基团优选的例子有：呋喃、苯并呋喃、噻吩、苯并噻吩、吡咯、吡唑、三唑、咪唑、噁唑、噁二唑、噻唑、四唑、吲哚、咔唑、吡咯并咪唑、吡咯并吡咯、噻吩并吡咯、噻吩并噻吩、呋喃并吡咯、呋喃并呋喃、噻吩并呋喃、苯并异噁唑、苯并异噻唑、苯并咪唑、吡啶、吡嗪、哒嗪、嘧啶、三嗪、喹啉、异喹啉、邻二氮萘、喹喔啉、菲啶、伯啶、喹唑啉、喹唑啉酮、及其衍生物。
在一个实施例中，本发明所述的L 1-L 3选自碳原子数为6～40的芳香基团或碳原子数为3～40的杂芳香基团。进一步的，L 1-L 3选自碳原子数为6～30的芳香基团或碳原子数为3～30的杂芳香基团。更进一步的，L 1-L 3选自碳原子数为6～20的芳香基团或碳原子数为3～20的杂芳香基团。
合适的可作为L 1-L 3的芳香基团或杂芳香基团的例子有，但不限于，苯、萘、蒽、菲、芘、吡啶、嘧啶、三嗪、芴、硫芴、硅芴、咔唑、噻吩、呋喃、噻唑、三苯胺、三苯基氧磷，四苯基硅、螺芴、螺硅芴等基团。
具体的，本发明所述的连接基团L 1-L 3可包含有如下结构式一种或多种组合：
Figure PCTCN2018119622-appb-000007
其中X每次出现时，可独立的选自N或CR 6；Y每次出现时，可独立的选自CR 7R 8，SiR 9R 10，NR 11或，C(＝O)，S，或O；R 6-R 11含义同R 1；
更进一步，本发明所述的连接基团L 1-L 3可选自如下结构单元，他们可以被进一步被取代：
Figure PCTCN2018119622-appb-000008
在本发明实施例中，有机化合物的能级结构，三线态能级E T、最高占有轨道能级HOMO、最低占有轨道能级LUMO起着重要的作用。以下对这些能级的确定做一介绍。
HOMO和LUMO能级可以通过光电效应进行测量，例如XPS(X射线光电子光谱法)和UPS(紫外光电子能谱)或通过循环伏安法(以下简称CV)。最近，量子化学方法，例如密度泛函理论(以下简称DFT)，也成为行之有效的计算分子轨道能级的方法。
有机材料的三线态能级E T可通过低温时间分辨发光光谱来测量，或通过量子模拟计算(如通过Time-dependent DFT)得到，如通过商业软件Gaussian 03W(Gaussian Inc.)，具体的模拟方法可参见WO2011141110或如下在实施例中所述。
应该注意，HOMO、LUMO、E T的绝对值取决于所用的测量方法或计算方法，甚至对于相同的方法，不同评价的方法，例如在CV曲线上起始点和峰点可给出不同的HOMO/LUMO值。因此，合理有意义的比较应该用相同的测量方法和相同的评价方法进行。本发明实施例的描述中，HOMO、LUMO、E T的值是基于Time-dependent DFT的模拟，但不影响其他测量或计算方法的应用。不同方法确定的能级值应进行相互标定。
在发明中，(HOMO-1)定义为第二高的占有轨道能级，(HOMO-2)为第三高的占有轨道能级，以此类推。(LUMO+1)定义为第二低的未占有轨道能级，(LUMO+2)为第三低的占有轨道能级，以此类推。
在一个比较优先的实施例中，按照本发明的化合物是至少部分被氘代，较好是10％的H被氘代，更好是20％的H被氘代，很好是30％的H被氘代，最好是40％的H被氘代。
按照本发明的化合物可以被用于有机电子器件的各种功能层。在一个优先的实施例中，按照本发明的化合物被用作空穴传输材料，空穴注入材料，及主体材料。
在某些优选的实施例中，按照本发明的化合物，其HOMO≥-5.5eV，较好是≥-5.2eV，更好是≥-5.1eV，最好是≥-5.0eV。
在某些优先的实施例中，按照本发明的化合物，其((HOMO-(HOMO-1))≥0.15eV，较好是≥0.25eV，更好是≥0.3eV，更更好是≥0.35eV，非常好是≥0.4eV，最好是≥0.5eV。
在某些实施例中，按照本发明的化合物，其LUMO≥-3.0eV，较好是≥-2.3eV，更好是≥-2.2eV，最好是≥-2.0eV。
在另一些优选的实施例中，按照本发明的化合物，其三线态能级E T≥2.4eV，较好是≥2.6eV，更好是≥2.7eV，最好是≥2.8eV。
作为空穴传输材料，空穴注入材料，及主体材料，空穴迁移率有时是非常重要的一个参数。
在一些优先的实施方案中，按照本发明的化合物具有较高的空穴迁移率，一般≥10 -5cm 2/V.s，较优≥10 -4cm 2/V.s，最优≥10 -3cm 2/V.s。
在另一些优先的实施例中，按照本发明的化合物的玻璃化温度≥100℃，较好是≥110℃，更好是≥120℃，最好是≥140℃。
在一个优选的实施例中，按照本发明所述的一种化合物，优选自但不限于如下结构：
Figure PCTCN2018119622-appb-000009
Figure PCTCN2018119622-appb-000010
Figure PCTCN2018119622-appb-000011
在某些实施例中，按照本发明的芳香胺化合物也具有发光性能，其发光波长在300到1000nm之间，较好是在350到900nm之间，更好是在400到800nm之间。这里指的发光是指光致发光或电致发光。
在某些优选的实施例中，按照本发明的芳香胺化合物，其光致或电致发光效率≥30％，较优是≥40％，更优是≥50％，最优是≥60％。
在某些实施例中，按照本发明的芳香胺化合物也可以是空穴传输材料或电子注入材料。
本发明还进一步涉及一种高聚物，其特征在于，包含至少一个含有通式(I)表示的结构单元的重复单元。
在一个优选的实施例中，其中的高聚物的合成方法选自SUZUKI-,YAMAMOTO-,STILLE-,NIGESHI-,KUMADA-,HECK-,SONOGASHIRA-,HIYAMA-,FUKUYAMA-,HARTWIG-BUCHWALD-和ULLMAN。
在一个优先的实施例中，按照本发明的高聚物，其玻璃化温度(Tg)≥100℃，优选为≥120℃，更优为≥140℃，更更优为≥160℃，最优为≥180℃。
在一个优先的实施例中，按照本发明的高聚物，其分子量分布(PDI)取值范围优选为1～5；较优选为1～4；更优选为1～3，更更优选为1～2，最优选为1～1.5。
在一个优先的实施例中，按照本发明的高聚物，其重均分子量(Mw)取值范围优选为1万～100万；较优选为5万～50万；更优选为10万～40万，更更优选为15万～30万，最优选为20万～25万。
本发明还提供一种混合物，其特征在于，包含有至少一种以上所述的芳香胺化合物或高聚物，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)，p-dopant，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WO 2011110277A1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。
在一个较优选的实施例中，所述的一种的混合物，包含至少一种按照本发明的芳香胺化合物或高聚物和一种p-dopant，其中所述的p-dopant重量百分比为≤10wt％，较好是≤9wt％，更好是≤7wt％,特别好是≤6wt％,最好是≤5wt％。
在某些实施例中，所述的一种混合物，包含至少一种按照本发明的芳香胺化合物或高聚物，和一种荧光主体材料。这样混合物可以作为荧光主体材料，可以进一步包含一荧光发光体，其中所述的荧光发光体重量百分比为≤10wt％，较好是≤9wt％，更好是≤8wt％,特别好是≤7wt％,最好是≤5wt％。
在另一个优选的实施例中，所述的一种的混合物，包含至少一种按照本发明的芳香胺化合物或高聚物和一种磷光主体材料。这样的混合物可以作为磷光主体材料，可以进一步包含一磷光发光体，其中所述的磷光发光体重量百分比为≤25wt％，较好是≤20wt％，更好是≤15wt％。
下面对荧光主体材料、单重态发光体、磷光主体材料、三重态发光体及p-dopant材料作一些详细的描述(但不限于此)：
1.单重态发光体(Singlet Emitter)
单重态发光体往往有较长的共轭π电子系统。迄今,已有许多例子，例如在JP2913116B和WO2001021729A1中公开的苯乙烯胺及其衍生物，在WO2008/006449和WO2007/140847中公开的茚并芴及其衍生物及在US7233019、KR2006-0006760中公开的芘的三芳胺衍生物。
在一个优先的实施方案中,单重态发光体可选自一元苯乙烯胺，二元苯乙烯胺，三元苯乙烯胺，四元苯乙烯胺，苯乙烯膦，苯乙烯醚和芳胺。
一个一元苯乙烯胺是指一化合物,它包含一个无取代或取代的苯乙烯基组和至少一个胺，最好是芳香胺。一个二元苯乙烯胺是指一化合物,它包含二个无取代或取代的苯乙烯基组和至少一个胺，最好是芳香胺。一个三元苯乙烯胺是指一化合物,它包含三个无取代或取代的苯乙烯基组和至少一个胺，最好是芳香胺。一个四元苯乙烯胺是指一化合物,它包含四个无取代或取代的苯乙烯基组和至少一个胺，最好是芳香胺。一个优选的苯乙烯是二苯乙烯,其可能会进一步被取代。相应的膦类和醚类的定义与胺类相似。芳基胺或芳香胺是指一种化合物，包含三个直接联接氮的无取代或取代的芳香环或杂环系统。这些芳香族或杂环的环系统中至少有一个优先选于稠环系统，并最好有至少14个芳香环原子。其中优选的例子有芳香蒽胺，芳香蒽二胺，芳香芘胺，芳香芘二胺，芳香屈胺和芳香屈二胺。一个芳香蒽胺是指一化合物，其中一个二元芳基胺基团直接联到蒽上,最好是在9的位置上。一个芳香蒽二胺是指一化合物，其中二个二元芳基胺基团直接联到蒽上,最好是在9,10的位置上。芳香芘胺，芳香芘二胺，芳香屈胺和芳香屈二胺的定义类似,其中二元芳基胺基团最好联到芘的1或1,6位置上.
基于乙烯胺及芳胺的单重态发光体的例子,也是优选的例子,可在下述专利文件中找到:WO 2006/000388,WO 2006/058737,WO 2006/000389,WO 2007/065549,WO 2007/115610,US 7250532 B2,DE 102005058557 A1,CN 1583691 A,JP 08053397 A,US 6251531 B1, US 2006/210830 A,EP 1957606 A1和US 2008/0113101 A1特此上述列出的专利文件中的全部内容并入本文作为参考。
基于均二苯乙烯极其衍生物的单重态发光体的例子有US 5121029。
进一步的优选的单重态发光体可选于茚并芴-胺和茚并芴-二胺，如WO 2006/122630所公开的，苯并茚并芴-胺和苯并茚并芴-二胺，如WO 2008/006449所公开的，二苯并茚并芴-胺和二苯并茚并芴-二胺，如WO2007/140847所公开的。
进一步优选的单重态发光体可选于基于芴的稠环体系，如US2015333277A1、US2016099411A1、US2016204355A1所公开的。
更加优选的单重态发光体可选于芘的衍生物，如US2013175509A1所公开的结构；芘的三芳胺衍生物，如CN102232068B所公开的含有二苯并呋喃单元的芘的三芳胺衍生物；其它具有特定结构的芘的三芳胺衍生物，如CN105085334A、CN105037173A所公开的。其他可用作单重态发光体的材料有多环芳烃化合物，特别是如下化合物的衍生物:蒽如9,10-二(2-萘并蒽)，萘,四苯，氧杂蒽，菲,芘(如2,5,8,11-四-t-丁基苝)，茚并芘，苯撑如(4,4’-双(9-乙基-3-咔唑乙烯基)-1,1’-联苯)，二茚并芘,十环烯,六苯并苯,芴，螺二芴,芳基芘(如US20060222886)，亚芳香基乙烯(如US5121029，US5130603),环戊二烯如四苯基环戊二烯,红荧烯，香豆素，若丹明，喹吖啶酮，吡喃如4(二氰基亚甲基)-6-(4-对二甲氨基苯乙烯基-2-甲基)-4H-吡喃(DCM),噻喃,双(吖嗪基)亚胺硼化合物(US 2007/0092753 A1),双(吖嗪基)亚甲基化合物,carbostyryl化合物,噁嗪酮,苯并恶唑,苯并噻唑,苯并咪唑及吡咯并吡咯二酮。一些单重态发光体的材料可在下述专利文件中找到:US 20070252517 A1,US 4769292,US 6020078,US 2007/0252517 A1,US 2007/0252517 A1。特此将上述列出的专利文件中的全部内容并入本文作为参考。
下面的表中列出一些合适的单重态发光体的例子:
Figure PCTCN2018119622-appb-000012
Figure PCTCN2018119622-appb-000013
2.三重态发光体(Triplet Emitter)
三重态发光体也称磷光发光体。在一个优先的实施方案中，三重态发光体是有通式M(L)n的金属络合物,其中M是一金属原子，L每次出现时可以是相同或不同，是一有机配体，它通过一个或多个位置键接或配位连接到金属原子M上,n是一个大于1的整数，较好选是1，2，3，4，5或6。可选地，这些金属络合物通过一个或多个位置联接到一个聚合物上，最好是通过有机配体。
在一个优先的实施方案中,金属原子M选于过渡金属元素或镧系元素或锕系元素,优先选择Ir,Pt,Pd,Au,Rh,Ru,Os,Sm,Eu,Gd,Tb,Dy,Re,Cu或Ag，特别优先选择Os,Ir,Ru,Rh,Re,Pd,Au或Pt。
优先地,三重态发光体包含有螯合配体，即配体，通过至少两个结合点与金属配位，特别优先考虑的是三重态发光体包含有两个或三个相同或不同的双齿或多齿配体。螯合配体有利于提高金属络合物的稳定性。
有机配体的例子可选自苯基吡啶衍生物，7,8-苯并喹啉衍生物，2(2-噻吩基)吡啶衍生物，2(1-萘基)吡啶衍生物，或2苯基喹啉衍生物。所有这些有机配体都可能被取代，例如被含氟或三氟甲基取代。辅助配体可优先选自乙酸丙酮或苦味酸。
在一个优先的实施方案中，可用作三重态发光体的金属络合物有如下形式：
Figure PCTCN2018119622-appb-000014
其中M是一金属,选于过渡金属元素或镧系或锕系元素,特别优先的是Ir,Pt,Au；
Ar 1每次出现时可以是相同或不同,是一个环状基团,其中至少包含有一个施主原子，即有一孤对电子的原子，如氮或磷，通过它环状基团与金属配位连接；Ar 2每次出现时可以是相同或不同,是一个环状基团,其中至少包含有一个C原子,通过它环状基团与金属连接；Ar 1和Ar 2由共价键联接在一起,可各自携带一个或多个取代基团，它们也可再通过取代基团联接在一起；L’每次出现时可以是相同或不同,是一个双齿螯合的辅助配体,最好是单阴离子双齿螯合配体；q1可以是0,1,2或3,优先地是2或3；q2可以是0,1,2或3,优先地是1或0。
一些三重态发光体的材料极其应用的例子可在下述专利文件和文献中找到:WO 200070655,WO 200141512,WO 200202714,WO 200215645,EP 1191613,EP 1191612,EP 1191614,WO 2005033244,WO 2005019373,US 2005/0258742,WO 2009146770,WO 2010015307,WO 2010031485,WO 2010054731,WO 2010054728,WO 2010086089,WO 2010099852,WO 2010102709,US 20070087219 A1,US 20090061681 A1,US 20010053462 A1,Baldo,Thompson et al.Nature 403,(2000),750-753,US 20090061681 A1,US 20090061681 A1,Adachi et al.Appl.Phys.Lett.78(2001),1622-1624,J.Kido et al.Appl.Phys.Lett.65(1994),2124,Kido et al.Chem.Lett.657,1990,US 2007/0252517 A1,Johnson et al.,JACS 105,1983,1795,Wrighton,JACS 96,1974,998,Ma et al.,Synth.Metals 94,1998,245,US 6824895,US 7029766,US 6835469,US 6830828,US 20010053462 A1,WO 2007095118 A1,US 2012004407A1,WO 2012007088A1,WO2012007087A1,WO 2012007086A1,US 2008027220A1,WO 2011157339A1,CN 102282150A,WO 2009118087A1,WO 2013107487A1,WO 2013094620A1,WO  2013174471A1,WO 2014031977A1,WO 2014112450A1,WO 2014007565A1,WO 2014038456A1,WO 2014024131A1,WO 2014008982A1,WO2014023377A1。特此将上述列出的专利文件和文献中的全部内容并入本文作为参考。
在下面的表中列出一些合适的三重态发光体的例子:
Figure PCTCN2018119622-appb-000015
Figure PCTCN2018119622-appb-000016
3.荧光主体材料
荧光主体材料又称单重态主体材料，荧光主体材料的例子并不受特别的限制，任何有机化合物都可能被用作为主体,只要其单重态能量比发光体,特别是单重态发光体或荧光发光体更高。
作为荧光主体材料使用的有机化合物的例子可选自含有环芳香烃化合物，如苯、联苯、三苯基、苯并、萘、蒽、萉、菲、芴、芘、屈、苝、薁；芳香杂环化合物，如二苯并噻吩、二苯并呋喃、二苯并硒吩、呋喃、噻吩、苯并呋喃、苯并噻吩、苯并硒吩、咔唑、吲哚咔唑、吡啶吲哚、吡咯二吡啶、吡唑、咪唑、三氮唑、异恶唑、噻唑、恶二唑、恶三唑、二恶唑、噻二唑、吡啶、哒嗪、嘧啶、吡嗪、三嗪、恶嗪、恶噻嗪、恶二嗪、吲哚、苯并咪唑、吲唑、吲哚嗪、苯并恶唑、苯异恶唑、苯并噻唑、喹啉、异喹啉、噌啉、喹唑啉、喹喔啉、萘、酞、蝶啶、氧杂蒽、吖啶、吩嗪、吩噻嗪、吩恶嗪、苯并呋喃吡啶、呋喃二吡啶、苯并噻吩吡啶、噻吩二吡啶、苯并硒吩吡啶和硒吩二吡啶；包含有2至10环结构的基团，它们可以是相同或不同类型的环芳香烃基团或芳香杂环基团，并彼此直接或通过至少一个以下的基团连结在一起，如氧原子、氮原子、硫原子、硅原子、磷原子、硼原子、链结构单元和脂肪环基团。
在一个优先的实施方案中，荧光主体材料可选于包含至少一个以下基团的化合物：
Figure PCTCN2018119622-appb-000017
其中，R 1可相互独立地选于如下的基团：氢、氘、烷基、烷氧基、氨基、烯、炔、芳烷基、杂烷基、芳基和杂芳基；n是一个从0到20的整数；X 1-X 8选于CH或N；X 9和X 10选于CR 1R 2或NR 1。R 2含义同R 1。
在一些优先的实施例中，荧光主体选自蒽的衍生物，如CN102224614 B、CN 100471827 C、CN 1914293 B、WO2015033559A1、US2014246657A1、WO2016117848A1、WO2016117861A1、WO2016171429A2、CN102369256B、CN102428158B等专利文献中所公开的。
下面的表中列出一些蒽基荧光主体材料的例子：
Figure PCTCN2018119622-appb-000018
在一些更加优先的实施例中，蒽基荧光主体材料是氘代的，即主体材料分子中含有至少一个以上的氘原子，这样的例子在CN102369256B、CN102428158B、CN102639671B、US2015021586A1等专利文献中所公开，具体的例子有：
Figure PCTCN2018119622-appb-000019
4.磷光主体材料
磷光主体材料又称三重态主体材料，三重态主体材料的例子并不受特别的限制，任何金属络合物或有机化合物都可能被用作为主体,只要其三重态能级比发光体,特别是三重态发光体或磷光发光体更高，可用作三重态主体(Host)的金属络合物的例子包括(但不限于)如下的一般结构:
Figure PCTCN2018119622-appb-000020
M是一金属；(Y 3-Y 4)是一两齿配体,Y 3和Y 4独立地选自C,N,O,P,和S；L是一个辅助配体；m是一整数，其值从1到此金属的最大配位数；在一个优先的实施方案中，可用作三重态主体的金属络合物有如下形式：
Figure PCTCN2018119622-appb-000021
(O-N)是一两齿配体,其中金属与O和N原子配位.m是一整数，其值从1到此金属的最大配位数；
在某一个实施方案中,M可选于Ir和Pt.
可作为三重态主体的有机化合物的例子选自包含有环芳香烃基的化合物，例如苯、联苯、三苯基苯、苯并芴；包含有芳香杂环基的化合物，如二苯并噻吩、二苯并呋喃、二苯并硒吩、呋喃、噻吩、苯并呋喃、苯并噻吩、苯并硒吩、咔唑、二苯并咔唑，吲哚咔唑、吡啶吲哚、吡咯二吡啶、吡唑、咪唑、三唑类、恶唑、噻唑、恶二唑、恶三唑、二恶唑、噻二唑、吡啶、哒嗪、嘧啶、吡嗪、三嗪类、恶嗪、恶噻嗪、恶二嗪、吲哚、苯并咪唑、吲唑、恶唑、二苯并恶唑、苯异恶唑、苯并噻唑、喹啉、异喹啉、邻二氮杂萘、喹唑啉、喹喔啉、萘、酞、蝶啶、氧杂蒽、吖啶、吩嗪、吩噻嗪、吩恶嗪、苯并呋喃吡啶、呋喃并吡啶、苯并噻吩吡啶、噻吩吡啶、苯并硒吩吡啶和硒吩苯并二吡啶；包含有2至10环结构的基团，它们可以是相同或不同类型的环芳香烃基团或芳香杂环基团，并彼此直接或通过至少一个以下的基团连结在一起,如氧原子、氮原子、硫原子、硅原子、磷原子、硼原子、链结构单元和脂肪环基团。其中，每个Ar可以进一步被取代，取代基可选为氢、氘、氰基、卤素、烷基、烷氧基、氨基、烯、炔、芳烷基、杂烷基、芳基和杂芳基。
在一个优先的实施方案中,三重态主体材料可选于包含至少一个以下基团的化合物:
Figure PCTCN2018119622-appb-000022
R 2-R 7的含义同R 1，X 9选于CR 1R 2或NR 1，Y选自CR 1R 2或NR 1或O或S。R 1，n，X 1-X 8，Ar 1～Ar 3的含义同上所述。
在下面的表中列出合适的三重态主体材料的例子但不局限于:
Figure PCTCN2018119622-appb-000023
5.p-dopant
近年来有很多已经公布的有机半导体在其导电率调控方法上引入了分子掺杂的概念。此种有机半导体材料可由具有良好的供电子或良好的吸电子性质的化合物组成。对于掺杂空穴传输材料所用的P型掺杂剂，强电子受体例如四氰基对苯醌二甲烷(TCNQ)或2,3,5,6-四氟四氰基-1,4-苯醌二甲烷(F4TCNQ)已为人熟知。可参考文章M.Pfeiffer,A.Beyer,T.Fritz,K.Leo,App.Phys.Lett.,73(22),3202-3204(1998)及J.Blochwitz,M.Pfeiffer,T.Fritz,K.Leo,App.Phys.Lett.,73(6),729-731(1998)。
由于TCNQ以及F4TCNQ在具体应用中的缺陷(分子量太小，挥发性过强)，可以使用一系列氢醌衍生物作为P型掺杂剂，其结构包括但不限于如下结构(专利TW200629362A)：
Figure PCTCN2018119622-appb-000024
其中R 8～R 19独立的为F、Cl、CN、NO 2、CF 3、全氟烃基、SO 3R 20、芳基或杂芳基，其中芳基及杂芳基由至含有一个取代的F、Cl、CN、NO 2、CF 3、全氟烃基、SO 3R；
R 20在每一次出现时，相同或不同的是，H、D、具有1至20个C原子的直链烷基、烷氧基或硫代烷氧基基团，或者具有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基团或者是甲硅烷基基团，或具有1至20个C原子的取代的酮基基团，或具有2至20个C原子的烷氧基羰基基团，或具有7至20个C原子的芳氧基羰基基团，氰基基团(-CN)，氨基甲酰基基团(-C(＝O)NH 2)，卤甲酰基基团(-C(＝O)-X其中X代表卤素原子),甲酰基基团(-C(＝O)-H)，异氰基基团，异氰酸酯基团，硫氰酸酯基团或异硫氰酸酯基团，羟基基团，硝基基团，CF 3基团，Cl，Br，F，可交联的基团或者具有5至40个环原子的取代或未取代的芳族或杂芳族环系，或具有5至40个环原子的芳氧基或杂芳氧基基团，或这些体系的组合，其中一个或多个基团R 2可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系；
其中A、B、C、D独立的选自C(CN) 2、(CF 3)C(CN)、(NO 2)C(CN)、C(卤素) 2、C(CF 3) 2、NCN、O、S、NR 20和以下结构：
Figure PCTCN2018119622-appb-000025
还有另一类以轴烯为核心的化合物，其特征为具有如下结构
Figure PCTCN2018119622-appb-000026
其中n2选自1～4的自然数；每一个X 1、X 2、X 3独立的选自C(CN) 2、(CF 3)C(CN)、(NO 2)C(CN)、C(卤素) 2、C(CF 3) 2、NCN、O、S、NR1及以下结构：
Figure PCTCN2018119622-appb-000027
R 8～R 15含义同上，其中X 1～X 3独立的选自C(CN) 2、(CF 3)C(CN)、(NO 2)C(CN)、C(卤素) 2、C(CF 3) 2、NCN、O、S、NR 1，其中Y＝CN、NO 2、COR 1或者全是卤素取代的烷基；芳基是取代或未取代的芳烃或者联芳基；杂芳基是取代或未取代的芳族杂环化合物或者二杂芳基；
Figure PCTCN2018119622-appb-000028
本发明的一个目的是为蒸镀型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≤1100g/mol，优选≤1000g/mol，很优选≤950g/mol，更优选≤900kg/mol，最优选≤800g/mol。
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≥700g/mol，优选≥800g/mol，很优选≥900g/mol，更优选≥1000g/mol，最优选≥1100g/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。
本发明的另一个目的是为印刷OLED提供材料的解决方案。
本发明进一步涉及一种组合物或油墨，其特征在于，包含如上任一项所述的芳香胺化合物、高聚物或混合物，及至少一种有机溶剂。
按照本发明的一种组合物，所述的至少一种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、-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机溶剂可选自：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机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，包含如上任一项所述的有机化合物或组合物，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。
本发明还涉及所述的一种组合物作为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，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，丝网印刷及喷墨印刷。凹版印刷，喷墨印刷将在本发明的实施例中应用。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，的详细信息请参见Helmut Kipphan主编的《印刷媒体手册:技术和生产方法》(Handbook of Print Media:Technologies and Production Methods),ISBN 3-540-67326-1。
如上所述的制备方法，其特征在于，所述的形成的一功能层，其厚度在5nm-1000nm。
本发明还涉及如上任一项所述芳香胺化合物、高聚物、混合物或组合物在有机电子器件中的应用。
一种有机电子器件，其特征在于，其功能层中包含如上任一项所述的芳香胺化合物、高聚物、或混合物。
所述的有机电子器件可选于，但不限于，有机发光二极管(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，特别优选的是有机电致发光器件，如OLED，OLEEC，有机发光场效应管。
在某些特别优先的实施例中，所述的有机电子器件是一种电致发光器件，其中包含有空穴注入层或空穴传输层，所述的空穴注入层或穴传输层至少包含一种如上所述的芳香胺化合物、高聚物、或混合物。
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1000nm之间，较好的是在350到900nm之间，更好的是在400到800nm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所进行的一定的改变，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.化合物的合成
Figure PCTCN2018119622-appb-000029
Figure PCTCN2018119622-appb-000030
实施例1：化合物1的合成
Figure PCTCN2018119622-appb-000031
中间体1的合成：
将15.0g 1-氟-2-硝基苯溶于300ml DMF,在氮气气氛下加入4.0g NaH。80℃搅拌30分钟，冷却后，加入11.4g吲哚。120℃搅拌12h.冷却后减压蒸馏除去DMF，加入二氯甲烷萃取分液并水洗至中性。旋干有机相后重结晶得到中间体1.
中间体2的合成：
将20.0g中间体1溶于400ml亚磷酸三乙酯，150℃搅拌12h。减压蒸馏除去多余的亚磷酸三乙酯，柱层析得到中间体2.
化合物1的合成：
将10.0g中间体2，28.5g中间体3，560mg醋酸钯，10ml 10％浓度的三叔丁基膦，5.8g叔丁醇钠溶于300ml甲苯，在氮气气氛下回流12h，得到化合物1。
实施例2：化合物2的合成
Figure PCTCN2018119622-appb-000032
化合物2的合成：
将10.0g中间体2，28.5g中间体3，560mg醋酸钯，10ml 10％浓度的三叔丁基膦，5.8g叔丁醇钠溶于300ml甲苯，在氮气气氛下回流12h，得到HT-2。
实施例3：化合物3的合成
Figure PCTCN2018119622-appb-000033
Figure PCTCN2018119622-appb-000034
中间体6的合成：
将20.0g中间体5，11.4g二苯并噻吩-4-硼酸，2.8g Pd(PPh 3) 4溶于300mlTHF和30ml水的混合溶剂中，氮气保护下回流12h。旋蒸除去溶剂，二氯甲烷萃取，水洗分液，有机相旋干后柱层析得到中间体6.
中间体7的合成：
将20.2g中间体6，12.6g联硼酸频哪醇酯，1.5g Pd(dppf)Cl 2和4.5g醋酸钾溶于300ml1,4-二氧六环中，氮气气氛下回流12h。旋干溶剂，柱层析得到中间体7.
中间体8的合成：
将19.4g中间体7，11.3g 1-溴-4-碘苯，2.2g Pd(PPh 3) 4和4.0g碳酸钾置于300ml甲苯、50ml乙醇和30ml水的混合溶液中，氮气气氛下回流12h。旋干溶剂，二氯甲烷萃取，水洗分液，柱层析得到中间体8.
化合物3的合成：
将10.0g中间体2，29.5g中间体8，560mg醋酸钯，10ml 10％浓度的三叔丁基膦，5.8g叔丁醇钠溶于300ml甲苯，在氮气气氛下回流12h。旋干溶剂，二氯甲烷萃取分液，柱层析，得到化合物3。
实施例4：化合物4的合成
Figure PCTCN2018119622-appb-000035
中间体9的合成：
将13.0g 1-氟-2-硝基苯溶于300ml DMF,在氮气气氛下加入4.0g NaH。80℃搅拌30分钟，冷却后，加入11.6g 5-溴吲哚。120℃搅拌12h.冷却后减压蒸馏除去DMF，加入二氯甲烷萃取分液并水洗至中性。旋干有机相后重结晶得到中间体9。
中间体10的合成：
将26.0g中间体9溶于400ml亚磷酸三乙酯，150℃搅拌12h。减压蒸馏除去多余的亚磷 酸三乙酯，柱层析得到中间体10.
中间体11的合成：
将7.8g 1-氟苯溶于200ml DMF,在氮气气氛下加入3.0g NaH。80℃搅拌30分钟，冷却后，加入20.0g中间体10。120℃搅拌12h.冷却后减压蒸馏除去DMF，加入二氯甲烷萃取分液并水洗至中性。旋干有机相后重结晶得到中间体11.
化合物4的合成：
将10.0g中间体11，6.6g中间体8，360mg醋酸钯，6.5ml 10％浓度的三叔丁基膦，4.0g叔丁醇钠溶于150ml甲苯，在氮气气氛下回流12h。旋干溶剂，二氯甲烷萃取分液，柱层析，得到化合物4。
实施例5：化合物5的合成
Figure PCTCN2018119622-appb-000036
中间体13的合成：
将15.0g 1-氟-2-硝基苯溶于300ml DMF,在氮气气氛下加入4.0g NaH。80℃搅拌30分钟，冷却后，加入19.6g 5-溴吲哚。120℃搅拌12h.冷却后减压蒸馏除去DMF，加入二氯甲烷萃取分液并水洗至中性。旋干有机相后重结晶得到中间体13。
中间体14的合成：
将26.0g中间体13溶于400ml亚磷酸三乙酯，150℃搅拌12h。减压蒸馏除去多余的亚磷酸三乙酯，柱层析得到中间体14。
中间体15的合成：
将7.8g 1-氟苯溶于200ml DMF,在氮气气氛下加入3.0g NaH。80℃搅拌30分钟，冷却后，加入20.0g中间体14。120℃搅拌12h.冷却后减压蒸馏除去DMF，加入二氯甲烷萃取分液并水洗至中性。旋干有机相后重结晶得到中间体15。
化合物5的合成：
将10.0g中间体11，6.6g中间体15，360mg醋酸钯，6.5ml 10％浓度的三叔丁基膦，4.0g叔丁醇钠溶于150ml甲苯，在氮气气氛下回流12h。旋干溶剂，二氯甲烷萃取分液，柱层析，得到化合物5。
2.2.化合物能级结构
有机重复结构单元的能量结构可通过量子计算得到，比如利用TD-DFT(含时密度泛函理论)通过Gaussian03W(Gaussian Inc.)，具体的模拟方法可参见WO2011141110。首先用半经验方法“Ground State/Semi-empirical/Default Spin/AM1”(Charge 0/Spin Singlet)来优化分子几何结构，然后有机分子的能量结构由TD-DFT(含时密度泛函理论)方法算得“TD-SCF/DFT/Default Spin/B3PW91”与基组“6-31G(d)”(Charge 0/Spin Singlet)。HOMO和LUMO能级按照下面的校准公式计算，S1和T1直接使用。
HOMO(eV)＝((HOMO(G)×27.212)-0.9899)/1.1206
LUMO(eV)＝((LUMO(G)×27.212)-2.0041)/1.385
其中HOMO(G)和LUMO(G)是Gaussian 09W的直接计算结果，单位为eV。结果如表1所示，其中ΔHOMO＝HOMO-(HOMO-1)：
表1
Figure PCTCN2018119622-appb-000037
3.OLED器件的制备及表征
在本实施例中，用化合物1、化合物4、化合物5、Ref-1、NPB作为空穴传输材料，DNTPD作为空穴注入材料，B3PYMPM作为电子传输材料，构造成器件结构为ITO/HATCN/空穴传输材料/BH:BD(95:5)/B3PYMPM/LiF/Al的电致发光器件。下面通过具体实施例来详细说明采用上述的OLED器件的制备过程：
Figure PCTCN2018119622-appb-000038
a、ITO(铟锡氧化物)导电玻璃基片的清洗：使用各种溶剂(例如氯仿、丙酮或异丙醇中的一种或几种)清洗，然后进行紫外臭氧处理；
b、DNTPD(60nm)、空穴传输材料(20nm)、BH:BD(95:5；20nm)、B3PYMPM(30nm)，LiF(1nm)、Al(100nm)在高真空(1×10 -6毫巴)中热蒸镀而成；
c、封装:器件在氮气手套箱中用紫外线硬化树脂封装。
各OLED器件的电流电压及发光(IVL)特性通过表征设备来表征，具体如表2所述。
表2
Figure PCTCN2018119622-appb-000039
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 (12)

  1. 一种如通式(I)所示的芳香胺化合物：
    Figure PCTCN2018119622-appb-100001
    其中：
    R 0、R 1、R 2每次出现时，相同或不同地选自H、或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(-CN)，氨基甲酰基(-C(＝O)NH 2)，卤甲酰基(-C(＝O)-X其中X代表卤素原子),甲酰基(-C(＝O)-H)，异氰基，异氰酸酯，硫氰酸酯或异硫氰酸酯，羟基，硝基，CF 3，Cl，Br，F，可交联的基团，或者具有5至40个环原子的取代或未取代的芳族或杂芳族环系，或具有5至40个环原子的芳氧基或杂芳氧基基团，或这些体系的组合，其中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系；
    L 1-L 3为连接基团，选自单键、芳香基团或杂芳香基团；
    Ar 1-Ar 6每次出现时，独立选自具有5至40个环原子的芳族或杂芳族环系，或具有5至40个环原子的芳氧基或杂芳氧基基团，或这些体系的组合，其中Ar 1与Ar 2之间、Ar 3与Ar 4之间及Ar 5与Ar 6之间以链接形成单环或多环的脂族或芳族环系，
    o、p、q互相独立地表示0至1的整数，并且o+p+q≥1；
    m、n互相独立地表示0至3的整数。
  2. 根据权利要求1所述的芳香胺化合物，其特征在于，所述化合物具有通式(II-1)-(II-8)所示的结构：
    Figure PCTCN2018119622-appb-100002
    Figure PCTCN2018119622-appb-100003
  3. 根据权利要求1-2中任一项所述的芳香胺化合物，其特征在于，所述Ar 1-Ar 6每次出现时，独立地选自以下结构：
    Figure PCTCN2018119622-appb-100004
    其中Z每次出现时，独立地选自N或CR 5，而且两个相邻的Z不能同时为N；当Z为与通式(I)中N相连时，Z为C；
    R 3、R 4、R 5含义同R 1；
    P表示具有3-10个环原子的饱和环烷烃或杂环烷烃；
    虚线表示所述基团与芳香胺的N原子连接的单键。
  4. 根据权利要求1-3任一项所述的芳香胺化合物，其特征在于，所述连接基团L 1-L 3包含如下结构式中的一种或多种组合：
    Figure PCTCN2018119622-appb-100005
    其中X每次出现时，独立地选自N或CR 6；Y每次出现时，独立地选自CR 7R 8，SiR 9R 10，NR 11或，C(＝O)，S，或O；R 6-R 11含义同R 1。
  5. 根据权利要求1-4任一项所述的芳香胺化合物，其特征在于，HOMO≥-5.5eV，HOMO表示芳香胺化合物的最高占有轨道能级。
  6. 一种聚合物，其特征在于，包含至少一个如通式(I)表示的重复结构单元。
  7. 一种混合物，其特征在于，包含至少一种如权利要求1-5中任一项所述的芳香胺化合物或如权利要求6所述的聚合物，及至少一种有机功能材料，所述有机功能材料可选自空穴注入材料、空穴传输材料、p-dopant、电子传输材料、电子注入材料、电子阻挡材料、空穴阻挡材料、发光材料、主体材料、和有机染料。
  8. 一种组合物，其特征在于，包含至少一种如权利要求1-5中任一项所述的芳香胺化合物或如权利要求6所述的聚合物或如权利要求7所述的混合物，及至少一种有机溶剂。
  9. 一种根据权利要求1-5任一项所述的芳香胺化合物或如权利要求6所述的聚合物或如权利要求7所述的混合物或如权利要求8所述的组合物在有机电子器件中的应用。
  10. 一种有机电子器件，其特征在于，至少包含一种如权利要求1至5任一项所述的芳香胺化合物或如权利要求6所述的聚合物或如权利要求7所述的混合物。
  11. 根据权利要求10所述的有机电子器件，其特征在于，所述有机电子器件为有机发光二极管、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。
  12. 根据权利要求10所述的有机电子器件是一种电致发光器件，其特征在于，包含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根据权利要求1至5中任一项所述的芳香胺化合物或权利要求6所述的聚合物或如权利要求7所述的混合物。
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