WO2021129337A1 - 一种有机化合物及有机电子器件 - Google Patents

一种有机化合物及有机电子器件 Download PDF

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WO2021129337A1
WO2021129337A1 PCT/CN2020/133469 CN2020133469W WO2021129337A1 WO 2021129337 A1 WO2021129337 A1 WO 2021129337A1 CN 2020133469 W CN2020133469 W CN 2020133469W WO 2021129337 A1 WO2021129337 A1 WO 2021129337A1
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groups
group
carbon atoms
substituted
organic compound
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PCT/CN2020/133469
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English (en)
French (fr)
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张晨
何锐锋
萧锡辉
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广州华睿光电材料有限公司
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Priority to CN202080061318.4A priority Critical patent/CN114341136B/zh
Publication of WO2021129337A1 publication Critical patent/WO2021129337A1/zh

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/06—Peri-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains three hetero rings
    • C07D487/16—Peri-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D498/06—Peri-condensed systems
    • 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

Definitions

  • the present invention relates to the field of electroluminescent materials, in particular to a compound based on a nitrogen-containing heterocyclic ring, an organic mixture and a composition containing the same, and its application in organic electronic devices.
  • Organic optoelectronic materials have diversity in synthesis, relatively low manufacturing costs, and excellent optical and electrical properties.
  • Organic light-emitting diodes have the advantages of wide viewing angle, fast response time, low working voltage, thin panel thickness, etc. in the application of optoelectronic devices (such as flat panel displays and lighting), and therefore have broad development potential.
  • Organic light-emitting diodes using fluorescent materials have the characteristics of high reliability, but their internal electroluminescence quantum The efficiency is limited to 25% because the ratio of the singlet excited state to the triplet excited state of the excitons generated by the current is 1:3.
  • organic light-emitting diodes using phosphorescent materials have achieved almost 100% internal electroluminescence quantum efficiency, and therefore, the development of phosphorescent light-emitting materials has been extensively studied.
  • a luminescent material can be used as a luminescent material together with a host material (host) to improve color purity, luminous efficiency, and stability.
  • host material host material
  • the host material/guest system is used as the light-emitting layer of the light-emitting device, the host material has a great influence on the efficiency and characteristics of the electroluminescent device, so the choice of the host material is very important.
  • CBP 4,4'-dicarbazole-biphenyl
  • BAlq bis(2-methyl)-8-quinolinol-4-phenyl aluminum (III)
  • BCP phenanthroline
  • the purpose of the present invention is to provide a type of N-containing fused ring organic compounds, polymers, mixtures, compositions and their applications, and aims to solve the problem of providing a new type of host material and improve the stability of the device. Sex and longevity.
  • Z is selected from a single bond, CR 1 R 2 , O, S or Ar 5 ;
  • Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 are each independently selected from substituted or unsubstituted aromatic groups with 6-30 ring atoms, or substituted or unsubstituted heterocyclic groups with 5-30 ring atoms Aromatic groups, or substituted or unsubstituted non-aromatic ring systems with 5-30 ring atoms;
  • R 1 and R 2 are independently selected from H, D, straight-chain alkyl groups having 1-20 carbon atoms, straight-chain alkoxy groups having 1-20 carbon atoms, and straight-chain alkoxy groups having 1-20 carbon atoms.
  • a polymer comprising at least one repeating unit, and the repeating unit includes a structure represented by the general formula (1).
  • a mixture comprising at least one of the above-mentioned compound and the above-mentioned polymer, and another organic functional material H2, and the other organic functional material H2 is selected from hole injection materials, hole transport materials, At least one of an electron transport material, an electron injection material, an electron blocking material, a hole blocking material, a luminous body, and a host material.
  • a composition comprising the above-mentioned compound, the above-mentioned high polymer, and at least one of the above-mentioned mixtures, and at least one organic solvent.
  • An organic electronic device comprising the above-mentioned compound, the above-mentioned high polymer, and at least one of the above-mentioned mixtures, or is prepared from the above-mentioned composition.
  • the present invention has the following beneficial effects:
  • the organic compound according to the present invention can be used as a host material.
  • a host material By condensing multiple six-membered or seven-membered rings at a designated position of a nitrogen-containing five-membered ring, the stability of molecules and the hole transport performance between molecules can be enhanced; at the same time, It can keep the molecule at an appropriate triplet energy level, prevent triplet excitons from flowing back from the guest to the host, improve device performance and extend device life.
  • the invention provides a solution for a light emitting device with low manufacturing cost, high efficiency, long life and low roll-off.
  • the electroluminescence efficiency and device lifetime can be further improved.
  • host material In the present invention, host material, host material and Host material have the same meaning and can be interchanged.
  • the singlet state and the singlet state have the same meaning and can be interchanged.
  • the triplet state and the triplet state have the same meaning and can be interchanged.
  • substituted means that the hydrogen atom in the substituted group is replaced by the substituent.
  • substituted or unsubstituted means that the defined group may be substituted or unsubstituted.
  • substituted it should be understood as being optionally substituted by a group acceptable in the art, including but not limited to: straight-chain alkyl having 1-20 carbon atoms, containing 3-20 carbon atoms Branched or cycloalkyl groups, heterocyclic groups with 3-20 ring atoms, aryl groups with 5-20 ring atoms, heteroaryl groups with 5-20 ring atoms, silyl groups, carbonyl groups, alkoxy groups Carbonyl, aryloxycarbonyl, carbamoyl, haloformyl, formyl, -NRR', cyano, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, trifluoro Methyl, nitro or halogen, and the above-mentioned groups can also be further substituted with substitu
  • the selected substituents include but are not limited to: straight-chain alkyl with 1-20 carbon atoms, with 3-20 A branched or cycloalkyl group with three carbon atoms, a heterocyclic group with 3-20 ring atoms, an aryl group with 5-10 ring atoms, a heteroaryl group with 5-10 ring atoms, -NRR', Cyano, hydroxy, trifluoromethyl, nitro or halogen;
  • R and R'in -NRR' are each independently substituted by groups acceptable in the art, including but not limited to H, having 1 A straight-chain alkyl group with 6 carbon atoms, a branched or cyclic alkyl group with 3-8 carbon atoms, a heterocyclic group with 3-8 ring atoms, an aryl group with 5-10 ring atoms or containing Heteroaryl groups with 5-10 ring atoms; among them, straight-chain alkyl groups with 1-6 carbon atoms, branched
  • the several groups may be the same or different from each other, for example: Several R 13 may be the same or different from each other.
  • 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-diarylfluorene, triarylamine, diaryl ether, etc., are also considered to be condensed aromatic ring systems for the purpose of this invention.
  • fused-ring aromatic groups include naphthalene, anthracene, fluoranthene, phenanthrene, triphenylene, perylene, naphthacene, pyrene, benzopyrene, acenaphthene, fluorene, and derivatives thereof.
  • fused heterocyclic aromatic groups are: benzofuran, benzothiophene, indole, carbazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrole, furofuran , Thienofuran, benzisoxazole, benzisothiazole, benzimidazole, quinoline, isoquinoline, o-naphthalene, quinoxaline, phenanthridine, primary pyridine, quinazoline, quinazolinone , And its derivatives.
  • aromatic group, aromatic, and aromatic ring system have the same meaning and can be interchanged.
  • heteroaromatic group heteroaromatic, and heteroaromatic ring system have the same meaning and can be interchanged.
  • adjacent groups means that these groups are bonded to the same carbon atom or bonded to adjacent carbon atoms. These definitions apply correspondingly to "adjacent substituents”.
  • the single bond connecting the substituent runs through the corresponding ring, which means that the substituent can be connected to an optional position of the ring, for example R is connected to any substitutable position of the benzene ring, such as Means Can be combined with An optional position on the six-membered ring forms a merged ring.
  • the energy level structure of the organic material plays a key role.
  • the following is an introduction to the determination of these energy levels.
  • HOMO and LUMO energy levels can be measured by photoelectric effects, such as XPS (X-ray Photoelectron Spectroscopy) and UPS (Ultraviolet Photoelectron Spectroscopy) or by cyclic voltammetry (hereinafter referred to as CV).
  • photoelectric effects such as XPS (X-ray Photoelectron Spectroscopy) and UPS (Ultraviolet Photoelectron Spectroscopy) or by cyclic voltammetry (hereinafter referred to as CV).
  • CV cyclic voltammetry
  • DFT density functional theory
  • the triplet energy level ET1 of organic materials can be measured by low-temperature time-resolved luminescence spectroscopy, or obtained by quantum simulation calculations (such as Time-dependent DFT), such as the commercial software Gaussian 09W ((Gaussian Inc.), specific simulation methods See WO2011141110 or as described in the examples below.
  • HOMO, LUMO, ET 1 depends on the measurement method or calculation method used, even for the same method, different evaluation methods, for example, the starting point and peak point on the CV curve can give different HOMO/ LUMO value. Therefore, reasonable and meaningful comparisons should be made with the same measurement method and the same evaluation method.
  • the values of HOMO, LUMO, and ET 1 are based on Time-dependent DFT simulation, but do not affect the application of other measurement or calculation methods.
  • the present invention relates to an organic compound, as shown in the general formula (1):
  • Z is selected from a single bond, CR 1 R 2 , O, S or Ar 5 ;
  • Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 are each independently selected from: substituted or unsubstituted aromatic groups with 6-30 ring atoms, or substituted or unsubstituted aromatic groups with 5-30 ring atoms Heteroaromatic groups, or substituted or unsubstituted non-aromatic ring systems with 5-30 ring atoms;
  • Z is selected from CR 1 R 2 , O or S; in another embodiment, Z is selected from Ar 5 .
  • Ar 1 , Ar 2 , Ar 3 , Ar 4 , and Ar 5 are each independently selected from: substituted or unsubstituted aromatic groups with 6-20 ring atoms, or substituted or unsubstituted ring atoms The number is 5-20 heteroaromatic group. In one embodiment, Ar 1 , Ar 2 , Ar 3 , and Ar 4 are all selected from substituted or unsubstituted aromatic groups or heteroaromatic groups with 6 ring atoms.
  • At least one of Ar 1 , Ar 2 , Ar 3 , and Ar 4 is selected from a fused ring aromatic group or a fused ring heteroaromatic group with 9-20 ring atoms.
  • Ar 2 or Ar 3 is selected from fused ring aromatic groups or fused ring heteroaromatic groups with 9-20 ring atoms.
  • Ar 1 , Ar 2 , Ar 3 , Ar 4 , and Ar 5 are each independently selected from any group (A-1)-(A-8):
  • X is selected from CR 3 or N; preferably, X is selected from CR 3 ; when X is the attachment site, X is selected from C;
  • (A-1)-(A-8) is selected from the following groups
  • the H atom on the ring may be further substituted by R 3.
  • Ar 1 , Ar 2 , Ar 3 , and Ar 4 are each independently selected from (A-1), (A-2), (A-3), or (A-4).
  • Ar 1 , Ar 2 , Ar 3 , and Ar 4 are all selected from (A-1); further, X is selected from CR 3 .
  • At least one of Ar 1 , Ar 2 , Ar 3 , and Ar 4 is selected from (A-2), (A-3) or (A-4); further, Ar 1 , Ar 2 , At least one of Ar 3 and Ar 4 is selected from (A-3)
  • Z is selected from single bond, CR 1 R 2 , O, S, (A-1)(A-2) or (A-3);
  • Z, Ar 2 or Ar 3 is selected from (A-3); further, (A-3) is selected from
  • the following substituents are preferably used: a straight-chain alkyl group having 1-6 carbon atoms, a branched group having 3-8 carbon atoms Chain or cyclic alkyl, 3-8 membered heterocyclic group, 5-10 membered aryl (preferably phenyl or naphthyl), 5-10 membered heteroaryl (preferably 5-6 membered heteroaryl), R 0 substituted 5-10 membered aryl group, or R 0 substituted 5-10 membered heteroaryl group; R 0 is selected from: straight chain alkyl with 1-6 carbon atoms, branched chain with 3-8 carbon atoms or Cyclic alkyl, phenyl or 6-membered heteroaryl.
  • the general formula (1) is selected from any structure of general formulas (2-1)-(2-8):
  • X, Y 1 , Y 2 , and Z have the same meaning as described above.
  • one of Y 1 and Y 2 is selected from a single bond.
  • Z in the general formulas (2-1)-(2-8) is selected from a single bond; further, X is selected from CR 3 ; furthermore, the general formulas (2-1)-(2- 8) Selected from the following general formulas:
  • the general formulas (2-1)-(2-8) are selected from the following general formulas:
  • Z is selected from CR 1 R 2 , O or S; further, Z is selected from C(CH 3 ) 2 , O or S.
  • Z is selected from Ar 5 .
  • Ar 5 is selected from (A-1), (A-2) or (A-3).
  • Z is selected from:
  • Ar 5 is selected from any of the following structures:
  • Z is selected from (A-1); further, Z is selected from benzene and its derivatives.
  • Z is selected from (A-2); further, Z is selected from naphthalene and derivatives thereof.
  • Z is selected from (A-3); further, Z is selected from carbazole, dibenzothiophene, dibenzofuran, fluorene and derivatives thereof.
  • general formula (1) is selected from any structure of general formulas (3-1)-(3-8):
  • X, Y 1 , Y 2 , and Z have the same meaning as described above.
  • one of Y 1 and Y 2 is selected from a single bond.
  • organic compound of the present invention is selected from the following general formulas:
  • Z in the general formula (4-1) or (4-2) is selected from CR 1 R 2 , O or S;
  • Y 1 in the general formula (4-3) or (4-4) is selected from O.
  • the organic compound according to the present invention contains at least any one of (B-1)-(B-3); preferably, at least one R 3 is selected from (B-1)-(B -3) Any structure:
  • X 1 is selected from CR 5 or N; preferably, at least one X 1 is selected from N;
  • L 1 is selected from a single bond, a substituted or unsubstituted aromatic group having 6-30 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5-30 ring atoms;
  • At least one R 3 in the general formulas (2-1)-(2-8) is selected from any structure (B-1)-(B-3).
  • At least one R 3 in the general formula (G1-1)-(G1-8) is selected from any structure (B-1)-(B-3).
  • At least one R 3 in the general formulas (G2-1)-(G2-8) is selected from any structure (B-1)-(B-3).
  • At least one R 3 in the general formulas (G3-1)-(G3-8) is selected from any structure (B-1)-(B-3).
  • R 3 in the general formulas (4-1)-(4-4) is selected from any structure (B-1)-(B-3).
  • At least one R 3 in the present invention is selected from any of the structures (B-1) to (B-3), and R 3 is derived from X and Y 1 .
  • the general formula (2-2)-(2-7), (3-4)-(3-6), (3-8), (G1-4)-(G1-7), In (G2-4)-(G2-7), (G3-4)-(G3-6), (G3-4), Y 2 is selected from a single bond; more preferably, Y 1 is selected from NR 3 ; further Ground, R 3 is selected from any structure (B-1)-(B-3).
  • (B-1)-(B-3) is selected from any structure (C-1)-(C-4):
  • L 1 in structural formula (B-1)-(B-3) or (C-1)-(C-4) is selected from a single bond.
  • L 1 in structural formula (B-1)-(B-3) or (C-1)-(C-4) is selected from substituted or unsubstituted aromatic groups with 6-20 ring atoms Groups, or substituted or unsubstituted heteroaromatic groups with 5-20 ring atoms; more preferably, L 1 is selected from substituted or unsubstituted aromatic groups with 6-15 ring atoms, or substituted or unsubstituted aromatic groups with 6-15 ring atoms Substituted heteroaromatic groups with 5-15 ring atoms.
  • L 1 is selected from the following groups:
  • X 1 and Y 3 have the same meaning as described above.
  • (B-1)-(B-3) is selected from any of the following structures:
  • each occurrence of R 5 is independently selected from H, linear alkyl having 1-6 carbon atoms, branched or cyclic alkyl having 3-8 carbon atoms, 6-10 Member aryl, 6-10 membered heteroaryl, phenyl substituted 6-10 membered aryl, or phenyl substituted 6-10 membered heteroaryl.
  • organic compounds according to the present invention are listed below, but not limited to them:
  • Organic functional materials include, but are not limited to, hole injection materials (HIM), hole transport materials (HTM), electron transport materials (ETM), electron injection materials (EIM), electron blocking materials (EBM), hole blocking materials (HBM), emitter (Emitter), host material (Host).
  • the organic compound according to the present invention is used as a host material, especially a phosphorescent host material.
  • a phosphorescent host material it must have an appropriate triplet energy level, namely E T1 .
  • the N-containing compound according to the invention has an E T1 ⁇ 2.2 eV; more preferably ⁇ 2.4 eV, most preferably ⁇ 2.6 eV.
  • the organic compound according to the present invention needs to have a more suitable resonance factor f(S1) to facilitate the transfer of excitons from the host to the guest and improve the luminous efficiency of the device.
  • f(S1) Preferably f(S1) ⁇ 0.01, more preferably f(S1) ⁇ 0.05, most preferably f(S1) ⁇ 0.08.
  • the organic compound according to the present invention needs to have a more suitable singlet-triplet energy level difference ⁇ E ST to facilitate the transfer of excitons from the host to the guest and improve the luminous efficiency of the device.
  • ⁇ E ST ⁇ 0.9 eV, more preferably ⁇ E ST ⁇ 0.6 eV, most preferably ⁇ E ST ⁇ 0.4 eV.
  • the compound ⁇ HOMO ((HOMO-(HOMO-1)) according to the present invention is preferably ⁇ 0.1 eV, more preferably ⁇ 0.25 eV, most preferably ⁇ 0.40 eV.
  • the compound ⁇ LUMO (((LUMO+1)-LUMO) according to the present invention is preferably ⁇ 0.10eV, more preferably ⁇ 0.20eV, most preferably ⁇ 0.30eV.
  • the organic compound according to the present invention has a light-emitting function, and its light-emitting wavelength is between 300 and 1000 nm, preferably between 350 and 900 nm, and more preferably between 400 and 800 nm.
  • the luminescence referred to here refers to photoluminescence or electroluminescence.
  • the present invention still further relates to a high polymer comprising at least one repeating unit containing the structural unit represented by the general formula (1).
  • the synthesis method of the polymer is selected from SUZUKI-, YAMAMOTO-, STILLE-, NIGESHI-, KUMADA-, HECK-, SONOGASHIRA-, HIYAMA-, FUKUYAMA-, HARTWIG-BUCHWALD- and ULLMAN.
  • the glass transition temperature (Tg) of the polymer according to the present invention is ⁇ 100°C, preferably ⁇ 120°C, more preferably ⁇ 140°C, even more preferably ⁇ 160°C, most preferably It is ⁇ 180°C.
  • the molecular weight distribution (PDI) of the polymer according to the present invention preferably ranges from 1 to 5; more preferably from 1 to 4; more preferably from 1 to 3, more preferably 1 ⁇ 2, most preferably 1 ⁇ 1.5.
  • the weight average molecular weight (Mw) of the polymer according to the present invention is preferably in the range of 10,000 to 1 million; more preferably 50,000 to 500,000; more preferably 100,000 to 40 10,000, more preferably 150,000 to 300,000, most preferably 200,000 to 250,000.
  • the present invention also relates to a mixture comprising an organic functional material H1, H1 is selected from the above-mentioned organic compounds or polymers, and at least another organic functional material H2.
  • the organic functional material H2 is selected from hole injection materials (HIM), hole transport materials (HTM), electron transport materials (ETM), electron injection materials (EIM), electron blocking materials (EBM), hole blocking materials (HBM), emitter (Emitter), host material (Host).
  • the light-emitting material is selected from singlet light emitters (fluorescent light emitters), triplet light emitters (phosphorescent light emitters), especially light-emitting organometallic complexes and organic thermally excited delayed fluorescent materials (TADF materials).
  • 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.
  • Organic functional materials can be small molecule and high polymer materials.
  • the organic mixture according to the present invention wherein at least one of H1 and H2 has a ⁇ LUMO ⁇ 0.1 eV, preferably ⁇ 0.2 eV, more preferably ⁇ 0.2 eV.
  • the ⁇ LUMO of H1 is ⁇ 0.1 eV, preferably ⁇ 0.2 eV, more preferably ⁇ 0.3 eV.
  • the organic mixture according to the present invention wherein at least one of H1 and H2 has ⁇ HOMO ⁇ 0.1 eV, preferably ⁇ 0.25 eV, more preferably ⁇ 0.4 eV.
  • the ⁇ HOMO of H2 is ⁇ 0.1 eV, preferably ⁇ 0.25 eV, more preferably ⁇ 0.4 eV.
  • the organic mixture wherein min((LUMO(H1)-HOMO(H2),LUMO(H2)-HOMO(H1)) ⁇ min(ET(H1),ET(H2 ))+0.1eV, where LUMO(H1), HOMO(H1) and ET(H1) are the lowest unoccupied orbit of H1, the highest occupied orbit, the energy level of the triplet state, LUMO(H2), HOMO(H2) and ET(H2) are the lowest unoccupied orbital, the highest occupied orbital, and the energy level of the triplet state of H2.
  • the organic mixture wherein 1) ⁇ E(S1-T1) of H1 ⁇ 0.60eV, preferably ⁇ 0.44eV, more preferably ⁇ 0.37eV, most preferably ⁇ 0.10 eV, and/or 2)
  • the LUMO of H2 is higher than the LUMO of H1, and the HOMO of H2 is lower than the HOMO of H1.
  • the molar ratio of H1 and H2 is from 2:8 to 8:2; the preferred molar ratio is from 3:7 to 7:3; the more preferred molar ratio is 4:6 to 6:4; the most preferred molar ratio is 5:5.
  • the difference between the molecular weights of H1 and H2 does not exceed 100 Dalton, preferably does not exceed 80 Dalton, more preferably does not exceed 60 Dalton, very preferably does not exceed 40 Dalton, and most preferably No more than 30Dalton.
  • the difference between the sublimation temperature of H1 and H2 is not more than 50K; the more preferred sublimation temperature difference is not more than 30K; the more preferred sublimation temperature difference is not more than 20K; The most preferable sublimation temperature difference does not exceed 10K.
  • at least one of H1 and H2 in the organic mixture according to the present invention has a glass transition temperature Tg ⁇ 100°C. In a preferred embodiment, at least one of H1 and H2 has a Tg ⁇ 120°C.
  • At least one has a Tg ⁇ 140°C, in a more preferred embodiment, at least one has a Tg ⁇ 160°C, and in a most preferred embodiment, at least one has a Tg ⁇ 180°C.
  • the mixture contains at least one N-containing organic compound or polymer according to the present invention and a luminescent material, and the luminescent material is selected from singlet luminophores, triplet State luminous body or TADF luminous body.
  • the mixture comprises at least one organic compound or polymer according to the present invention and a singlet luminophore, wherein the weight percentage of the singlet luminophore is ⁇ 10wt% , Preferably ⁇ 9wt%, more preferably ⁇ 8wt%, particularly preferably ⁇ 7wt%, most preferably ⁇ 5wt%.
  • the mixture contains at least one organic compound or polymer according to the present invention and a triplet luminophore, wherein the weight percentage of the triplet luminophore is ⁇ 25wt% , Preferably ⁇ 20wt%, more preferably ⁇ 15wt%.
  • the mixture contains at least one N-containing organic compound or polymer according to the present invention, a triplet luminophore and a host material.
  • the N-containing organic compound according to the present invention can be used as an auxiliary luminescent material, and its weight ratio to the triplet luminescent body is from 1:2 to 2:1.
  • the energy level of the exciplex of the mixture according to the invention is higher than that of the phosphorescent emitter.
  • the mixture contains at least one N-containing organic compound or polymer according to the present invention and one TADF material, wherein the weight percentage of the TADF host material is ⁇ 15wt%, preferably ⁇ 10wt%, more preferably ⁇ 5wt%.
  • the mixture contains an N-containing organic compound according to the present invention, and another host material.
  • the organic compound according to the present invention can be used as the second host, and its weight percentage can be 30% to 70%.
  • the mixture of another organic functional material H2 contains the structural formula shown in structural formula (7) or (8):
  • R 13 is selected from H, D, linear alkyl groups having 1-20 carbon atoms, linear alkoxy groups having 1-20 carbon atoms, linear thioalkoxy groups having 1-20 carbon atoms Groups, branched or cyclic alkyl groups with 3-20 carbon atoms, branched or cyclic alkoxy groups with 3-20 carbon atoms, branched chains or rings with 3-20 carbon atoms Shaped thioalkoxy groups, silyl groups with 3-20 carbon atoms, substituted keto groups with 1-20 carbon atoms, alkoxy groups with 2-20 carbon atoms Carbonyl group, aryloxycarbonyl group with 7-20 carbon atoms, cyano group (-CN), carbamoyl group, haloformyl group, formyl group, isocyano group , Isocyanate group, thiocyanate group, isothiocyanate group, hydroxyl group, nitro group, CF3 group, Cl, Br, F, crosslinkable group, with 5
  • Ar 6 and Ar 7 are each independently selected from substituted or unsubstituted aromatic groups having 6 to 30 ring atoms, substituted or unsubstituted heteroaromatic groups having 5 to 30 ring atoms, or substituted or unsubstituted ⁇ non-aromatic ring group with 5 to 30 ring atoms;
  • L 2 is selected from single bond, substituted or unsubstituted aryl group having 6 to 30 ring atoms, substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms, or substituted or unsubstituted 5 to 30 A non-aromatic ring group with three ring atoms;
  • Any two adjacent groups in Ar 6 , Ar 7 , and L 2 may be connected to each other to form a ring.
  • H2 is selected from the following general formulas:
  • the structural formula (8) can be selected from the structure shown in the formula (9):
  • # indicates the connection site.
  • H2 is selected from the following general formulas:
  • L 2 is m is 1, 2, 3, 4 or 5; furthermore, m is 2;
  • R 13 is selected from H, R 14 is H, a 5-10 membered aryl group, or a 5-10 membered heteroaryl group. Further, R 14 is H, phenyl or naphthyl, and further, R 13 is selected from H,
  • the organic functional material H2 is selected from the following structures, but is not limited thereto, wherein H in the structure can be further substituted arbitrarily.
  • An object of the present invention is to provide a material solution for vapor-deposited OLED.
  • the organic compound according to the present invention has a molecular weight ⁇ 1200 g/mol, preferably ⁇ 1100 g/mol, very preferably ⁇ 1000 g/mol, more preferably ⁇ 950 g/mol, and most preferably ⁇ 900 g/mol.
  • Another object of the present invention is to provide a material solution for printed OLEDs.
  • the organic compound according to the present invention has a molecular weight ⁇ 800 g/mol, preferably ⁇ 900 g/mol, very preferably ⁇ 1000 g/mol, more preferably ⁇ 1100 g/mol, and most preferably ⁇ 1200 g/mol.
  • the organic 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 organic compound or polymer or mixture as described above, and at least one organic solvent; the at least one organic solvent is selected from aromatic or heteroaromatic , Ester, aromatic ketone or aromatic ether, aliphatic ketone or aliphatic ether, alicyclic or olefin compound, or borate or phosphate compound, or a mixture of two or more solvents.
  • 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 organic compound or polymer or mixture according to the present invention, preferably 0.1 to 15 wt%, more preferably 0.2 to 5 wt%, most preferably It is 0.25 to 3 wt%.
  • 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.
  • the present invention also provides an application of the above-mentioned organic compound, polymer, mixture or composition in an organic electronic device.
  • the organic electronic device can be selected from, but not limited to, an organic light emitting diode (OLED), Organic photovoltaic cells (OPV), organic light-emitting cells (OLEEC), organic field effect tubes (OFET), organic light-emitting field effect tubes, organic lasers, organic spintronic devices, organic sensors and organic plasmon emitting diodes (Organic Plasmon) Emitting Diode) etc., OLED is particularly preferred.
  • OLED organic light emitting diode
  • OLED Organic photovoltaic cells
  • OLED organic light-emitting cells
  • OFET organic field effect tubes
  • organic lasers organic spintronic devices
  • organic sensors and organic plasmon emitting diodes Organic Plasmon
  • Organic Plasmon Organic Plasmon Emitting Diode
  • the present invention further relates to an organic electronic device comprising at least one organic compound, polymer or mixture as described above.
  • an organic electronic device includes at least one cathode, an anode, and a functional layer located between the cathode and the anode, wherein the functional layer contains at least one organic compound as described above.
  • the organic electronic device can be selected from, but not limited to, organic light emitting diodes (OLED), organic photovoltaic cells (OPV), organic light emitting cells (OLEEC), organic field effect transistors (OFET), organic light emitting field effect transistors, organic Lasers, organic spintronic devices, organic sensors and Organic Plasmon Emitting Diodes, etc., particularly preferably organic electroluminescent devices, such as OLED, OLEEC, and organic light emitting field effect transistors.
  • OLED organic light emitting diodes
  • OOV organic photovoltaic cells
  • OEEC organic light emitting cells
  • OFET organic field effect transistors
  • organic light emitting field effect transistors organic Lasers
  • organic spintronic devices organic sensors and Organic Plasmon Emitting Diodes, etc.
  • organic electroluminescent devices such as OLED, OLEEC, and organic light emitting field effect transistors.
  • the light-emitting layer of the electroluminescent device includes an organic compound or mixture or polymer as described above.
  • the light-emitting layer of the electroluminescent device includes an organic compound as described above, or an organic compound as described above and a phosphorescent light-emitting material, or an An organic compound as described above and a host material, or an organic compound as described above and a TADF material.
  • 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 the electron transport layer (ETL) or the 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.
  • cathode material of the device of the present invention 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 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.
  • Synthesis of 1-3 Add 1-1 (15.0g), 1-2 (13.5g), Pd(PPh 3 ) 4 (0.5g) and potassium carbonate (12.9g) into 200ml 1,4-dioxane/ In a mixed solvent of water (volume ratio 8:1), reflux for 12 hours under a nitrogen atmosphere. After cooling, most of the solvent was removed by distillation under reduced pressure, and the remaining material was extracted with dichloromethane and washed with water three times. The organic phase is collected, the solvent is removed by rotary evaporation, and the obtained crude product is column chromatography to obtain 1-3. MS(ASAP): 482.40.
  • the synthesis of material 2 refers to the synthesis of 1-3, except that 1-1 is replaced with 2-8, and 1-2 is replaced with 2-9. MS (ASAP): 575.69.
  • the synthesis of material 3 refers to the synthesis of 1-3, except that 1-1 is replaced with 3-6, and 1-2 is replaced with 3-7.
  • the synthesis of 4-3 refers to the synthesis of 1-3, except that 1-1 is replaced with 4-1, and 1-2 is replaced with 4-2.
  • the synthesis of 4-6 refers to the synthesis of 1-6, except that 1-4 is replaced with 4-4, and 1-5 is replaced with 4-5.
  • the synthesis of material 4 refers to the synthesis of material 1, except that 1-7 is replaced with 4-7.
  • the synthesis of 5-2 refers to the synthesis of 1-3, except that 1-1 is replaced with 5-1, and 1-2 is replaced with 3-7. MS (ASAP): 398.47.
  • the synthesis of 5-3 refers to the synthesis of 2-3, except that 2-1 is replaced with 5-2, and 2-2 is replaced with 3-1.
  • the synthesis of 6-4 refers to the synthesis of 1-3, except that 1-1 is replaced with 6-3, and 1-2 is replaced with 6-2. MS (ASAP): 724.25.
  • Synthesis of material 7 Dissolve 7-5 (10.0g) in dry THF (100ml), slowly add methylmagnesium bromide (1M, 28ml) dropwise at 0°C in a nitrogen atmosphere. After the addition, the mixture was continuously stirred and gradually returned to room temperature, and the stirring was continued for 3 hours. After the reaction, the reaction was quenched by adding water, extracted and washed with water for liquid separation. The organic phase was collected, and the solvent was removed by rotary evaporation of the organic phase. The resulting crude product was poured into 100 ml of acetic acid and stirred at 80°C for 6 hours.
  • the synthesis of 8-1 refers to the synthesis of 1-6, except that 1-4 is replaced with 8-1, and 1-5 is replaced with 8-2.
  • the synthesis of 8-4 refers to the synthesis of 1-7, except that 1-6 is replaced with 8-3.
  • the synthesis of 9-3 refers to the synthesis of 1-6, except that 1-4 is replaced with 9-1, and 1-5 is replaced with 9-2.
  • the synthesis of material 9 refers to the synthesis of 1-3, except that 1-1 is replaced with 9-7, and 1-2 is replaced with 9-8.
  • the synthesis of 10-1 refers to the synthesis of 1-6, except that 1-4 is replaced with 2-4, and 1-5 is replaced with 3-2.
  • the synthesis of 10-3 refers to the synthesis of 1-6, except that 1-4 is replaced with 10-2, and 1-5 is replaced with 10-1.
  • the synthesis of 11-3 refers to the synthesis of 1-6, except that 1-4 is replaced with 11-2, and 1-5 is replaced with 11-1.
  • the synthesis of 11-4 refers to the synthesis of 1-7, except that 1-6 is replaced with 11-3.
  • the synthesis of material 11 refers to the synthesis of material 1, the difference is that 1-7 is replaced with 11-4.
  • the synthesis of 12-3 refers to the synthesis of 1-6, except that 1-4 is replaced with 12-2, and 1-5 is replaced with 12-1.
  • the synthesis of material 12 refers to the synthesis of material 1, except that 1-7 is replaced with 12-4. MS (ASAP): 827.99.
  • the synthesis of 13-2 refers to the synthesis of 1-6, except that 1-4 is replaced with 13-1, and 1-5 is replaced with 11-1.
  • the energy levels of organic compound materials can be obtained through quantum calculations, such as Gaussian09W (Gaussian Inc.) using TD-DFT (Time-dependent Density Functional Theory), and the specific simulation method can be found in WO2011141110.
  • HOMO and LUMO energy levels are calculated according to the following calibration formula, S 1 , T 1 and resonance factor f(S 1 ) are used directly.
  • HOMO(eV) ((HOMO(G) ⁇ 27.212)-0.9899)/1.1206
  • HOMO(G) and LUMO(G) are the direct calculation results of Gaussian 09W, and the unit is Hartree.
  • the results are shown in Table 1:
  • the LUMO energy levels of materials 1 to 9, and 11 to 13 are in the range of -2.78 to -2.98 eV, which can be used for electronic host materials; material 1, material 3, material 4, and material 6
  • the HOMO energy level of material 7, material 9 to material 13 is in the range of -5.31 ⁇ -5.66eV, which can be used as a hole-type host material; the triplet energy level of material 1 to material 13 is higher than 2.20eV, indicating these
  • the materials can be used as red light main materials.
  • H2-1 and H2-2 are two materials that satisfy the H2 general formula of the present invention.
  • Material 2, material 3, material 5, material 6, material 8, material 11 to material 13 are blended with H2-1 respectively, or material 2, material 3, material 11 are blended with H2-2 respectively, all satisfy min(( LUMO(H1)-HOMO(H2),LUMO(H2)-HOMO(H1)) ⁇ min(ET(H1),ET(H2))+0.1eV This condition indicates that these materials are compatible with H2-1 or H2-
  • the mixture of 2 can form an exciplex as a co-host material.
  • the device structure is ITO/HATCN/HTM/host material (material 1): RD/ETM: Liq/Liq/Al.
  • the mass ratio of the host material to the RD is 95:5.
  • the specific preparation process is as follows:
  • 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 UV ozone plasma treatment
  • HATCN (30nm), HTM (50nm), host material: RD (40nm), ETM: Liq (30nm), Liq (1nm), Al (100nm) heat in high vacuum (1 ⁇ 10 -6 mbar) Vapor-deposited
  • Encapsulation The device is encapsulated with ultraviolet hardening resin in a nitrogen glove box.
  • the preparation of the OLED device refers to device example 1, the difference is that the host material is replaced with the compound shown in Table 2 or a blended mixture according to a mass ratio of 1:1.
  • Example 8 Material 8 2.3 126 Device Example 9 Material 9 2.2 125 Device Example 10 Material 10 2.4 133 Device Example 11 Material 11 2.6 137 Device Example 12 Material 12 2.5 132 Device Example 13 Material 13 2.2 136 Device Example 14 Comparative example 1 1 100 Device Example 15 H2-1 1.2 108 Device Example 16 H2-2 1.1 104 Device Example 17 Material 6: H2-1 3.5 148 Device Example 18 Material 11: H2-2 3.1 145
  • the current and voltage (J-V) characteristics of each OLED device are characterized by characterization equipment, and important parameters such as efficiency, lifetime and external quantum efficiency are recorded at the same time.
  • Table 2 compares the lifetime and external quantum efficiency of OLED devices.
  • the lifetime LT95 is the time when the brightness drops to 95% of the initial brightness @1000nits under a constant current.
  • the LT95 and the external quantum efficiency are calculated in comparison with the device embodiment 14 (corresponding to the comparative example 1), that is, the lifetime of the device embodiment 14 is 1, and the external quantum efficiency is 100.
  • the device life of device embodiment 3 to device embodiment 13 is significantly higher than that of other single-body embodiments (corresponding to device embodiment 1 and device embodiment 2), because the compounds used in these embodiments have a larger density. Ring system and better stability, better carrier transfer ability between molecules.
  • Example 17 of the device using the mixture of the present invention as the main body corresponding to a mixture of material 6:H2-1 at a mass ratio of 1:1
  • Example 18 (corresponding to a mixture of material 11:H2-2 at a mass ratio of 1:1) has relatively higher device lifetime and external quantum efficiency (both more than 25%), because the co-host has a relatively more balanced hole /Electron transport performance, and form an exciton complex with TADF effect in the energized state, which increases the exciton utilization efficiency. It can be seen that the luminous efficiency and lifetime of the OLED device prepared by using the organic mixture of the present invention are significantly improved.

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Abstract

一种电致发光领域中的含氮杂环化合物和包含其的有机混合物和组合物及其在有机电子器件中的应用。所述化合物可作为主体材料应用于电致发光器件中，特别是OLED器件中。所述化合物可通过与合适的客体特别是磷光客体或TADF发光体配合，能提高其作为电致发光器件的发光效率及寿命，还提供了一种制造成本低、效率高、寿命长、低滚降的发光器件的解决方案。

Description

一种有机化合物及有机电子器件
本申请要求于2019年12月23日提交中国专利局、申请号为201911333160.7发明名称为“一种有机化合物及有机电子器件”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
本发明涉及电致发光材料领域，尤其涉及一种基于含氮杂环的化合物，包含其的有机混合物、和组合物，及其在有机电子器件中的应用。
背景技术
有机光电材料在合成上具有多样性，制造成本相对较低以及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)的应用方面具有广视角、反应时间快、工作电压低、面板厚度薄等优势，因而具有广阔的发展潜力。
为了提高有机发光二极管的发光效率，各种基于荧光和磷光的发光材料体系已被开发出来，使用荧光材料的有机发光二极管具有可靠性高的特点，但其在电气激发下其内部电致发光量子效率被限制为25％，这是因为电流产生的激子的单重激发态和三重激发态的比例为1:3。与此相反，使用磷光材料的有机发光二极管已经取得了几乎100％的内部电致发光量子效率，因此磷光发光材料的开发已被广泛研究。
发光材料(客体)可与基质材料(主体)一起用作发光材料以改善颜色纯度、发光效率和稳定性。由于当使用主体材料/客体体系作为发光器件的发光层时，主体材料对电致发光器件的效率和特性影响很大，因此主体材料的选择很重要。
目前，4,4’-二咔唑-联苯(CBP)是已知的最广泛用做磷光物质的基质材料。近年来，日本先锋公司(Pioneer)等开发了一种高性能有机电致发光器件，其使用BAlq(二(2-甲基)-8-羟基喹啉合-4-苯基苯酚铝(III))、菲罗啉(BCP)等化合物作为基质。
在现有材料设计中，人们倾向于采用含有电子传输基团和空穴传输基团进行组合，设计成双极性传输的主体，有益于电荷传输的平衡。利用双极性传输的分子做主体，能够获得不错的器件性能。但所获得的器件性能和寿命仍有待提高。
因此，现有技术，特别是主体材料解决方案还有待于改进和发展。
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含N稠环有机化合物、高聚物、混合物、组合物及其应用，旨在解决提供一类新型的主体材料，提高器件的稳定性和寿命。
本发明的技术方案如下：
一种有机化合物，如通式(1)所示：
Figure PCTCN2020133469-appb-000001
其中：
Z选自单键、CR 1R 2、O、S或Ar 5；
Ar 1、Ar 2、Ar 3、Ar 4、Ar 5分别独立选自取代或未取代的环原子数为6-30的芳香基团，或取代或未取代的环原子数为5-30的杂芳香基团，或取代或未取代的环原子数为5-30的非芳香环系；
R 1，R 2分别独立地选自H、D、具有1-20个碳原子的直链烷基、具有1-20个碳原子的直链烷氧基、具有1-20个碳原子的直链硫代烷氧基基团、具有3-20个碳原子的支链或环状的烷基、具有3-20个碳原子的支链或环状的烷氧基、具有3-20个碳原子的支链或环状的硫代烷氧基基团、具有3-20个碳原子的甲硅烷基基团、具有1-20个碳原子的取代的酮基基团、具有2-20个碳原子的烷氧基羰基基团、具有7-20个碳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、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、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、具有5-40个环原子的取代或未取代的芳香基团或杂 芳香基团、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。
一种高聚物，包含至少一个重复单元，所述重复单元包含有通式(1)表示的结构。
一种混合物，包含上述的化合物和上述的聚合物中的至少一种，及另一种有机功能材料H2，所述的另一种有机功能材料H2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，发光体和主体材料中的至少一种。
一种组合物，包含上述的化合物，上述的高聚物，和上述的混合物中的至少一种，及至少一种有机溶剂。
一种有机电子器件，包含上述的化合物，上述的高聚物，和上述的混合物中的至少一种，或者由如上述的组合物制备而成。
与现有技术相比，本发明具有如下有益效果：
按照本发明涉及的有机化合物可作为主体材料，通过在含氮五元环的指定位置稠合多个六元环或者七元环，能够增强分子的稳定性和分子间空穴传输性能；同时，能够使分子保持合适的三线态能级，防止三线态激子从客体向主体倒流，提高器件性能、延长器件寿命。本发明提供了一种制造成本低、效率高、寿命长、低滚降的发光器件的解决方案。另外，与合适的客体材料搭配或另一具有空穴传输性质或具有双极性性质的主体搭配形成共主体，可获进一步提升的电致发光效率及器件寿命。
具体实施方式
为了便于理解本发明，下面将对本发明进行更全面的描述。但是，本发明可以以许多不同的形式来实现，并不限于本文所描述的实施例。相反地，提供这些实施例的目的是使对本发明的公开内容的理解更加透彻全面。
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本发明。本文所使用的术语“和/或”包括一个或多个相关的所列项目的任意的和所有的组合。本发明提供一种有机化合物及其在有机电致发光器件中的应用，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。
在本发明中，主体材料、基质材料和Host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，“取代”表示被取代基中的氢原子被取代基所取代。
本发明中，“取代或未取代”表示所定义的基团可以被取代，也可以不被取代。当所定义的基团被取代时，应理解为任选被本领域可接受的基团所取代，包括但不限于：具有1-20个碳原子的直链烷基、含有3-20个碳原子的支链或环烷基、具有3-20个环原子的杂环基、具有5-20个环原子的芳基、具有5-20个环原子的杂芳基、硅烷基、羰基、烷氧基羰基、芳氧基羰基、氨基甲酰基、卤甲酰基、甲酰基、-NRR′、氰基、异氰基、异氰酸酯基、硫氰酸酯基、异硫氰酸酯基、羟基、三氟甲基、硝基或卤素，且上述基团也可以进一步被本领域可接受取代基取代，所选取代基包括但不限于：具有1-20个碳原子的直链烷基、具有3-20个碳原子的支链或环烷基、具有3-20个环原子的杂环基、具有5-10个环原子的芳基、具有5-10个环原子的杂芳基、-NRR′、氰基、羟基、三氟甲基、硝基或卤素；可理解的，-NRR′中的R和R′各自独立地为本领域可接受的基团所取代，包括但不限于H、具有1-6个碳原子的直链烷基、具有3-8个碳原子的支链或环烷基、具有3-8个环原子的杂环基、含有5-10个环原子的芳基或含有5-10个环原子的杂芳基；其中，具有1-6个碳原子的直链烷基、具有3-8个碳原子的支链或环烷基、具有3-8个环原子的杂环基、具有5-10个环原子的芳基或具有5-10个环原子的杂芳基任选进一步被取代，包括但不限于以下取代基：具有1-6个碳原子的直链烷基、具有3-8个碳原子的支链或环烷基、具有5-10个环原子的芳基(优选为苯基或萘基)或具有5-10个环原子的杂芳基。
本发明中，当存在数个用相同符号表示的基团，数个基团彼此之间可以相同或不同，例如：
Figure PCTCN2020133469-appb-000002
中数个的R 13彼此可以相同或不同。
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。
具体地，稠环芳香基团的例子有：萘、蒽、荧蒽、菲、苯并菲、二萘嵌苯、并四苯、芘、苯并芘、苊、芴、及其衍生物。
具体地，稠杂环芳香基团的例子有：苯并呋喃、苯并噻吩、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、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。
在本发明中，芳香基团，芳族，芳香环系具有相同的含义，可以互换。
在本发明中，杂芳香基团，杂芳族，杂芳香环系具有相同的含义，可以互换。
在本发明中，“相邻基团”是指这些基团键合至同一碳原子或键合至相邻的碳原子上。这些定义相应的适用于“相邻取代基”。
本发明中，取代基相连的单键贯穿相应的环，表述该取代基可与环的任选位置连接，例如
Figure PCTCN2020133469-appb-000003
中R与苯环的任一可取代位点相连，如
Figure PCTCN2020133469-appb-000004
表示
Figure PCTCN2020133469-appb-000005
可与
Figure PCTCN2020133469-appb-000006
中六元环上任选位置形成并环。
在本发明实施例中，有机材料的能级结构，三线态能级ET1、最高占有轨道能级HOMO、最低未占有轨道能级LUMO起着关键的作用。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ET1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 09W((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、ET 1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、ET 1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。
本发明涉及一种有机化合物，如通式(1)所示：
Figure PCTCN2020133469-appb-000007
其中：
Z选自单键、CR 1R 2、O、S或Ar 5；
Ar 1、Ar 2、Ar 3、Ar 4、Ar 5分别独立选自：取代或未取代的环原子数为6-30的芳香基团，或取代或未取代的环原子数为5-30的杂芳香基团，或取代或未取代的环原子数为5-30的非芳香环系；
R 1，R 2分别独立地选自：H、D、具有1-20个碳原子的直链烷基、具有1-20个碳原子的直链烷氧基、具有1-20个碳原子的直链硫代烷氧基基团、具有3-20个碳原子的支链或环状的烷基、具有3-20个碳原子的支链或环状的烷氧基、具有3-20个碳原子的支链或环状的硫代烷氧基基团、具有3-20个碳原子的甲硅烷基基团、具有1-20个碳原子的取代的酮基基团、具有2-20个碳原子的烷氧基羰基基团、具有7-20个碳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、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、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、具有5-40个环原子的取代或未取代的芳香基团或杂芳香基团、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。
在一实施例中，Z选自CR 1R 2、O或S；在另一实施例中，Z选自Ar 5。
在一实施例中，Ar 1、Ar 2、Ar 3、Ar 4、Ar 5分别独立选自：取代或未取代的环原子数为6-20的芳香基团，或取代或未取代的环原子数为5-20的杂芳香基团。在一实施例中，Ar 1、Ar 2、Ar 3、Ar 4均选自环原子数为6的取代或未取代的芳香基团或杂芳香基团。
在一实施例中，Ar 1、Ar 2、Ar 3、Ar 4中至少有一个选自环原子数为9-20的稠环芳香基团或稠环杂芳香基团。优选地，Ar 2或Ar 3选自选自环原子数为9-20的稠环芳香基团或稠环杂芳香基团。
在一实施例中，Ar 1、Ar 2、Ar 3、Ar 4、Ar 5分别独立选自(A-1)-(A-8)任一基团：
Figure PCTCN2020133469-appb-000008
其中：
X选自CR 3或N；优选地，X选自CR 3；当X为连接位点时，X选自C；
Y 1、Y 2分别独立地选自单键、NR 3、CR 3R 4、SiR 3R 4、O、S、S(＝O) 2或S(＝O)，Y 1、Y 2不同时选自单键；
R 3-R 4分别独立地选自H、D、具有1-20个碳原子的直链烷基、具有1-20个碳原子的直链烷氧基、具有1-20个碳原子的直链硫代烷氧基基团、具有3-20个碳原子的支链或环状的烷基、具有3-20个碳原子的支链或环状的烷氧基、具有3-20个碳原子的支链或环状的硫代烷氧基基团、具有3-20个碳原子的甲硅烷基基团、具有1-20个碳原子的取代的酮基基团、具有2-20个碳原子的烷氧基羰基基团、具有7-20个碳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、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、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、具有5-40个环原子的取代或未取代的芳香基团或杂芳香基团、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。
进一步地，(A-1)-(A-8)选自以下基团
Figure PCTCN2020133469-appb-000009
Figure PCTCN2020133469-appb-000010
其中：环上的H原子可以进一步被R 3取代。
在一优选地实施例中，Ar 1、Ar 2、Ar 3、Ar 4各自独立选自(A-1)、(A-2)(A-3)或(A-4)。
在一实施例中，Ar 1、Ar 2、Ar 3、Ar 4均选自(A-1)；更进一步地，X选自CR 3。
在一实施例中，Ar 1、Ar 2、Ar 3、Ar 4中至少有一个选自(A-2)、(A-3)或(A-4)；进一步地，Ar 1、Ar 2、Ar 3、Ar 4中至少有一个选自(A-3)
在一实施例中，Z选自单键、CR 1R 2、O、S、(A-1)(A-2)或(A-3)；
进一步，Z、Ar 2或Ar 3选自(A-3)；进一步，(A-3)选自
Figure PCTCN2020133469-appb-000011
进一步地，各实施例中，当芳香基团和杂芳香基团被进一步取代时，优选采用以下取代基：具有1-6个碳原子的直链烷基、具有3-8个碳原子的支链或环状的烷基、3-8元杂环基、5-10元芳基(优选苯基或萘基)、5-10元杂芳基(优选5-6元杂芳基)、R 0取代5-10元芳基、或R 0取代5-10元杂芳基；R 0选自：具有1-6个碳原子的直链烷基、具有3-8个碳原子的支链或环状的烷基、苯基或6元杂芳基。
需要说明的是，当芳香基团和杂芳香基团被进一步取代时，进一步取代的基团数目无特别限定，且各取代基可以相同或不同。
在一实施例中，通式(1)选自通式(2-1)-(2-8)任一结构：
Figure PCTCN2020133469-appb-000012
其中：X、Y 1、Y 2、Z含义同上所述。优选地，Y 1、Y 2中有一个选自单键。
在一实施例中，通式(2-1)-(2-8)中Z选自单键；进一步地，X选自CR 3；更进一步地，通式(2-1)-(2-8)选自如下通式：
Figure PCTCN2020133469-appb-000013
在一实施例中，通式(2-1)-(2-8)选自如下通式：
Figure PCTCN2020133469-appb-000014
其中，Z选自CR 1R 2、O或S；更进一步地，Z选自C(CH 3) 2、O或S。
在一实施例中，上述的有机化合物，Z选自Ar 5。优选地，Ar 5选自(A-1)、(A-2)或(A-3)。
在一实施例中，Z选自：
Figure PCTCN2020133469-appb-000015
其中：*表示稠合位点。
更进一步地，Y 1、Y 2分别独立地选自单键、-NPh、-C(CH 3) 2、-Si(CH 3) 2、O、S、S(＝O) 2或S(＝O)；Y 1、Y 2不同时选自单键；在一实施例中，Y 1为O、Y 2为C(CH 3) 2；在一实施例中，Y 1为O或S，Y 2为单键；
在一实施例中，上述的有机化合物，Ar 5选自以下任一结构：
Figure PCTCN2020133469-appb-000016
。在一实施例中，Z选自(A-1)；进一步地，Z选自苯及其衍生物。
在一实施例中，Z选自(A-2)；进一步地，Z选自萘及其衍生物。
在一实施例中，Z选自(A-3)；进一步地，Z选自咔唑、二苯并噻吩、二苯并呋喃、芴及其衍生物。
进一步地，通式(1)选自通式(3-1)-(3-8)任一结构：
Figure PCTCN2020133469-appb-000017
其中：X、Y 1、Y 2、Z含义同上所述。优选地，Y 1、Y 2中有一个选自单键。
进一步地，通式(3-1)-(3-8)选自如下通式：
Figure PCTCN2020133469-appb-000018
在一实施例中，本发明所述的有机化合物选自如下通式：
Figure PCTCN2020133469-appb-000019
进一步，通式(4-1)或(4-2)中Z选自CR 1R 2、O或S；
进一步，通式(4-3)或(4-4)中Y 1选自O。
在一实施例中，按照本发明所述的有机化合物，至少包含(B-1)-(B-3)中任一结构；优选地，至少一个R 3选自(B-1)-(B-3)任一结构：
Figure PCTCN2020133469-appb-000020
其中：
X 1选自CR 5或N；优选地，至少一个X 1选自N；
Y 3独立地选自NR 5、CR 5R 6、SiR 5R 6、O、S、S(＝O) 2或S(＝O)；
L 1选自单键，取代或未取代的具有6-30个环原子的芳香基团，或取代或未取代的具有5-30个环原子的杂芳香基团；
R 5-R 6分别独立地选自H、D、具有1-20个碳原子的直链烷基、具有1-20个碳原子的直链烷氧基、具有1-20个碳原子的直链硫代烷氧基基团、具有3-20个碳原子的支链或环状的烷基、具有3-20个碳原子的支链或环状的烷氧基、具有3-20个碳原子的支链或环状的硫代烷氧基基团、具有3-20个碳原子的 甲硅烷基基团、具有1-20个碳原子的取代的酮基基团、具有2-20个碳原子的烷氧基羰基基团、具有7-20个碳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、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、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、具有5-40个环原子的取代或未取代的芳香基团或杂芳香基团、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 5-R 6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；#表示连接位点。
进一步地，通式(2-1)-(2-8)中至少一个R 3选自(B-1)-(B-3)任一结构。
进一步地，通式(G1-1)-(G1-8)中至少一个R 3选自(B-1)-(B-3)任一结构。
进一步地，通式(G2-1)-(G2-8)中至少一个R 3选自(B-1)-(B-3)任一结构。
进一步地，通式(G3-1)-(G3-8)中至少一个R 3选自(B-1)-(B-3)任一结构。
进一步地，通式(4-1)-(4-4)中R 3选自(B-1)-(B-3)任一结构。
需要说明的时，本发明所述的至少一个R 3选自(B-1)-(B-3)任一结构中R 3来自X及Y 1。
在一实施例中，通式(2-2)-(2-7)，(3-4)-(3-6)，(3-8)，(G1-4)-(G1-7)，(G2-4)-(G2-7)，(G3-4)-(G3-6)，(G3-4)中，Y 2选自单键；更优选地，Y 1选自NR 3；进一步地，R 3选自(B-1)-(B-3)任一结构。
在一实施例中，(B-1)-(B-3)选自(C-1)-(C-4)任一结构：
Figure PCTCN2020133469-appb-000021
在一实施例中，结构式(B-1)-(B-3)或(C-1)-(C-4)中L 1选自单键。
在一实施例中，结构式(B-1)-(B-3)或(C-1)-(C-4)中L 1选自取代或未取代的具有6-20个环原子的芳香基团，或取代或未取代的具有5-20个环原子的杂芳香基团；更优选地，L 1选自取代或未取代的具有6-15个环原子的芳香基团，或取代或未取代的具有5-15个环原子的杂芳香基团。
在一个实施例中，L 1选自如下基团：
Figure PCTCN2020133469-appb-000022
其中：X 1，Y 3含义同上所述。
在一实施例中，(B-1)-(B-3)选自如下任一结构：
Figure PCTCN2020133469-appb-000023
在一实施例中，R 5每次出现独立地选自H、具有1-6个碳原子的直链烷基、具有3-8个碳原子的支链或环状的烷基、6-10元芳基、6-10元杂芳基、苯基取代6-10元芳基、或苯基取代6-10元杂芳基。
以下列出按照本发明所述的有机化合物，但不限于此：
Figure PCTCN2020133469-appb-000024
Figure PCTCN2020133469-appb-000025
Figure PCTCN2020133469-appb-000026
Figure PCTCN2020133469-appb-000027
Figure PCTCN2020133469-appb-000028
其中：以上结构的H原子可以进一步被取代。
按照发明所述的有机化合物，可以作为功能材料用于电子器件中。有机功能材料包括，但不限于，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),发光体(Emitter),主体材料(Host)。
在一个特别优选的实施例中，按照本发明所述的有机化合物是作为主体材料，特别是磷光主体材料。作为磷光主体材料必须有适当的三线态能级，即E T1。在某些实施例中，按照发明的含N化合物，其E T1≥2.2eV；更好是≥2.4eV,最好是≥2.6eV。
在一个优先的实施方案中,按照本发明所述的有机化合物需要有较为合适的谐振因子f(S1)，便于激子从主体向客体的转移，提高器件的发光效率。较好是f(S1)≥0.01，更好是f(S1)≥0.05，最好是f(S1)≥0.08。
在另一个优先的实施方案中,按照本发明所述的有机化合物需要有较为合适的单线态-三线态能级差ΔE ST，便于激子从主体向客体的转移，提高器件的发光效率。较好是ΔE ST≤0.9eV,更好是ΔE ST≤0.6eV，最好是ΔE ST≤0.4eV。
按照本发明所述的有机化合物作为主体材料时，需要合适的ΔHOMO和ΔLUMO。
在某些优先的实施例中，按照本发明所述的化合物ΔHOMO即((HOMO-(HOMO-1))优选≥0.1eV，更好是≥0.25eV,最好是≥0.40eV。
在某些优先的实施例中，按照本发明所述的化合物ΔLUMO即(((LUMO+1)-LUMO)优选≥0.10eV，更好是≥0.20eV,最好是≥0.30eV。
在某些实施例中，按照本发明所述的有机化合物具有发光功能，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。本发明还进一步涉及一种高聚物，包含至少一个含有通式(1)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。
本发明还涉及一种混合物，包括一种有机功能材料H1，H1选自如上所述的有机化合物或高聚物，以及至少还包含另一种有机功能材料H2。所述的有机功能材料H2选自空穴注入材料(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),发光体(Emitter),主体材料(Host)。发光材料选自单重态发光体(荧光发光体)、三重态发光体(磷光发光体)，特别是发光有机金属络合物和有机热激发延迟荧光材料(TADF材料)。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。有机功能材料可以是小分子和高聚物材料。
在某些优先的实施例中，按照本发明的有机混合物，其中H1和H2中至少有一个其ΔLUMO≥0.1eV，较好是≥0.2eV，更好是≥0.2eV。
在一个较为优先的实施例中，按照本发明的有机混合物，其中H1的ΔLUMO≥0.1eV，较好是≥0.2eV，更好是≥0.3eV。
在某些优先的实施例中，按照本发明的有机混合物，其中H1和H2中至少有一个其ΔHOMO≥0.1eV，较好是≥0.25eV，更好是≥0.4eV。
在一个较为优先的实施例中，按照本发明的有机混合物，其中H2的ΔHOMO≥0.1eV，较好是≥0.25eV，更好是≥0.4eV，。
在某些优先的实施例中，所述的有机混合物，其中min((LUMO(H1)-HOMO(H2),LUMO(H2)-HOMO(H1))≤min(ET(H1),ET(H2))+0.1eV，其中LUMO(H1)，HOMO(H1)及ET(H1)分别是H1的最低未占有轨道，最高占有轨道，三线态的能级，LUMO(H2)，HOMO(H2)及ET(H2)分别是H2的最低未占有轨道，最高占有轨道，三线态的能级。较为优先的是min((LUMO(H1)-HOMO(H2),LUMO(H2)-HOMO(H1))≤min(ET(H1),ET(H2))；更为优先的是min((LUMO(H1)-HOMO(H2),LUMO(H2)-HOMO(H1))≤min(E T(H1),E T(H2))-0.1eV；
在某些更为优先的实施例中，所述的有机混合物，其中1)H1的ΔE(S1-T1)≤0.60eV，较好是≤0.44eV，更好是≤0.37eV，最好是≤0.10eV，和/或2)H2的LUMO高于H1的LUMO，且H2的HOMO低于H1的HOMO。
在一个优选的实施例中，所述的有机混合物，其中H1和H2的摩尔比为从2：8到8：2；优选的摩尔比为3:7到7:3；更加优选的摩尔比为4:6到6:4；最优选的摩尔比为5:5。
在一个优选的实施例中，所述的有机混合物，其中H1和H2的分子量的差不超过100Dalton，较好是不超过80Dalton，更好是不超过60Dalton，非常好是不超过40Dalton，最好是不超过30Dalton。
在另一个优选的实施例中，所述的有机混合物，其中H1和H2的升华温度的差不超过50K；较优选的升华温度的差不超过30K；更加优选的升华温度的差不超过20K；最优选的升华温度的差不超过10K。在一个优选的实施例中，按照本发明的有机混合物中的H1和H2，至少有一个其玻璃化温度Tg≥100℃，在一个优选的实施例中，至少有一个其Tg≥120℃，在一个较为优选的实施例中，至少有一个其Tg≥140℃，在一个更为优选的实施例中，至少有一个其Tg≥160℃，在一个最为优选的实施例中，至少有一个其Tg≥180℃。
在一个较优选的实施例中，所述的混合物，包含至少一种按照本发明的含N有机化合物或高聚物和一种发光材料，所述的发光材料选自单重态发光体，三重态发光体或TADF发光体。
在某些实施例中，所述的混合物，包含至少一种按照本发明的有机化合物或高聚物和一种单重态发光体，其中所述的单重态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％。
在一个特别优选的实施例中，所述的混合物，包含至少一种按照本发明的有机化合物或高聚物和一种三重态发光体，其中所述的三重态发光体重量百分比为≤25wt％，较好是≤20wt％，更好是≤15wt％。在另一个优选的实施例中，所述的混合物，包含至少一种按照本发明的含N有机化合物或高聚物、一种三重态发光体和一种主体材料。在这种实施例中，按照本发明的含N有机化合物可以作为辅助发光材料，其与三重态发光体重量比从1:2到2:1。在另一种优选的实施例中，按照本发明的混合物的激基络合物的能级高于所述的磷光发光体。
在另一个更优选的实施例中，所述的混合物，包含至少一种按照本发明的含N有机化合物或高聚物，和一种TADF材料，其中所述的TADF主体材料的重量百分比为≤15wt％，较好是≤10wt％，更好是≤5wt％。
在一个非常优选的实施例中，所述的混合物包含一种按照本发明的含N有机化合物，和另一种主体材料。这里按照本发明的有机化合物可以作为第二主体，其重量百分比可在30％～70％。
本发明中对单重态发光体，三重态发光体、TADF材料及主体材料的详细描述详见专利WO2018095390A1。
在某些优选的实施例中，所述的混合物另一种有机功能材料H2包含如结构式(7)或(8)所示的结构结构式：
Figure PCTCN2020133469-appb-000029
其中：
R 13选自H、D、具有1-20个碳原子的直链烷基、具有1-20个碳原子的直链烷氧基、具有1-20个碳原子的直链硫代烷氧基基团、具有3-20个碳原子的支链或环状的烷基、具有3-20个碳原子的支链或环状的烷氧基、具有3-20个碳原子的支链或环状的硫代烷氧基基团、具有3-20个碳原子的甲硅烷基基团、具有1-20个碳原子的取代的酮基基团、具有2-20个碳原子的烷氧基羰基基团、具有7-20个碳原子的芳氧基羰基基团、氰基基团(-CN)、氨基甲酰基基团、卤甲酰基基团、甲酰基基团、异氰基基团、异氰酸酯基团、硫氰酸酯基团、异硫氰酸酯基团、羟基基团、硝基基团、CF3基团、Cl、Br、F、可交联的基团、具有5-40个环原子的取代或未取代的芳香基团或杂芳香基团、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或结构式(8)；且至少有一个R 13具有结构式(8)所示结构；
Ar 6，Ar 7各自独立地选自取代或者未取代的具有6至30个环原子的芳香基团，取代或者未取代的具有5至30个环原子的杂芳香基团，或者取代或者未取代的具有5至30个环原子的非芳香族环基；
L 2选自单键，取代或者未取代的具有6至30个环原子的芳基，取代或者未取代的具有5至30个环原子的杂芳基，或者取代或者未取代的有5至30个环原子的非芳香族环基；
Ar 6，Ar 7，L 2中任意两个相邻基团可以相互连接成环。
进一步地，H2选自如下通式：
Figure PCTCN2020133469-appb-000030
在一实施例中，结构式(8)可选自式(9)所示的结构：
Figure PCTCN2020133469-appb-000031
其中：#表示连接位点。
在某些优选的实施例中，H2选自如下通式：
Figure PCTCN2020133469-appb-000032
在某些优选的实施例中，L 2为
Figure PCTCN2020133469-appb-000033
m为1、2、3、4或5；更进一步地，m为2；
在某些优选的实施例中，R 13选自H、
Figure PCTCN2020133469-appb-000034
R 14为H、5-10元芳基或5-10元杂芳基。更进一步地，R 14为H、苯基或萘基，进一步地，R 13选自H、
Figure PCTCN2020133469-appb-000035
优选的,有机功能材料H2选自以下的结构，但不限于此，其中结构中的H可以进一步被任意取代。
Figure PCTCN2020133469-appb-000036
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，按照本发明所述的有机化合物，其分子量≤1200g/mol，优选≤1100g/mol，很优选≤1000g/mol，更优选≤950g/mol，最优选≤900g/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，按照本发明所述的有机化合物，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，按照本发明所述的有机化合物，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有机化合物或高聚物或混合物，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％的按照本发明的有机化合物或高聚物或混合物，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，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。
本发明还提供一种如上所述的有机化合物、高聚物、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，优选将所述含N有机化合物或高聚物用于OLED器件的发光层。
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有机化合物、高聚物或混合物。一般地，此种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有机化合物。所述的有机电子器件可选于，但不限于，有机发光二极管(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。
在某些优先的实施例中，所述的电致发光器件，其发光层包含一种如上所述的有机化合物或混合物或高聚物。
在某些优先的实施例中，所述的电致发光器件，其发光层包含一种如上所述的有机化合物，或包含一种如上所述的有机化合物和一种磷光发光材料，或包含一种如上所述的有机化合物和一种主体材料，或包含一种如上所述的有机化合物和一种TADF材料。
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
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。
实施例1
Figure PCTCN2020133469-appb-000037
1-3的合成：将1-1(15.0g)、1-2(13.5g)、Pd(PPh 3) 4(0.5g)和碳酸钾(12.9g)加入200ml1,4-二氧六环/水(体积比8:1)混合溶剂中，在氮气气氛下回流12h。冷却后，减压蒸馏除去大部分溶剂，剩余物质用二氯甲烷萃取并水洗三次。收集有机相，旋蒸除去溶剂，所得粗产品柱层析得到1-3。MS(ASAP)：482.40。
1-4的合成：将1-3(15.0g)、联硼酸频哪醇酯(7.9g)、Pd(dppf)Cl 2(0.5g)、醋酸钾(6.1g)加入1,4-二氧六环(120ml)中。氮气气氛下，回流8h。冷却后，减压蒸馏浓缩反应液，然后重结晶得到中间体1-4。MS(ASAP)：447.32。
1-6的合成将1-4(10.0g)、1-5(5.4g)、Pd(PPh 3) 4(0.2g)和碳酸钾(5.5g)加入150ml1,4-二氧六环/水(体积比8:1)混合溶剂中，在氮气气氛下回流12h。冷却后，减压蒸馏除去大部分溶剂，剩余物质用二氯甲烷萃取并水洗三次。收集有机相，旋蒸除去溶剂，所得粗产品经过柱层析纯化得到1-6。MS(ASAP)：608.13。
1-7的合成：将1-6(8.0g)和碳酸铯(8.6g)溶于150mlDMF中，140℃搅拌6h。冷却后，减压蒸馏浓缩反应液，剩余物用二氯甲烷萃取并水洗三次，收集有机相。有机相旋蒸除去溶剂后重结晶得到1-7。MS(ASAP)：588.13。
材料1的合成：将1-7(5.0g)溶于120mlDMAC中，加入Pd(OAc) 2(0.1g)、P(Cy 3).HBF 4(0.44g)和碳酸铯(5.5g)。在氮气气氛下145℃反应12h。冷却后，减压蒸馏除去大部分溶剂。将剩余反应液倒入大量水中，过滤得滤饼。滤饼重结晶得到材料1。MS(ASAP)：588.13。
实施例2
Figure PCTCN2020133469-appb-000038
2-3的合成：将2-1(8.0g)、2-2(10.2)和碳酸铯(31.5g)溶于100mlDMF中，120℃搅拌12h。冷却后，减压蒸馏浓缩反应液，然后水洗，二氯甲烷萃取。有机相旋蒸除去溶剂后重结晶得到2-3。MS(ASAP)：356.65。
2-5的合成参照1-6的合成，不同之处在于将1-4替换为2-4，并将1-5替换为2-3。MS(ASAP)：388.29。
2-6的合成：将2-5(10.0g)溶于120mlDMAC中，加入Pd(OAc) 2(0.5g)、三环己基膦四氟硼酸盐(1.9g)和碳酸铯(25.2g)。在氮气气氛下145℃反应20h。冷却后，减压蒸馏除去大部分溶剂。将剩余反应液用二氯甲烷萃取并水洗三次。收集有机相，有机相柱层析得到2-6。MS(ASAP)：315.38。
2-7的合成：将2-6(7.0g)溶于二氯甲烷中，在室温避光搅拌下将NBS(1.2g)溶于二氯甲烷中缓慢滴加。然后室温搅拌2h。反应结束后，反应液经水洗分液，有机相旋蒸除去溶剂，柱层析后得到2-7。MS(ASAP)：394.27。
2-8的合成参照1-4的合成，不同之处在于将1-3替换为2-7。MS(ASAP)：441.34。
材料2的合成参照1-3的合成，不同之处在于将1-1替换为2-8，并将1-2替换为2-9。MS(ASAP)：575.69。
实施例3
Figure PCTCN2020133469-appb-000039
3-2的合成参照2-3的合成，不同之处在于将2-2替换为3-1。MS(ASAP)：401.10。
3-3的合成将3-2(15.0g)、2-4(11.7g)、Pd(PPh 3) 4(0.3g)和碳酸钾(15.5g)加入200ml1,4-二氧六环/水(体积比8:1)混合溶剂中，在氮气气氛下回流12h。冷却后，减压蒸馏除去大部分溶剂，剩余物质用二氯甲烷萃取并水洗三次。收集有机相，旋蒸除去溶剂，所得粗产品柱层析纯化得到3-3。MS(ASAP)：464.39。
3-4的合成参照2-6的合成，不同之处在于将2-5替换为3-3。MS(ASAP)：391.47。
3-5的合成参照2-7的合成，不同之处在于将2-6替换为3-4。MS(ASAP)：470.37。
3-6的合成参照1-4的合成，不同之处在于将1-3替换为3-5。MS(ASAP)：517.44。
材料3的合成参照1-3的合成，不同之处在于将1-1替换为3-6，并将1-2替换为3-7。MS(ASAP)：622.73。
实施例4
Figure PCTCN2020133469-appb-000040
4-3的合成参照1-3的合成，不同之处在于将1-1替换为4-1，并将1-2替换为4-2。MS(ASAP)：466.34。
4-4的合成参照1-4的合成，不同之处在于将1-3替换为4-3。MS(ASAP)：513.40。
4-6的合成参照1-6的合成，不同之处在于将1-4替换为4-4，并将1-5替换为4-5。MS(ASAP)：642.13。
4-7的合成参照1-7的合成，不同之处在于将1-6替换为4-6。MS(ASAP)：622.12。
材料4的合成参照材料1的合成，不同之处在于将1-7替换为4-7。MS(ASAP)：585.67。
实施例5
Figure PCTCN2020133469-appb-000041
5-2的合成参照1-3的合成，不同之处在于将1-1替换为5-1，并将1-2替换为3-7。MS(ASAP)：398.47。
5-3的合成参照2-3的合成，不同之处在于将2-1替换为5-2，并将2-2替换为3-1。MS(ASAP)：632.06。
5-4的合成：将5-3(14.0g)、联硼酸频哪醇酯(11.3g)、Pd(dppf)Cl 2(0.5g)、醋酸钾(6.6g)加入1,4-二氧六环(180ml)中。在氮气气氛下回流8h。冷却后，旋蒸除去大部分溶剂，所得粗产品经重结晶得到中间体5-4。MS(ASAP)：726.49。
5-6的合成：将5-4(10.0g)、5-5(6.1g)、Pd(PPh 3) 4(0.5g)和碳酸钾(5.7g)加入200ml1,4-二氧六环/水(体积比8:1)混合溶剂中，在氮气气氛下回流6h。冷却后，减压蒸馏除去大部分溶剂，剩余物质用二氯甲烷萃取并水洗三次，收集有机相，旋蒸除去溶剂并重结晶得到5-6。MS(ASAP)：799.72。材料5的合成参照2-6的合成，不同之处在于将2-5替换为5-6。MS(ASAP)：726.80。
实施例6
Figure PCTCN2020133469-appb-000042
6-2的合成：将6-1(15.0g)、3-7(10.9g)溶于140ml干燥的DMSO中，加入DMAP(1.6g)、碳酸铯(26.7g)，140℃回流6h。冷却后，减压蒸馏除去大部分溶剂，浓缩后的反应液倒入大量水中并搅拌30min。抽滤，滤饼经重结晶纯化得到6-2。MS(ASAP)：598.52。
6-4的合成参照1-3的合成，不同之处在于将1-1替换为6-3，并将1-2替换为6-2。MS(ASAP)：724.25。
6-5的合成参照1-7的合成，不同之处在于将1-6替换为6-4。MS(ASAP)：704.25。
材料6的合成参照材料1的合成，不同之处在于将1-7替换为6-5。MS(ASAP)：667.79。
实施例7
Figure PCTCN2020133469-appb-000043
7-3的合成：将7-1(15.0g)、7-2(6.0g)溶于120ml邻二甲苯中，并加入铜粉(120mg)、CuCl(180mg)，1，10-菲啰啉(330mg)和碳酸铯(3.5g)。在氮气气氛下，150℃搅拌24h。冷却后过滤，减压蒸馏除去大部分溶剂，浓缩的反应液经过柱层析纯化得到7-3。MS(ASAP)：729.65。
7-4的合成参照1-6的合成，不同之处在于将1-4替换为2-3，并将1-5替换为7-3。MS(ASAP)：716.30
7-5的合成参照材料1的合成，不同之处在于将1-7替换为7-4。MS(ASAP)：724.84。
材料7的合成：将7-5(10.0g)溶于干燥的THF(100ml)中，在氮气气氛中于0℃缓慢滴加甲基溴化镁(1M,28ml)。滴加完后不断搅拌并逐渐恢复室温，并继续搅拌3h。反应完后，加水淬灭反应，萃取并水洗分液。收集有机相，有机相旋蒸除去溶剂，将所得粗产品倒入100ml醋酸中，80℃搅拌6小时。冷却后减压蒸馏除去大部分溶剂，将浓缩后的反应液倒入水中，加入碱溶液调整pH至中性，二氯甲烷萃取并水洗数次。收集有机相，有机相旋蒸除去溶剂后重结晶得到材料7。MS(ASAP)：706.87。
实施例8
Figure PCTCN2020133469-appb-000044
8-1的合成参照1-6的合成，不同之处在于将1-4替换为8-1，并将1-5替换为8-2。MS(ASAP)：665.17。
8-4的合成参照1-7的合成，不同之处在于将1-6替换为8-3。MS(ASAP)：646.15。
材料8的合成参照材料1的合成，不同之处在于将1-7替换为8-4。MS(ASAP)：609.69。
实施例9
Figure PCTCN2020133469-appb-000045
9-3的合成参照1-6的合成，不同之处在于将1-4替换为9-1，并将1-5替换为9-2。MS(ASAP)：504.02。
9-4的合成参照1-7的合成，不同之处在于将1-6替换为9-3。MS(ASAP)：484.01。
9-5的合成参照材料1的合成，不同之处在于将1-7替换为9-4。MS(ASAP)：447.56。
9-6的合成参照2-7的合成，不同之处在于将2-6替换为9-5。MS(ASAP)：526.45。
9-7的合成参照1-4的合成，不同之处在于将1-3替换为9-7。MS(ASAP)：573.52。
材料9的合成参照1-3的合成，不同之处在于将1-1替换为9-7，并将1-2替换为9-8。MS(ASAP)：691.81。
实施例10
Figure PCTCN2020133469-appb-000046
10-1的合成参照1-6的合成，不同之处在于将1-4替换为2-4，并将1-5替换为3-2。MS(ASAP)：419.73。
10-3的合成参照1-6的合成，不同之处在于将1-4替换为10-2，并将1-5替换为10-1。MS(ASAP)：596.55。
材料10的合成参照2-6的合成，不同之处在于将2-5替换为10-3。MS(ASAP)：523.64。
实施例11
Figure PCTCN2020133469-appb-000047
11-3的合成参照1-6的合成，不同之处在于将1-4替换为11-2，并将1-5替换为11-1。MS(ASAP)：769.28。
11-4的合成参照1-7的合成，不同之处在于将1-6替换为11-3。MS(ASAP)：749.27。
材料11的合成参照材料1的合成，不同之处在于将1-7替换为11-4。MS(ASAP)：712.81。
实施例12
Figure PCTCN2020133469-appb-000048
12-3的合成参照1-6的合成，不同之处在于将1-4替换为12-2，并将1-5替换为12-1。MS(ASAP)：884.46。
12-4的合成参照1-7的合成，不同之处在于将1-6替换为12-3。MS(ASAP)：864.45。
材料12的合成参照材料1的合成，不同之处在于将1-7替换为12-4。MS(ASAP)：827.99。
实施例13
Figure PCTCN2020133469-appb-000049
13-2的合成参照1-6的合成，不同之处在于将1-4替换为13-1，并将1-5替换为11-1。MS(ASAP)：819.34。
13-3的合成参照1-7的合成，不同之处在于将1-6替换为13-2。MS(ASAP)：799.33。
材料13的合成参照材料1的合成，不同之处在于将1-7替换为13-3。MS(ASAP)：762.87。
2、有机化合物能级计算
有机化合物材料的能级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Gaussian09W(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，S 1，T 1和谐振因子f(S 1)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Hartree。结果如表一所示：
Figure PCTCN2020133469-appb-000050
Figure PCTCN2020133469-appb-000051
Figure PCTCN2020133469-appb-000052
如表1所示，材料1至材料9、材料11至材料13的LUMO能级均在-2.78～-2.98eV范围内，可用于电子型主体材料；材料1、材料3、材料4、材料6、材料7、材料9至材料13的HOMO能级在-5.31～-5.66eV范围内，可用作空穴型主体材料；材料1至材料13的三线态能级均高于2.20eV，说明这些材料均可作为红光主体材料。H2-1、H2-2是满足本发明所述H2通式的两种材料。
材料2、材料3、材料5、材料6、材料8、材料11至材料13分别与H2-1共混,或者材料2、材料3、材料11分别与H2-2共混，均满足min((LUMO(H1)-HOMO(H2),LUMO(H2)-HOMO(H1))≤min(ET(H1),ET(H2))+0.1eV这一条件，表明这些材料与H2-1或H2-2的混合物可形成激基复合物，作为共主体材料。
3、器件制备及检测
器件实施例1
器件结构为ITO/HATCN/HTM/主体材料(材料1):RD/ETM:Liq/Liq/Al。其中主体材料与RD的质量比为95:5。具体的制备过程如下：
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、HATCN(30nm),HTM(50nm),主体材料:RD(40nm)，ETM:Liq(30nm)，Liq(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。
Figure PCTCN2020133469-appb-000053
OLED器件的制备参照器件实施例1，不同之处在于将主体材料换成表2所示化合物或者按照质量比为1:1共混的混合物。
表2：OLED器件性能比较
OLED器件 主体材料 LT95@1000nits 外量子效率(相对值)
器件实施例1 材料1 1.9 122
器件实施例2 材料2 2.1 115
器件实施例3 材料3 2.3 133
器件实施例4 材料4 2.6 135
器件实施例5 材料5 2.2 129
器件实施例6 材料6 2.5 142
器件实施例7 材料7 2.8 136
器件实施例8 材料8 2.3 126
器件实施例9 材料9 2.2 125
器件实施例10 材料10 2.4 133
器件实施例11 材料11 2.6 137
器件实施例12 材料12 2.5 132
器件实施例13 材料13 2.2 136
器件实施例14 对比例1 1 100
器件实施例15 H2-1 1.2 108
器件实施例16 H2-2 1.1 104
器件实施例17 材料6：H2-1 3.5 148
器件实施例18 材料11：H2-2 3.1 145
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。表2是OLED器件寿命及外量子效率比较，其中的寿命LT95是在恒定电流下,亮度下降到初始亮度@1000nits的95％时的时间。这里LT95、外量子效率是相对比器件实施例14(对应对比例1)而计算的，即以器件实施例14的寿命为1，外量子效率为100。
从表2可以看出，器件实施例1至器件实施例13的器件外量子效率和寿命明显高于器件实施例14(主体材料为对比例1)。这是由于本发明所示的材料同时具有给电子性质的七元环共轭体系和吸电子取代基，因而具有较为平衡的空穴、电子传输能力，而对比例材料缺乏吸电子取代基导致空穴、电子传输不平衡；同时，材料1至材料13的HOMO能级均低于对比例1(-5.14eV)，这是器件实施例1至器件实施例13器件效率和寿命高于对比例的另一个原因。其中，器件实施例3至器件实施例13的器件寿命明显高于其它单主体实施例(对应器件实施例1、器件实施例2)，这是因为这些实施例所使用的化合物具有更大的稠环体系和更好的稳定性，载流子在分子间的传输能力更好。
采用本发明所述混合物做共主体的器件实施例17(对应材料6：H2-1按质量比1:1的混合物)、器件
实施例18(对应材料11：H2-2按质量比1:1的混合物)具有相对更高的器件寿命和外量子效率(均超过25％)，这是因为共主体具有相对更加平衡的空穴/电子传输性能，并且在通电状态下形成了具有TADF效应的激基复合物，增加了激子利用效率。可见，采用本发明的有机混合物制备的OLED器件，其发光效率和寿命均得到明显提高。

Claims (19)

  1. 一种有机化合物，其特征在于：如通式(1)所示：
    Figure PCTCN2020133469-appb-100001
    其中：
    Z选自单键、CR 1R 2、O、S或Ar 5；
    Ar 1、Ar 2、Ar 3、Ar 4、Ar 5分别独立选自：取代或未取代的环原子数为6-30的芳香基团，或取代或未取代的环原子数为5-30的杂芳香基团，或取代或未取代的环原子数为5-30的非芳香环系；
    R 1、R 2分别独立地选自：H、D、具有1-20个碳原子的直链烷基、具有1-20个碳原子的直链烷氧基、具有1-20个碳原子的直链硫代烷氧基基团、具有3-20个碳原子的支链或环状的烷基、具有3-20个碳原子的支链或环状的烷氧基、具有3-20个碳原子的支链或环状的硫代烷氧基基团、具有3-20个碳原子的甲硅烷基基团、具有1-20个碳原子的取代的酮基基团、具有2-20个碳原子的烷氧基羰基基团、具有7-20个碳原子的芳氧基羰基基团、氰基基团、氨基甲酰基基团、卤甲酰基基团、甲酰基基团、异氰基基团、异氰酸酯基团、硫氰酸酯基团、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、具有5-40个环原子的取代或未取代的芳香基团或杂芳香基团、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。
  2. 根据权利要求1所述的有机化合物，其特征在于：Ar 1、Ar 2、Ar 3、Ar 4、Ar 5分别独立选自(A-1)-(A-8)任一基团：
    Figure PCTCN2020133469-appb-100002
    其中：
    X选自CR 3或N；
    Y 1、Y 2独立地选自：单键、NR 3、CR 3R 4、SiR 3R 4、O、S、S(＝O) 2或S(＝O)，Y 1、Y 2不同时选自单键；
    R 3、R 4分别独立地选自：H、D、具有1-20个碳原子的直链烷基、具有1-20个碳原子的直链烷氧基、具有1-20个碳原子的直链硫代烷氧基基团、具有3-20个碳原子的支链或环状的烷基、具有3-20个碳原子的支链或环状的烷氧基、具有3-20个碳原子的支链或环状的硫代烷氧基基团、具有3-20个碳原子的甲硅烷基基团、具有1-20个碳原子的取代的酮基基团、具有2-20个碳原子的烷氧基羰基基团、具有7-20个碳原子的芳氧基羰基基团、氰基基团、氨基甲酰基基团、卤甲酰基基团、甲酰基基团，、异氰基基团、异氰酸酯基团、硫氰酸酯基团、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、具有5-40个环原子的取代或未取代的芳香基团或杂芳香基团、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。
  3. 根据权利要求2所述的有机化合物，其特征在于：Ar 1、Ar 2、Ar 3、Ar 4均独立选自(A-1)-(A-4)任一基团。
  4. 根据权利要求3所述的有机化合物，其特征在于：通式(1)具有通式(2-1)-(2-8)任一结构：
    Figure PCTCN2020133469-appb-100003
  5. 根据权利要求2所述的有机化合物，其特征在于：Ar 5选自(A-1)、(A-2)或(A-3)。
  6. 根据权利要求5所述的有机化合物，其特征在于：通式(1)具有(3-1)-(3-8)任一结构：
    Figure PCTCN2020133469-appb-100004
  7. 根据权利要求2所述的有机化合物，其特征在于：Z、Ar 2和Ar 3中有一个选自
    Figure PCTCN2020133469-appb-100005
  8. 根据权利要求7所述的有机化合物，其特征在于：通式(1)具有(4-1)-(4-4)任一结构：
    Figure PCTCN2020133469-appb-100006
  9. 根据权利要求2-8任一项所述的有机化合物，其特征在于：所述化合物至少包含一个选自(B-1)-(B-3)的基团：
    Figure PCTCN2020133469-appb-100007
    其中：
    X 1选自CR 5或N；
    Y 3独立地选自NR 5、CR 5R 6、SiR 5R 6、O、S、S(＝O) 2或S(＝O)；
    L 1选自：单键，取代或未取代的具有6-30个环原子的芳香基团，或取代或未取代的具有5-30个环原子的杂芳香基团；
    R 5-R 6分别独立地选自：H、D、具有1-20个碳原子的直链烷基、具有1-20个碳原子的直链烷氧基、具有1-20个碳原子的直链硫代烷氧基基团、具有3-20个碳原子的支链或环状的烷基、具有3-20个碳原子的支链或环状的烷氧基、具有3-20个碳原子的支链或环状的硫代烷氧基基团、具有3-20个碳原子的甲硅烷基基团、具有1-20个碳原子的取代的酮基基团、具有2-20个碳原子的烷氧基羰基基团、具有7-20个碳原子的芳氧基羰基基团、氰基基团、氨基甲酰基基团、卤甲酰基基团、甲酰基基团、异氰基基团、异氰酸酯基团、硫氰酸酯基团、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、具有5-40个环原子的取代或未取代的芳香基团或杂芳香基团、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；
    #表示连接位点。
  10. 根据权利要求9所述的有机化合物，其特征在于：至少一个R 3选自(B-1)-(B-3)任一结构。
  11. 根据权利要求9所述的有机化合物，其特征在于：(B-1)-(B-3)选自(C-1)-(C-4)任一结构：
    Figure PCTCN2020133469-appb-100008
  12. 根据权利要求9所述的有机化合物，其特征在于：L 1选自：单键、6元芳基或6元杂芳基；和/或R 5选自：H、具有1-6个碳原子的直链烷基、具有3-8个碳原子的支链或环状的烷基、6-10元芳基、6-10元杂芳基、苯基取代6-10元芳基、或苯基取代6-10元杂芳基。
  13. 一种高聚物，其特征在于：包含至少一个重复单元，所述重复单元包含权利要求1-12任一项所述的有机化合物。
  14. 一种混合物，其特征在于：包括有机功能材料H1，所述H1选自权利要求1-12任一项所述的有机化合物和权利要求13所述的高聚物中的至少一种，及另一种有机功能材料H2，所述的另一种有机功能材料H2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、发光体和主体材料中的至少一种。
  15. 根据权利要求14所述的混合物，其特征在于：所述的另一种有机功能材料H2包含如结构式(7)或(8)所示的结构的化合物：
    Figure PCTCN2020133469-appb-100009
    其中：
    R 13选自H、D、具有1-20个碳原子的直链烷基、具有1-20个碳原子的直链烷氧基、具有1-20个碳原子的直链硫代烷氧基基团、具有3-20个碳原子的支链或环状的烷基、具有3-20个碳原子的支链或环状的烷氧基、具有3-20个碳原子的支链或环状的硫代烷氧基基团、具有3-20个碳原子的甲硅烷基基团、具有1-20个碳原子的取代的酮基基团、具有2-20个碳原子的烷氧基羰基基团、具有7-20个碳原子的芳氧基羰基基团、氰基基团、氨基甲酰基基团、卤甲酰基基团、甲酰基基团、异氰基基团、异氰酸酯基团、硫氰酸酯基团、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、具有5-40个环原子的取代或未取代的芳香基团或杂芳香基团、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或结构式(8)；且至少有一个R 13具有结构式(8)所示结构；
    Ar 6，Ar 7各自独立地选自取代或者未取代的具有6至30个环原子的芳香基团，取代或者未取代的具有5至30个环原子的杂芳香基团，或者取代或者未取代的具有5至30个环原子的非芳香族环基；
    L 2选自单键，或取代或者未取代的具有6至30个环原子的芳基，取代或者未取代的具有5至30个环原子的杂芳基，或者取代或者未取代的有5至30个环原子的非芳香族环基；
    Ar 6，Ar 7，L 2中任意两个相邻基团可相互连接成环。
  16. 根据权利要求15所述的混合物，其特征在于：L 2为
    Figure PCTCN2020133469-appb-100010
    m为1、2、3、4或5；
    R 13选自H、
    Figure PCTCN2020133469-appb-100011
    R 14为H、5-10元芳基或5-10元杂芳基。
  17. 根据权利要求15所述的混合物，其特征在于：min((LUMO(H1)-HOMO(H2),LUMO(H2)-HOMO(H1))≤min(ET(H1),ET(H2))+0.1eV，其中，LUMO(H1)指H1的最低未占有轨道，HOMO(H1)指H1最高占有轨道，ET(H1)指H1的三线态的能级，LUMO(H2)指H2的最低未占有轨道，HOMO(H2)指H2的最高占有轨道，ET(H2)指H2的三线态的能级。
  18. 一种组合物，其特征在于：包含如权利要求1-12任一项所述的有机化合物，如权利要求13所述的高聚物，和如权利要求14-17任一项所述的混合物中的至少一种，及至少一种有机溶剂。
  19. 一种有机电子器件，其特征在于：包含如权利要求1-12任一项所述的有机化合物，如权利要求13所述的高聚物，如权利要求14-17任一项所述的混合物中的至少一种，或者由如权利要求18所述的组合物制备而成。
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