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WO2019128849A1 - 有机化合物、高聚物、有机混合物、组合物及其在有机电子器件的应用 - Google Patents

有机化合物、高聚物、有机混合物、组合物及其在有机电子器件的应用 Download PDF

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WO2019128849A1
WO2019128849A1 PCT/CN2018/122488 CN2018122488W WO2019128849A1 WO 2019128849 A1 WO2019128849 A1 WO 2019128849A1 CN 2018122488 W CN2018122488 W CN 2018122488W WO 2019128849 A1 WO2019128849 A1 WO 2019128849A1
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organic
atoms
organic compound
compound
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French (fr)
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杨曦
潘君友
王璞
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Guangzhou Chinaray Optoelectronic Materials Ltd
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Guangzhou Chinaray Optoelectronic Materials Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/76—Dibenzothiophenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • 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
    • C07D471/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
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    • 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]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] 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 the field of organic electroluminescence technology, and in particular to an organic compound, a mixture and a composition thereof, and its use in the field of organic electroluminescence.
  • OLEDs Organic light-emitting diodes
  • OLEDs are regarded as the most promising next-generation display technology by the industry because of their light weight, active illumination, wide viewing angle, high contrast ratio, high luminous efficiency, low energy consumption, easy preparation of flexible and large-sized panels. .
  • OLEDs Organic light-emitting diodes
  • the host material is the key.
  • OLED light-emitting devices are generally prepared by using a single-host material in combination with an illuminant, but a single-host material causes a different carrier transport rate, causing device efficiency to be rolled off at high brightness, resulting in shortened device life.
  • the use of a double-body material can alleviate some of the problems caused by a single body, especially through a suitable material combination, the selected dual-body material can effectively form a composite exciplex, greatly improving the luminous efficiency and lifetime of the device.
  • One technique achieves low-roll-off, high-efficiency OLEDs by utilizing a co-host capable of forming a composite exciplex and a metal complex as a phosphorescent emitter.
  • the vapor deposition process can be greatly simplified, and the device life can be remarkably improved.
  • the organic electroluminescent element exhibits good efficiency and longevity, is easy to repeat in the manufacture and operation of the device, and the material synthesis is simple.
  • An embodiment of the invention provides an organic compound of the formula (I):
  • L 1 is selected from a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or these systems
  • a combination wherein one or more groups may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and/or with a ring to which the group is bonded.
  • S is 0 or 1.
  • A is a structure represented by the general formula (II), and B is a structure represented by the general formula (III):
  • X 1 is selected from the group consisting of O, S, CR 105 R 106 and SiR 108 R 109 .
  • X 2 is selected from the group consisting of NR 110 , CR 111 R 112 , and SiR 113 R 114 .
  • n is an integer from 0 to 5.
  • p is an integer from 0-8.
  • t is an integer from 0-8.
  • the present invention also provides a high polymer comprising a repeating unit comprising a structure as shown in the formula (1).
  • the present invention also provides an organic mixture comprising an organic compound as described above, and at least another organic functional material, the other organic functional material being selectable from a hole (also called a hole) injection or Transmission material, hole blocking material, electron injecting or transporting material, electron blocking material, organic matrix material, singlet illuminant (fluorescent illuminant), triplet illuminant (phosphorescent illuminant), thermally excited delayed fluorescent material (TADF) Materials) and organic dyes.
  • a hole also called a hole
  • hole also called a hole
  • hole also called a hole injection or Transmission material
  • hole blocking material electron injecting or transporting material
  • electron blocking material electron blocking material
  • organic matrix material organic matrix material
  • singlet illuminant fluorescent illuminant
  • triplet illuminant phosphorescent illuminant
  • thermally excited delayed fluorescent material (TADF) Materials thermally excited delayed fluorescent material
  • the organic mixture as described above contains at least one organic compound as described above as the first organic compound (H1) and one second organic compound (H2) having electron transporting properties.
  • the molar ratio of the first organic compound (H1) to the second organic compound (H2) ranges from 1:9 to 9:1.
  • the present invention also provides a composition comprising an organic compound or polymer as described above, or an organic mixture as described above, and at least one organic solvent.
  • the present invention also provides an organic electronic device comprising an organic compound or polymer as described above, or an organic mixture as described above.
  • the organic electronic device may be selected from an organic light emitting diode, an organic photovoltaic cell, an organic light emitting battery, an organic field effect transistor, an organic light emitting field effect transistor, an organic laser, an organic spintronic device, an organic sensor, and Organic plasmon emitting diode.
  • the organic electronic device as described above is an organic electroluminescent device comprising a light-emitting layer comprising an organic compound or polymer as described above, or an organic mixture as described above.
  • An organic compound according to the present invention has excellent hole transport properties and stability, and forms a co-host with another body having electron transport properties or bipolar properties, thereby obtaining improved electroluminescence efficiency and device. life.
  • FIG. 1 is a structural view of a light emitting device according to an embodiment of the present invention, in which 101 is a substrate, 102 is an anode, 103 is a hole injection layer (HIL) or a hole transport layer (HTL), and 104 is a light emitting layer, 105 It is an electron injection layer (EIL) or an electron transport layer (ETL), and 106 is a cathode.
  • HIL hole injection layer
  • HTL hole transport layer
  • ETL electron transport layer
  • ETL electron transport layer
  • the host material In the present invention, the host material, the matrix material, the Host material, and the Matrix material have the same meaning and are interchangeable.
  • metal organic complexes metal organic complexes, metal organic complexes, and organometallic complexes have the same meaning and are interchangeable.
  • composition printing ink, ink, and ink have the same meaning and are interchangeable.
  • the present invention provides an organic compound of the formula (I):
  • L 1 is selected from a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or these systems
  • a combination wherein one or more groups may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and/or with a ring to which the group is bonded.
  • L 1 is the same or different, a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 30 ring atoms, or an aryloxy group having 5 to 30 ring atoms or A heteroaryloxy group, or a combination of these systems, wherein one or more groups may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and/or with a ring to which the group is bonded.
  • L 1 is the same or different, a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 20 ring atoms, or an aryloxy group having 5 to 20 ring atoms or A heteroaryloxy group, or a combination of these systems, wherein one or more groups may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and/or with a ring to which the group is bonded.
  • L 1 is the same or different, and is a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 15 ring atoms, or an aryloxy group having 5 to 15 ring atoms or A heteroaryloxy group, or a combination of these systems, wherein one or more groups may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and/or with a ring to which the group is bonded.
  • L 1 is the same or different, a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 10 ring atoms, or an aryloxy group having 5 to 10 ring atoms or A heteroaryloxy group, or a combination of these systems, wherein one or more groups may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and/or with a ring to which the group is bonded.
  • L 1 is benzene, naphthalene, phenanthrene, triphenylene, diphenyl, terphenyl, or one or more carbon atoms of these structures are replaced by an N atom.
  • L 1 is diphenyl. In a preferred embodiment, L 1 is naphthalene. In a preferred embodiment, L 1 is benzene.
  • the aromatic ring system of the present invention is included in the ring system More carbon atoms, better Carbon atoms, heteroaromatic ring systems are included in the ring system More carbon atoms, better One carbon atom, and at least one hetero atom, provided that the total number of carbon atoms and heteroatoms is at least 4.
  • the heteroatoms are preferably selected from Si, N, P, O, S and/or Ge, particularly preferably from Si, N, P, O and/or S, more particularly preferably from N, O or S.
  • the above aromatic ring system or aromatic group means a hydrocarbon group containing at least one aromatic ring, and includes a monocyclic group and a polycyclic ring system.
  • the heteroaromatic ring or heteroaromatic group described above refers to a hydrocarbon group (containing a hetero atom) containing at least one heteroaromatic ring, and includes a monocyclic group and a polycyclic ring system.
  • 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 rings of the polycyclic ring is aromatic or heteroaromatic.
  • aromatic or heteroaromatic ring systems include not only aromatic or heteroaromatic systems, but also multiple aryl or heteroaryl groups may also be interrupted by short non-aromatic units ( ⁇ 10%).
  • Non-H atoms preferably less than 5% of non-H atoms, such as C, N or O atoms).
  • systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, etc., are also considered to be aromatic ring systems for the purposes of the present invention.
  • examples of the aromatic group are: benzene, naphthalene, anthracene, phenanthrene, perylene, tetracene, anthracene, benzopyrene, triphenylene, anthracene, anthracene, snail, and derivatives thereof.
  • heteroaromatic groups are: furan, benzofuran, dibenzofuran, thiophene, benzothiophene, dibenzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole , thiazole, tetrazole, anthracene, oxazole, pyrroloimidazole, pyrrolopyrrol, thienopyrrole, thienothiophene, furopyrrol, furanfuran, thienofuran, benzisoxazole, benzisothiazole , benzimidazole, pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, o-naphthyridine, quinoxaline, phenanthridine, pyridine, quinazoline, quinazolinone,
  • S is 0 or 1.
  • S is zero.
  • A is a structure represented by the general formula (II), and B is a structure represented by the general formula (III):
  • X 1 is selected from the group consisting of O, S, CR 105 R 106 , SiR 108 R 109 ; preferably, X 1 is selected from O or S.
  • X 2 is selected from NR 110 , CR 111 R 112 , SiR 113 R 114 ; preferably, X 2 is selected from NR 110 or CR 111 R 112 ; more preferably, X 2 is selected from NR 110 .
  • At least one set of adjacent R 104 of formula (III) can be bonded to the ring.
  • R 101 -R 114 are D, or a linear alkyl, alkoxy or thioalkoxy group having from 1 to 10 C atoms, or from 3 to 10 C atoms. a branched or cyclic alkyl, alkoxy or thioalkoxy group, or a substituted or unsubstituted silyl group, or a substituted ketone group having 1 to 10 C atoms, or 2 to 10
  • n is an integer of 0-8, preferably an integer of 0-6, more preferably an integer of 0-4, and most preferably an integer of 0-2.
  • n is an integer of 0-5, preferably an integer of 0-4, more preferably an integer of 0-2.
  • p is an integer of 0-8, preferably an integer of 0-6, more preferably an integer of 0-4, and most preferably an integer of 0-2.
  • t is an integer from 0-8. Preferably, it is an integer of 0-6, more preferably an integer of 0-4, and most preferably an integer of 0-2.
  • the organic compound according to the invention is selected from the group consisting of:
  • X1 is selected from the group consisting of O, S, and CR 105 R 106 . It is preferably O or S.
  • Ar 1 is selected from a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or these systems
  • a combination wherein one or more groups may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and/or with a ring to which the group is bonded.
  • Ar 1 is the same or different, a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 30 ring atoms, or an aromatic oxygen having 5 to 30 ring atoms. Or a heteroaryloxy group, or a combination of these systems, wherein one or more groups may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and/or with a ring to which the group is bonded .
  • Ar 1 is the same or different, a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 20 ring atoms, or an aromatic oxygen having 5 to 20 ring atoms. Or a heteroaryloxy group, or a combination of these systems, wherein one or more groups may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and/or with a ring to which the group is bonded .
  • Ar 1 is the same or different, a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 15 ring atoms, or an aromatic oxygen having 5 to 15 ring atoms. Or a heteroaryloxy group, or a combination of these systems, wherein one or more groups may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and/or with a ring to which the group is bonded .
  • Ar 1 is benzene, naphthalene, phenanthrene, triphenylene, diphenyl, terphenyl, or one or more carbon atoms of these structures are replaced by an N atom.
  • Ar 1 is diphenyl. In a preferred embodiment, Ar 1 is benzene. In other preferred embodiments, Ar 1 is dibenzofuran. In other preferred embodiments, Ar 1 is dibenzothiophene. In other preferred embodiments, Ar 1 is ⁇ . In other preferred embodiments, Ar 1 is a thread.
  • the L 1 or Ar 1 are each independently selected from one or more of the following structural groups:
  • a 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 respectively represent CR 501 or N;
  • R 501 -R 505 is H, or D, or a linear alkyl, alkoxy or thioalkoxy group having from 1 to 10 C atoms, or from 3 to 10 C atoms
  • a branched or cyclic alkyl, alkoxy or thioalkoxy group is either a silyl group, or a substituted keto group having from 1 to 10 C atoms, or from 2 to 10
  • the above L 1 or Ar 1 is selected from one or more combinations comprising structural groups wherein the H on the ring can be optionally substituted:
  • a described in the general formula (I) is selected from the structures shown below:
  • the broken line is a single bond in which the structure shown is connected to L 1 .
  • the B described in the formula (I) is selected from the structures shown below:
  • the broken line is a single bond in which the structure shown is connected to L 1 .
  • 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 present invention also relates to a method for synthesizing the organic compound, wherein the reaction is carried out using a raw material containing a reactive group.
  • active materials comprise at least one leaving group, for example, bromine, iodine, boric acid or a boronic ester.
  • Suitable reactions to form C-C linkages are well known to those skilled in the art and are described in the literature.
  • Particularly suitable and preferred coupling reactions are SUZUKI, STILLE and HECK coupling reactions.
  • the organic compound according to any one of the embodiments of the present invention has excellent hole transport properties and stability, and forms a co-host with another body having electron transport properties or bipolar properties, thereby obtaining improved electroluminescence. Efficiency and device lifetime.
  • 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 invention also provides an organic mixture comprising an organic compound or polymer as described above, and at least another organic functional material, the other organic functional material being selectable in a cavity (also called electricity) Hole) injection or transport material, hole blocking material, electron injecting or transporting material, electron blocking material, organic matrix material, singlet illuminant (fluorescent illuminant), triplet illuminant (phosphorescent illuminant), thermal excitation delay Fluorescent materials (TADF materials) and organic dyes.
  • Various 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 organic mixture comprises at least one organic compound or polymer and electron transport material (ETM) according to the invention.
  • ETM electron transport material
  • the organic mixture comprises at least one organic compound or polymer according to the invention and a luminescent material selected from the group consisting of singlet illuminants (fluorescent luminescence) Body), a triplet emitter (phosphorescent emitter) or a TADF emitter.
  • a luminescent material selected from the group consisting of singlet illuminants (fluorescent luminescence) Body), a triplet emitter (phosphorescent emitter) or a TADF emitter.
  • the organic mixture comprises at least one organic compound or polymer according to the present invention and a fluorescent illuminant, wherein the fluorescent illuminant has a weight percentage of ⁇ 10% by weight, preferably It is ⁇ 9 wt%, more preferably ⁇ 8 wt%, particularly preferably ⁇ 7 wt%, and most preferably ⁇ 5 wt%.
  • the organic mixture comprises at least one organic compound or polymer according to the invention and a phosphorescent emitter, wherein the phosphorescent emitter has a weight percentage of ⁇ 25 wt%, Preferably, it is ⁇ 20 wt%, more preferably ⁇ 15 wt%.
  • the organic mixture comprises at least one organic compound or polymer according to the invention, a phosphorescent emitter and a host material.
  • the organic compound according to the invention is co-hosted with said host material in a weight ratio of from 1:9 to 9:1; in a preferred embodiment, according to the invention
  • the organic compound forms an exciplex with the host material and has an energy level higher than that of the phosphorescent emitter.
  • the mixture comprises one less organic compound or polymer according to the invention, and a TADF material.
  • the function of the TADF material is preferably 1) forming a phosphorescent co-host material with the organic compound according to the invention, wherein the weight ratio is from 1:9 to 9:1; 2) the illuminant, wherein the weight percentage of the TADF material It is ⁇ 15 wt%, preferably ⁇ 10 wt%, more preferably ⁇ 8 wt%.
  • the organic mixture as described above comprises at least one organic compound as described above as the first organic compound (H1) and a second organic compound (H2), said at least The diorganic compound (H2) has an electron transporting property.
  • the at least second organic compound has electron transport properties and also has hole transport properties.
  • the molar ratio of the first organic compound (H1) to the second organic compound (H2) ranges from 1:9 to 9:1.
  • the molar ratio of the first organic compound (H1) to the second organic compound (H2) ranges from 3:7 to 7:3.
  • the molar ratio of the first organic compound (H1) to the second organic compound (H2) ranges from 4:6 to 6:4.
  • the molar ratio of the first organic compound (H1) to the second organic compound (H2) is 5:5.
  • the second organic compound (H2) comprises a fluorine group, or a cyano group or has any one of the following formulas:
  • a is an integer of 1-3;
  • X 1 -X 8 is selected from CR 801 or N, and at least one is N;
  • Z 1 -Z 3 is a single bond or C(R 801 ) 2 or O or S.
  • R 801 may be selected from the group consisting of hydrogen, hydrazine, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl.
  • the second organic compound (H2) has a structure represented by the formula (IV).
  • Z 4 , Z 5 , Z 6 are selected from N or CR 901 , and at least one of Z 4 , Z 5 , and Z 6 is an N atom.
  • Ar 13 to Ar 15 are the same or different, and are 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 non-aromatic group having 5 to 40 ring atoms, or a combination of these systems, wherein the one or more groups may be further substituted with R 902, or R 902 form a ring system may be further substituted with the group.
  • each of Ar 13 to Ar 15 may be independently selected from the above groups.
  • Ar 13 to Ar 15 are the same or different, and are substituted or unsubstituted, substituted or unsubstituted aromatic or heteroaromatic ring systems having 5 to 20 ring atoms, or Deuterated or undeuterated aryloxy or heteroaryloxy group having 5 to 20 ring atoms, or a combination of these systems, wherein one or more groups may be bonded to each other and/or to the group
  • the combined ring forms a monocyclic or polycyclic aliphatic or aromatic ring system.
  • Ar 13 to Ar 15 are the same or different, and are substituted or unsubstituted, substituted or unsubstituted aromatic or heteroaromatic ring systems having 5 to 15 ring atoms, or Is a deuterated or undeuterated aryloxy or heteroaryloxy group having 5 to 15 ring atoms, or a combination of these systems, wherein one or more groups may be and/or with the group
  • the bonded ring forms a monocyclic or polycyclic aliphatic or aromatic ring system.
  • b, u, v are independently 1 or 2 or 3, preferably 1.
  • Ar 13 -Ar 15 in the formula (IV), when multiple occurrences, may be the same or differently selected from one of the following structural groups or Their combination:
  • d is 1 or 2 or 3 or 4.
  • Suitable examples of the second organic compound (H2) are listed below, but are not limited to:
  • the organic mixture is used in a luminescent layer in an organic electroluminescent device. Due to stability or process considerations, there are sometimes some special requirements for H1 and H2.
  • the organic mixture according to the invention wherein at least one of H1 and H2, preferably H2, ((LUMO+1)-LUMO) ⁇ 0.1 eV, preferably ⁇ 0.15 eV, More preferably, it is ⁇ 0.20 eV, more preferably ⁇ 0.25 eV, and most preferably ⁇ 0.30 eV.
  • the organic mixture according to the invention wherein at least one of H1 and H2, preferably H1, (HOMO-(HOMO-1)) ⁇ 0.2 eV, preferably ⁇ 0.25 eV More preferably, it is ⁇ 0.30 eV, more preferably ⁇ 0.35 eV, and most preferably ⁇ 0.40 eV.
  • the organic mixture wherein the molar ratio of H1 to H2 is from 2:8 to 8:2; the preferred molar ratio is from 3:7 to 7:3; a more preferred molar ratio is 4:6 to 6:4, the best is 5:5.
  • the organic mixture of H1 and H2 which has at least a glass transition temperature T g ⁇ 100 °C, in a preferred embodiment, at least one of its T g ⁇ 120 °C in a more preferred embodiment, which has a T g ⁇ 140 °C at least, in a more preferred embodiment, at least one of its T g ⁇ 160 °C, in a most preferred embodiment, at least There is a T g ⁇ 180 ° C.
  • the sublimation temperature of the first organic compound (H1) and the second organic compound (H2) does not differ by more than 30K.
  • the organic mixture, the first organic compound (H1) and the second organic compound (H2) have a sublimation temperature difference of not more than 20K.
  • the organic mixture, the first organic compound (H1) and the second organic compound (H2) have a sublimation temperature difference of not more than 10K.
  • the first organic compound (H1) and the second organic compound (H2) have the same sublimation temperature.
  • the first organic compound (H1) and the second organic compound (H2) have a molecular weight difference of not more than 100 g/mol, preferably not more than 90 g/mol, in accordance with the organic mixture of the present invention. It is preferably not more than 80 g/mol, preferably not more than 60 g/mol.
  • the present invention also provides another organic mixture comprising a first organic compound (H1) and a second organic compound (H2) as described above, and at least another organic functional material, said another organic function Materials can be selected for hole (also known as hole) injection or transport material (HIM/HTM), hole blocking material (HBM), electron injecting or transporting material (EIM/ETM), electron blocking material (EBM), organic matrix Host, singlet emitter (fluorescent emitter), triplet emitter (phosphorescent emitter), thermally excited delayed fluorescent material (TADF material) and organic dye; preferably selected from phosphorescent emitters and TADF materials.
  • hole also known as hole injection or transport material
  • HBM hole blocking material
  • EIM/ETM electron injecting or transporting material
  • EBM electron blocking material
  • organic matrix Host singlet emitter
  • phosphorescent emitter triplet emitter
  • TADF material thermally excited delayed fluorescent material
  • organic dye preferably selected from phosphorescent emitters and TADF materials.
  • organic functional materials are described
  • ETM ETM
  • fluorescent or singlet emitters phosphorescent or triplet emitters
  • TADF materials are described in more detail below (but are not limited thereto).
  • ETM material examples are not particularly limited, and any metal complex or organic compound may be used as the ETM as long as they can transport electrons.
  • the preferred organic ETM material may be selected from the group consisting of tris(8-hydroxyquinoline)aluminum (AlQ3), phenazine, phenanthroline, anthracene, phenanthrene, anthracene, diterpene, spirobifluorene, p-phenylacetylene, pyridazine, pyrazine.
  • the compound useful as an ETM is a molecule comprising at least one of the following groups
  • R 1 may be selected from the group consisting of hydrogen, deuterium, halogen atoms (F, Cl, Br, I), cyano, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl,
  • the aryl group and the heteroaryl group when R 1 is selected from an aryl group or a heteroaryl group, R 1 has the same meaning as Ar 1 , and Ar 1 to Ar 5 have the same meanings as described above.
  • N2 is an integer from 0 to 20;
  • X 1 -X 8 is selected from CR 1 or N.
  • examples of metal complexes that can be used as ETM include, but are not limited to, the following general structures.
  • (ON) or (NN) is a bidentate ligand in which the metal is coordinated to O, N or N, N;
  • L is an ancillary ligand;
  • r1 is an integer from 1 to the maximum of the metal Number of digits.
  • L 3-r1 r1 is 1 or 2 or 3; when r1 is 3, the subscript 3-r1 of L is 0, indicating that L is absent.
  • L 2-r1 r1 is 1 or 2; when r1 is 2, the subscript 2-r1 of L is 0, indicating that L is absent.
  • the example of the triplet host material is not particularly limited, and any metal complex or organic compound may be used as the host as long as its triplet energy level is higher than that of the illuminant, particularly the triplet illuminant or the phosphorescent illuminant.
  • metal complexes that can be used as a triplet host include, but are not limited to, the following general structure:
  • M3 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
  • r2 is a An integer whose value ranges from 1 to the maximum coordination number of this metal
  • the metal complex that can be used as the triplet host has the following form:
  • (ON) is a bidentate ligand in which the metal is coordinated to the O and N atoms, and r2 is an integer having a value from 1 to the maximum coordination number of the metal; in one embodiment, M3 is optional. 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 2 , X 1 - X 8 and Ar 1 to Ar 3 have the same meanings as described above.
  • triplet host materials examples include:
  • 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.
  • 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
  • TDF Thermally activated delayed fluorescent luminescent material
  • the thermally activated delayed fluorescent luminescent material is a third generation organic luminescent material developed after organic fluorescent materials and organic phosphorescent materials.
  • Such materials generally have a small singlet-triplet energy level difference ( ⁇ Est), and triplet excitons can be converted into singlet exciton luminescence by anti-intersystem crossing. This can make full use of the singlet excitons and triplet excitons formed under electrical excitation.
  • the quantum efficiency in the device can reach 100%.
  • the material structure is controllable, the property is stable, the price is cheap, no precious metal is needed, and the application prospect in the OLED field is broad.
  • the TADF material needs to have a small singlet-triplet energy level difference, preferably ⁇ Est ⁇ 0.3 eV, and secondarily ⁇ Est ⁇ 0.25 eV, more preferably ⁇ Est ⁇ 0.20 eV, and most preferably ⁇ Est ⁇ 0.1 eV.
  • the TADF material has a relatively small ⁇ Est, and in another preferred embodiment, the TADF has a better fluorescence quantum efficiency.
  • TADF luminescent materials can be found in the following patent documents: CN103483332(A), TW201309696(A), TW201309778(A), TW201343874(A), TW201350558(A), US20120217869(A1), WO2013133359(A1), WO2013154064( A1), Adachi, et.al. Adv. Mater., 21, 2009, 4802, Adachi, et. al. Appl. Phys. Lett., 98, 2011, 083302, Adachi, et. al. Appl. Phys. Lett ., 101, 2012, 093306, Adachi, et. al. Chem.
  • TADF luminescent materials are listed in the table below:
  • 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 organic compound according to the invention has a molecular weight of ⁇ 1100 g/mol, preferably ⁇ 1000 g/mol, very preferably ⁇ 950 g/mol, more preferably ⁇ 900 g/mol, most preferably ⁇ 800 g/mol.
  • Another object of the invention is to provide a material solution for printing OLEDs.
  • the organic compound according to the invention has 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 organic 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 present invention also provides a composition comprising an organic compound or polymer as described above, or an organic mixture as described above, and at least one organic solvent.
  • 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% by weight to 20% by weight of the organic compound, preferably 0.1% by weight to 15% by weight, more preferably 0.2% by weight to 10% by weight, most preferably 0.25% by weight. Up to 5 wt% of organic compound.
  • a composition according to the invention wherein said solvent is selected from the group consisting of aromatic or heteroaromatic, ester, aromatic ketone or aromatic ether, aliphatic ketone or aliphatic ether, fat a cyclic or olefinic compound, or an inorganic ester compound such as a boronic acid ester or a phosphate ester, or a mixture of two or more solvents.
  • said solvent is selected from the group consisting of aromatic or heteroaromatic, ester, aromatic ketone or aromatic ether, aliphatic ketone or aliphatic ether, fat a cyclic or olefinic compound, or an inorganic ester compound such as a boronic acid ester or a phosphate ester, or a mixture of two or more solvents.
  • a composition according to the invention comprises at least 50% by weight of an aromatic or heteroaromatic solvent; preferably at least 80% by weight of an aromatic or heteroaromatic solvent; particularly preferably at least 90% by weight Aromatic or heteroaromatic solvents.
  • aromatic or heteroaromatic solvents are, but are not limited to, 1-tetralone, 3-phenoxytoluene, acetophenone, 1-methoxynaphthalene, p-diisopropyl Benzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, dipentylbenzene, o-diethylbenzene, Diethylbenzene, p-diethylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, butylbenzene, dodecylbenzene , 1-methylnaphthalene, 1,2,4-trichlorobenzene,
  • suitable and preferred solvents are aliphatic, cycloaliphatic or aromatic hydrocarbons, amines, thiols, amides, nitriles, esters, ethers, polyethers, alcohols, glycols or polyols.
  • the alcohol represents a suitable class of solvent.
  • Preferred alcohols include alkylcyclohexanols, especially methylated aliphatic alcohols, naphthols and the like.
  • the solvent may be a cycloalkane such as decalin.
  • the solvent may be used singly or as a mixture of two or more organic solvents.
  • the composition according to the present invention comprises an organic functional compound as described above and at least one organic solvent, and may further comprise another organic solvent, and examples of another organic solvent include (but not limited to): methanol, ethanol, 2-methoxyethanol, dichloromethane, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, methylene Toluene, p-xylene, 1,4 dioxane, acetone, methyl ethyl ketone, 1,2 dichloroethane, 3-phenoxytoluene, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydronaphthalene, decalin, hydra
  • the solvent particularly suitable for the present invention is a solvent having Hansen solubility parameters in the following ranges:
  • ⁇ d (dispersion force) is in the range of 17.0 to 23.2 MPa 1/2 , especially in the range of 18.5 to 21.0 MPa 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 organic solvent is selected in consideration of its boiling point parameter.
  • the organic solvent has a boiling point of ⁇ 150 ° C; preferably ⁇ 180 ° C; more preferably ⁇ 200 ° C; more preferably ⁇ 250 ° C; optimally ⁇ 275 ° C or ⁇ 300 ° C.
  • the boiling points within these ranges are beneficial for preventing nozzle clogging of the inkjet printhead.
  • the organic solvent can be evaporated from the solvent system to form a film comprising the functional material.
  • composition in accordance with the present invention a composition in accordance with the present invention
  • the organic solvent is selected in consideration of its surface tension parameter. Suitable ink surface tension parameters are suitable for a particular substrate and a particular printing method.
  • the organic solvent has a surface tension at 25 ° C of from about 19 dyne / cm to 50 dyne / cm; more preferably from 22 dyne / cm to 35 dyne / cm; Most preferably in the range of 25 dyne/cm to 33 dyne/cm.
  • the ink according to the invention has a surface tension at 25 ° C in the range of from about 19 dyne/cm to 50 dyne/cm; more preferably in the range of from 22 dyne/cm to 35 dyne/cm; preferably in 25 dyne/ Cm to the 33dyne/cm range.
  • compositions according to the invention wherein the organic solvent is selected taking into account the viscosity parameters of the ink.
  • the viscosity can be adjusted by different methods, such as by selection of a suitable organic solvent and concentration of functional materials in the ink.
  • the organic solvent has a viscosity of less than 100 cps; more preferably less than 50 cps; most preferably from 1.5 to 20 cps.
  • the viscosity herein refers to the viscosity at ambient temperature at the time of printing, and is usually 15 to 30 ° C, preferably 18 to 28 ° C, more preferably 20 to 25 ° C, and most preferably 23 to 25 ° C.
  • Compositions so formulated will be particularly suitable for ink jet printing.
  • the composition according to the invention has a viscosity at 25 ° C in the range of from about 1 cps to about 100 cps; more preferably in the range of from 1 cps to 50 cps; more preferably in the range of from 1.5 cps to 20 cps.
  • the ink obtained by the organic solvent satisfying the above boiling point and surface tension parameters and viscosity parameters can form a functional material film having uniform thickness and composition properties.
  • the present invention also provides an organic electronic device comprising an organic compound or polymer as described above, or an organic mixture as described above.
  • the organic electronic device can be selected from 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. , organic lasers, organic spintronic devices, organic sensors and organic plasmon emitting diodes (Organic Plasmon Emitting Diode).
  • OLED organic light emitting diode
  • OCV organic photovoltaic cell
  • OFET organic field effect transistor
  • organic lasers organic spintronic devices
  • organic sensors and organic plasmon emitting diodes Organic Plasmon Emitting Diode.
  • the organic electronic device as described above is an organic electroluminescent device comprising at least one light-emitting layer comprising an organic compound or polymer as described above, or an organic mixture as described above.
  • Another object of the present invention is to provide a method of producing the above electronic device.
  • the above compound or mixture is formed into a functional layer on a substrate by evaporation, or a functional layer is formed on a substrate together with at least one other organic functional material by a co-evaporation method, Or coating the above composition on a substrate by printing or coating to form a functional layer, wherein the printing or coating method may be selected from, but not limited to, inkjet printing, Nozzle Printing, Typography, screen printing, dip coating, spin coating, knife coating, roller printing, torsion roll printing, lithography, flexographic printing, rotary printing, spraying, brushing or pad printing, slit type extrusion Coating, etc.
  • the invention further relates to the use of the composition as a printing ink in the preparation of an organic electronic device, 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 functional layer is formed to have a thickness of 5 nm to 1000 nm.
  • the invention further relates to an organic electronic device comprising at least one organic compound or polymer according to the invention, or at least a functional layer prepared using the composition according to the invention.
  • an organic electronic device comprises at least one cathode, an anode and a functional layer between the cathode and the anode, wherein the functional layer comprises at least one organic compound as described above.
  • the organic electronic device described above is an electroluminescent device, particularly an OLED (shown in Figure 1), comprising a substrate (101), an anode (102), at least A light emitting layer (104), a cathode (106).
  • OLED shown in Figure 1
  • the substrate (101) may 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-
  • the anode (102) may comprise a conductive metal or metal oxide, or a conductive polymer.
  • the anode can easily inject holes into a hole injection layer (HIL) or a hole transport layer (HTL) or 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 (106) can comprise 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 comprise other functional layers such as a hole injection layer (HIL) or a hole transport layer (HTL) (103), an electron blocking layer (EBL), an electron injection layer (EIL) or an electron transport layer (ETL) (105). ), a 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 layer (104) is vacuum-deposited, the evaporation source of which comprises a compound or mixture according to the invention.
  • the light-emitting layer (104) is prepared by printing the composition according to the present invention.
  • the electroluminescent device according to the invention 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 organic electronic 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 invention further relates to an electronic device comprising an organic electronic device according to the invention, including, but not limited to, a display device, a lighting device, a light source, a sensor and the like.
  • reaction solution was neutralized to a pH of about 9 with a 5% Na solution, and then extracted with dichloromethane and water and then aqueous three portions. The organic phase was combined, washed with brine, dried and concentrated. /PE (1:10) was purified by column to give white solid compound 4.1 (12.0 g , yield 40%).
  • Example 1 Example 15, Comparative Example 1: Preparation and Characterization of OLED Devices:
  • OLED device structure and materials used in each layer are OLED device structure and materials used in each layer:
  • HIL MoO 3
  • HTL a triarylamine derivative; specifically NPD
  • Host Compound 1-15, Comparative Compound 1 as the first host; Compound A-Compound C as the second host; molar ratio of 1:1; Dopant: Ir(ppy) 3 .
  • the energy level of the organic compound material can be obtained by quantum calculation, for example, by TD-DFT (time-dependent density functional theory) by Gaussian 09W (Gaussian Inc.), and the specific simulation method can be found in WO2011141110.
  • TD-DFT time-dependent density functional theory
  • Gaussian 09W Gaussian Inc.
  • 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, T1 and the resonance factor f(S1) 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, the unit is Hartree. The results are shown in the following table:
  • Example First subject Second subject Example 1 Compound 1 Compound A
  • Example 2 Compound 2 Compound A
  • Example 3 Compound 3 Compound B
  • Example 4 Compound 4 Compound B Example 5 Compound 5 Compound B Example 6 Compound 6 Compound B Example 7 Compound 7 Compound C Example 8 Compound 8 Compound C Example 9 Compound 9 Compound C Example 10 Compound 10 Compound C Example 11 Compound 11 Compound C Example 12 Compound 12 Compound C Example 13 Compound 13 Compound C Comparative Example 1 Comparative compound 1 Compound A
  • the device structure used is as follows:
  • a, cleaning of the conductive glass substrate when used for the first time, can be washed with a variety of solvents, such as chloroform, ketone, isopropyl alcohol, and then UV ozone plasma treatment;
  • HIL 5 nm
  • HTL 50 nm
  • Host 10%
  • Dopant 40 nm
  • ETL 40 m
  • thermally evaporated in a high vacuum (1 x 10 -6 mbar, mbar).
  • cathode Liq / Al (1nm / 150nm) in a high vacuum (1 ⁇ 10 -6 mbar) in the thermal evaporation;
  • the device is encapsulated in a nitrogen glove box with an ultraviolet curable resin.
  • J-V current-voltage
  • Example 2 3.6 73 12080
  • Example 3 3.6 73 12000
  • Example 4 3.6 70 12120
  • Example 5 3.7 75 11080
  • Example 6 3.6 73 11000
  • Example 7 3.6 78 12110
  • Example 8 3.6 71 12050
  • Example 9 3.6 71 11990
  • Example 10 3.6 75 12090
  • Example 13 3.6 73 12110 Comparative Example 1 3.9 59 6180

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Abstract

本发明涉及一种有机化合物，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。本发明还涉及了包含有按照本发明的有机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。本发明还进一步涉及了使用按照本发明的组合物制备的有机电子器件，及制备方法。通过器件结构优化，可达到较佳的器件性能，特别是可实现高性能的OLED器件，对全彩显示和照明应用提供了较好的材料和制备技术选项。

Description

有机化合物、高聚物、有机混合物、组合物及其在有机电子器件的应用
本申请要求于2017年12月27日提交中国专利局、申请号为201711451356.7发明名称为“有机化合物及其在有机电子器件的应用”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
本发明涉及有机电致发光技术领域，特别是涉及一种有机化合物，混合物及组合物，及其在有机电致发光领域的应用。
背景技术
有机发光二极管(OLED)具有质轻、主动发光、视角广、对比度高、发光效率高、能耗低、易制备柔性和大尺寸面板等优异性能，被业界视为最有希望的下一代显示技术。为了提高有机发光二极管的发光效率，推进有机发光二极管大范围产业化进程，目前急需解决有机发光二极管的关键问题为发光性能和寿命。
要获得高性能的有机发光二极管，主体材料是关键。目前制备OLED发光器件，一般采用单主体材料搭配发光体制备，但单主体材料会引起载流子传输速率不同，引起器件效率在高亮度下滚降(Roll-off)严重，从而导致器件寿命缩短。用双主体材料可以减弱单主体所带来的一些问题，尤其是通过合适的材料搭配，所选用的双主体材料能有效形成复合受激态(exciplex)，大幅提高器件的发光效率及寿命。一种技术通过利用能形成复合受激态(exciplex)的共主体(Co-host)，另加一金属配合物作为磷光发光体，实现了低Roll-off、高效率的OLEDs。
进一步，在蒸镀器件中，通过将双主体材料预先形成共混物或有机合金，可以大大简化蒸镀工艺，并且显著提升器件寿命。
目前，仍需进一步改进材料，特别是适合形成共主体的主体材料体系，尤其特别是具有空穴传输性质的p型主体材料。并通过与n型主体或双极性主体搭配形成共主体，使有机电致发光元件中体现良好的效率和寿命，在器件的制造与操作中易于重复，且材料合成简单。
发明内容
基于此，本发明的目的是提供一种有机化合物及其在电子器件中的应用。
具体技术方案如下：
本发明一实施例提供一种如通式(I)所示的有机化合物：
A——(L 1)s——B      (I)
其中，
L 1选自具有5至40个环原子的取代或未取代的芳族或杂芳族环系，或是具有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。
S为0或1。
A为具有通式(II)所示的结构，B为具有通式(III)所示的结构：
Figure PCTCN2018122488-appb-000001
其中，
X 1选自O、S、CR 105R 106、SiR 108R 109。
X 2选自NR 110、CR 111R 112、SiR 113R 114。
R 101-R 114是取代基，相互独立地选自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，或者 是取代或无取代的甲硅烷基，或具有1至20个C原子的取代的酮基，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。
m为0-8的整数。n为0-5的整数。p为0-8的整数。t为0-8的整数。
本发明还提供一种高聚物，包含一重复单元，所述重复单元包含一如通式(1)所示的结构。
本发明还提供一种有机混合物，包括一种如上所述的有机化合物，及至少另一种有机功能材料，所述的另一种有机功能材料可选于空穴(也称电洞)注入或传输材料，空穴阻挡材料，电子注入或传输材料，电子阻挡材料，有机基质材料，单重态发光体(荧光发光体)，三重态发光体(磷光发光体)、热激发延迟荧光材料(TADF材料)及有机染料。
如上所述的有机混合物，包含有至少一种如上所述的有机化合物作为第一有机化合物(H1)和一种第二有机化合物(H2)，所述至少第二有机化合物具有电子传输特性。优先的，第一有机化合物(H1)与第二有机化合物(H2)的摩尔比范围为1:9至9:1。
本发明还提供一种组合物，包含有一种如上所述的有机化合物或高聚物，或一种如上所述有机混合物，及至少一种有机溶剂。
本发明还提供一种有机电子器件，包含一种如上所述的有机化合物或高聚物，或一种如上任所述有机混合物。
所述的有机电子器件，所述有机电子器件可选于有机发光二极管、有机光伏电池、有机发光电池、有机场效应管、有机发光场效应管、有机激光器、有机自旋电子器件、有机传感器及有机等离激元发射二极管。
如上所述的有机电子器件是一有机电致发光器件，其中包含有一发光层，所述的发光层包含有一种如上所述的有机化合物或高聚物，或一种如上所述有机混合物。
本发明的一个或多个实施例的细节在下面的附图和描述中提出。本发明的其它特征、目的和优点将从说明书、附图以及权利要求书变得明显。
有益效果：
按照本发明的一种有机化合物，具有优异的空穴传输性质及稳定性，与另一具有电子传输性质或具有双极性性质的主体搭配形成共主体，可获得提升的电致发光效率及器件寿命。
附图说明
为了更好地描述和说明这里公开的那些发明的实施例和/或示例，可以参考一幅或多幅附图。用于描述附图的附加细节或示例不应当被认为是对所公开的发明、目前描述的实施例和/或示例以及目前理解的这些发明的最佳模式中的任何一者的范围的限制。
图1是按照本发明的一个实施例的发光器件结构图，图中101是基板，102是阳极，103是空穴注入层(HIL)或空穴传输层(HTL)，104是发光层，105是电子注入层(EIL)或电子传输层(ETL)，106是阴极。
发明的详细说明：
为了便于理解本发明，下面将参照相关附图对本发明进行更全面的描述。附图中给出了本发明的较佳实施例。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。
在本发明中，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。
在本发明中，金属有机络合物，金属有机配合物，有机金属配合物具有相同的含义，可以互换。
在本发明中，组合物、印刷油墨、油墨、和墨水具有相同的含义，可以互换。
本发明提供一种如通式(I)所示的有机化合物：
A——(L 1)s——B      (I)
其中，
L 1选自具有5至40个环原子的取代或未取代的芳族或杂芳族环系，或是具有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。
在某些实施例中，L 1相同或不同的是具有5至30个环原子的取代或未取代的芳族或杂芳族环系，或是具有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。
在某些实施例中，L 1相同或不同的是具有5至20个环原子的取代或未取代的芳族或杂芳族环系，或是具有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。
在某些实施例中，L 1相同或不同的是具有5至15个环原子的取代或未取代的芳族或杂芳族环系，或是具有5至15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。
在某些实施例中，L 1相同或不同的是具有5至10个环原子的取代或未取代的芳族或杂芳族环系，或是具有5至10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。
在另一些优先的实施例中，L 1是苯、萘、菲、苯并菲、二联苯、三联苯，或这些结构中的一个或多个碳原子被N原子取代。
在一个优先的实施例中，L 1是二联苯。在一个优先的实施例中，L 1是萘。在一个优先的实施例中，L 1是苯。
在一个较为优先的实施例中，本发明所提到的芳香环系在环系中包含
Figure PCTCN2018122488-appb-000002
个碳原子，更优是
Figure PCTCN2018122488-appb-000003
个碳原子，杂芳香环系在环系中包含
Figure PCTCN2018122488-appb-000004
个碳原子，更优是
Figure PCTCN2018122488-appb-000005
个碳原子，和至少一个杂原子，条件是碳原子和杂原子的总数至少为4。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，更加特别优选选自N、O或S。
以上所述的芳香环系或芳族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。以上所述的杂芳香环系或杂芳族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，至少一个是芳族的或杂芳族的。对于本发明的目的，芳香族或杂芳香族环系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(<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芳香族环系。
具体地，芳族基团的例子有：苯、萘、蒽、菲、二萘嵌苯、并四苯、芘、苯并芘、三亚苯、苊、芴、螺芴及其衍生物。
具体地，杂芳族基团的例子有：呋喃、苯并呋喃、二苯并呋喃、噻吩、苯并噻吩、二苯并噻吩、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。
S为0或1。
在一个更为优先的实施例中，S为0。
A为具有通式(II)所示的结构，B为具有通式(III)所示的结构：
Figure PCTCN2018122488-appb-000006
其中，
X 1选自O、S、CR 105R 106、SiR 108R 109；优选地，X 1选自O或S。
X 2选自NR 110、CR 111R 112、SiR 113R 114；优选地，X 2选自NR 110或CR 111R 112；更优选地，X 2选自NR 110。
R 101-R 114是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，或者是取代或无取代的甲硅烷基，或具有1至20个C原子的取代的酮基，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。
在某些优选的实施例中，通式(III)至少有一组相邻的R 104可以键合成环。
在一些较为优先的实施例中，R 101-R 114是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，或者具有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，或者是取代或无取代的甲硅烷基，或具有1至10个C原子的取代的酮基，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。
m为0-8的整数，较优为0-6的整数，更优为0-4的整数，最优为0-2的整数。
n为0-5的整数，较优为0-4的整数，更优为0-2的整数。
p为0-8的整数，较优为0-6的整数，更优为0-4的整数，最优为0-2的整数。
t为0-8的整数。较优为0-6的整数，更优为0-4的整数，最优为0-2的整数。
在一个较为优先的实施例中，按照本发明所述的有机化合物选自具有以下任一通式所示的结构：
Figure PCTCN2018122488-appb-000007
Figure PCTCN2018122488-appb-000008
其中，
X1选自O、S、CR 105R 106。较优为O或S。
Ar 1选自具有5至40个环原子的取代或未取代的芳族或杂芳族环系，或是具有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。
在某些优先的实施例中，Ar 1相同或不同的是具有5至30个环原子的取代或未取代的芳族或杂芳族环系，或是具有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。
在某些优先的实施例中，Ar 1相同或不同的是具有5至20个环原子的取代或未取代的芳族或杂芳族环系，或是具有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。
在某些优先的实施例中，Ar 1相同或不同的是具有5至15个环原子的取代或未取代的芳族或杂芳族环系，或是具有5至15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。
在另一些优先的实施例中，Ar 1是苯、萘、菲、苯并菲、二联苯、三联苯，或这些结构中的一个或多个碳原子被N原子取代。
在一个优先的实施例中，Ar 1是二联苯。在一个优先的实施例中，Ar 1是苯。在另一些优先的实施例中，Ar 1是二苯并呋喃。在另一些优先的实施例中，Ar 1是二苯并噻吩。在另一些优先的实施例中，Ar 1是芴。在另一些优先的实施例中，Ar 1是螺芴。
在一个优先的实施例中，按照本发明的有机化合物，所述的L 1或Ar 1分别独立地选自如下结构基团中的一种或多种组合：
Figure PCTCN2018122488-appb-000009
其中，
A 1、A 2、A 3、A 4、A 5、A 6、A 7、A 8分别独立表示CR 501或N；
Y 1选自CR 502R 503、SiR 504R 505、NR 506、C(＝O)、S或O；
R 501-R 505是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 3，R 4，R 5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。
较优地，R 501-R 505是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基团，或者具有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基团或者是甲硅烷基基团，或具有1至10个C原子的取代的酮基基团，或具有2至10个C原子的烷氧 基羰基基团，或具有7至10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。
在某些较为优先的实施例中，上述的L 1或Ar 1选于包含如下结构基团中的一种或多种组合，其中环上的H可以被任意取代：
Figure PCTCN2018122488-appb-000010
在某些非常优先的实施例中，按照本发明的有机化合物，通式(I)中所述的A选自以下所示的结构：
Figure PCTCN2018122488-appb-000011
其中，虚线为所示结构与L 1相连接的单键。
在另一些非常优先的实施例中按照本发明的有机化合物，通式(I)中所述的B选自以下所示的结构：
Figure PCTCN2018122488-appb-000012
其中，虚线为所示结构与L 1相连接的单键。
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。
下面列举按照本发明的有机化合物的例子，但不仅限于此：
Figure PCTCN2018122488-appb-000013
Figure PCTCN2018122488-appb-000014
Figure PCTCN2018122488-appb-000015
Figure PCTCN2018122488-appb-000016
本发明还涉及一种按照所述有机化合物的合成方法，其中使用含有活性基团的原料进行反应。这些活性原料包含至少一种离去基团，例如，溴，碘，硼酸或硼酸酯。形成C-C连接的适当的反应是本领域技术人员熟知的并描述于文献中，特别适当和优选的偶联反应是SUZUKI，STILLE和HECK偶联反应。
按照本发明的任意一实施例的有机化合物，具有优异的空穴传输性质及稳定性，与另一具有电子传输性质或具有双极性性质的主体搭配形成共主体，可获得提升的电致发光效率及器件寿命。本发明还进一步涉及一种高聚物，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。
本发明还提供一种有机混合物，包括一种如上所述的有机化合物或高聚物，及至少另一种有机功能材料，所述的另一种有机功能材料可选于空穴(也称电洞)注入或传输材料，空穴阻挡材料，电子注入或传输材料，电子阻挡材料，有机基质材料，单重态发光体(荧光发光体)，三重态发光体(磷光发光体)、热激发延迟荧光材料(TADF材料)及有机染料。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。
在一个优选的实施例中，所述的有机混合物，包含至少一种按照本发明的有机化合物或高聚物和电子传输材料(ETM)。
在一个较优选的实施例中，所述的有机混合物，包含至少一种按照本发明的有机化合物或高聚物和一种发光材料，所述的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)或TADF发光体。
在某些实施例中，所述的有机混合物，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％。
在一个优选的实施例中，所述的有机混合物，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％。
在另一个优选的实施例中，所述的有机混合物，包含至少一种按照本发明的有机化合物或高聚物、一种磷光发光体和一种主体材料。在这种实施例中，按照本发明的有机化合物与所述的一种主体材料作为共主体，其重量比从1:9到9:1；在一种优选的实施例中，按照本发明的有机化合物与所述的一种主体材料形成激基络合物，其能级高于所述的磷光发光体。
在另一个更优选的实施例中，所述的一种混合物，包含少一种按照本发明的有机化合物 或高聚物，和一种TADF材料。其中TADF材料的功能优选为，1)与按照本发明的有机化合物形成磷光共主体材料，其间的重量比从1:9到9:1；2)发光体，其中所述的TADF材料的重量百分比为≤15wt％，较好是≤10wt％，更好是≤8wt％。
在一个最为优先的实施例中，如上所述的有机混合物，包含有至少一种如上所述的有机化合物作为第一有机化合物(H1)和一种第二有机化合物(H2)，所述至少第二有机化合物(H2)具有电子传输特性。
较为优选的，所述至少第二的有机化合物具有电子传输特性的同时也具有空穴传输特性。
一般的，第一有机化合物(H1)与第二有机化合物(H2)的摩尔比范围为1:9至9:1。
优选地，第一有机化合物(H1)与第二有机化合物(H2)的摩尔比范围为3:7至7:3。
更优地，第一有机化合物(H1)与第二有机化合物(H2)的摩尔比范围为4:6至6:4。
最优地，第一有机化合物(H1)与第二有机化合物(H2)的摩尔比为5:5。
在优先的实施例中，上述的有机混合物，所述的第二有机化合物(H2)包含有氟基、或氰基或具有以下通式中的任一基团：
Figure PCTCN2018122488-appb-000017
其中，
a是1-3的整数；X 1–X 8选自于CR 801或N，并且至少有一个是N；Z 1-Z 3为单键或C(R 801) 2或O或S。R 801可选自于如下的基团：氢、氘、烷基、烷氧基、氨基、烯、炔、芳烷基、杂烷基、芳基和杂芳基。
更为优先的，以上所述的有机混合物，所述的第二有机化合物(H2)具有通式(IV)所示的结构，
Figure PCTCN2018122488-appb-000018
其中，
Z 4，Z 5，Z 6选于N或CR 901，且Z 4，Z 5，Z 6中至少一个为N原子。
Ar 13～Ar 15相同或不同的是具有5至40个环原子的芳族或杂芳族环系，或是具有5至40个环原子的芳氧基或杂芳氧基基团，或是具有5至40个环原子的非芳香族基团，或这些体系的组合，其中一个或多个基团可进一步被R 902取代，或R 902可以进一步与所取代的基团形成环系。Ar 13～Ar 15中任一个为多个时，各Ar 13～Ar 15均可独立地选自上述基团。
在一些较为优先的实施例中，Ar 13～Ar 15相同或不同的是氘代或未氘代的具有5至20个环原子的取代或未取代的芳族或杂芳族环系，或是氘代或未氘代的具有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。
在一些更为优先的实施例中，Ar 13～Ar 15相同或不同的是氘代或未氘代的具有5至15个环原子的取代或未取代的芳族或杂芳族环系，或是氘代或未氘代的具有5至15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。
R 901、R 902在每一次出现时，相同或不同的是，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。
更优地，R 901、R 902在每一次出现时，相同或不同的是，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基团，或者具有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基团或者是甲硅烷基基团，或具有1至10个C原子的取代的酮基基团，或具有2至10个C原子的烷氧基羰基基团，或具有7至10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。
b、u、v独立地为1或2或3，优选为1。
在某些实施例中，按照本发明所述的有机混合物，通式(IV)中的Ar 13-Ar 15在多次出现时，可相同或不同地选自如下结构基团中的一种或它们的组合：
Figure PCTCN2018122488-appb-000019
其中，d是1或2或3或4。
下面列出合适的可作为第二有机化合物(H2)的例子，但不限于：
Figure PCTCN2018122488-appb-000020
Figure PCTCN2018122488-appb-000021
在一个非常优选的实施例中，所述的有机混合物用于有机电致发光器件中的发光层。出于稳定性或工艺的考虑，有时会对H1和H2有一些特别的要求。
在一个较为优选的实施例中，按照本发明的有机混合物，其中H1和H2中至少有一个,优选是H2，其((LUMO+1)-LUMO)≥0.1eV，较好是≥0.15eV，更好是≥0.20eV，更更好是≥0.25eV，最好是≥0.30eV。
在另一个较为优选的实施例中，按照本发明的有机混合物，其中H1和H2中至少有一个，优选是H1,其(HOMO-(HOMO-1))≥0.2eV，较好是≥0.25eV，更好是≥0.30eV，更更好是≥0.35eV，最好是≥0.40eV。
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,最优是5:5。
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T g≥100℃，在一个优选的实施例中，至少有一个其T g≥120℃，在一个较为优选的实施例中，至少有一个其T g≥140℃，在一个更为优选的实施例中，至少有一个其T g≥160℃，在一个最为优选的实施例中，至少有一个其T g≥180℃。
在某些实施例中，按照本发明的有机混合物，所述的第一有机化合物(H1)和第二有机化合物(H2)的升华温度差别不超过30K。
优选地，所述的有机混合物，所述的第一有机化合物(H1)和第二有机化合物(H2)的升华温度差别不超过20K。
更优地，所述的有机混合物，所述的第一有机化合物(H1)和第二有机化合物(H2)的升华温度差别不超过10K。
最优地，按照本发明所述的一种有机混合物，所述的第一有机化合物(H1)和第二有机化合物(H2)的升华温度相同。
在某些优先实施例中，按照本发明的有机混合物，所述的第一有机化合物(H1)和第二有机化合物(H2)的分子量差别不超过100g/mol，较好不超过90g/mol，更好不超过80g/mol，最好不超过60g/mol。
本发明还提供另一种有机混合物，包括一种如上所述的第一有机化合物(H1)和第二有机化合物(H2)，及至少另一种有机功能材料，所述的另一种有机功能材料可选于空穴(也称电洞)注入或传输材料(HIM/HTM)，空穴阻挡材料(HBM)，电子注入或传输材料(EIM/ETM)，电子阻挡材料(EBM)，有机基质材料(Host)，单重态发光体(荧光发光体)，三重态发光体(磷光发光体)、热激发延迟荧光材料(TADF材料)及有机染料；优先选自磷光发光体和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。
下面对ETM，荧光发光材料或单重态发光体，磷光发光材料或三重态发光体，和TADF材料作一些较详细的描述(但不限于此)。
1.ETM
ETM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ETM，只要它们可以传输电子。优先的有机ETM材料可选自三(8-羟基喹啉)铝(AlQ3)、吩嗪、菲罗啉、蒽、菲、芴、二芴、螺二芴、对苯乙炔、哒嗪、吡嗪、三嗪、三唑、咪唑、喹啉、异喹啉、喹噁啉、噁唑、异噁唑、噁二唑、噻二唑、吡啶、吡唑、吡咯、嘧啶、吖啶、芘、苝、反茚并芴、顺茚并、二苯并-茚并芴、茚并萘、苯并蒽、氮磷杂环戊二烯、氮硼杂环戊二烯、芳香酮类、内酰胺及它们的衍生物。
一方面,可用作ETM的化合物是至少包含一个以下基团的分子
Figure PCTCN2018122488-appb-000022
Figure PCTCN2018122488-appb-000023
R 1可选于如下的基团：氢、氘、卤原子(F,Cl,Br,I)、氰基、烷基、烷氧基、氨基、烯、炔、芳烷基、杂烷基、芳基和杂芳基，当R 1选自芳基或杂芳基时，R 1含义同Ar 1，Ar 1～Ar 5含义同上所述。n2是一个从0到20的整数；X 1-X 8选于CR 1或N。
另一方面，可用作ETM的金属络合物的例子包括(但不限于)如下的一般结构
Figure PCTCN2018122488-appb-000024
(O-N)或(N-N)是一种两齿配体,其中金属与O,N或N,N配位；L是一个辅助配体；r1是一整数，其值从1到此金属的最大配位数。在L 3-r1的一个具体示例中，r1为1或2或3；当r1为3时，L的下标3-r1为0，代表L不存在。在L 2-r1的一个具体示例中，r1为1或2；当r1为2时，L的下标2-r1为0，代表L不存在。
在下面的表中列出合适的可作ETM化合物的例子:
Figure PCTCN2018122488-appb-000025
2.三重态主体材料(Triplet Host):
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 PCTCN2018122488-appb-000026
M3是一金属；(Y 3-Y 4)是一种两齿配体,Y 3和Y 4独立地选自C,N,O,P,和S；L是一个辅助配体；r2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 PCTCN2018122488-appb-000027
(O-N)是一种两齿配体,其中金属与O和N原子配位，r2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,M3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 PCTCN2018122488-appb-000028
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，n2，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 PCTCN2018122488-appb-000029
Figure PCTCN2018122488-appb-000030
3.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 7250532B2,DE 102005058557A1,CN 1583691A,JP 08053397A,US 6251531B1,US 2006/210830A,EP 1957606A1和US 2008/0113101A1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US5121029。
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(US2007/0092753A1),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:US20070252517A1,US4769292,US 6020078,US 2007/0252517A1,US 2007/0252517A1。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 PCTCN2018122488-appb-000031
4.热激活延迟荧光发光材料(TADF)：
传统有机荧光材料只能利用电激发形成的25％单线态激子发光，器件的内量子效率较低(最高为25％)。尽管磷光材料由于重原子中心强的自旋-轨道耦合增强了系间穿越，可以有效利用电激发形成的单线态激子和三线态激子发光，使器件的内量子效率达到100％。但磷光材料昂贵，材料稳定性差，器件效率滚降严重等问题限制了其在OLED中的应用。热激活延迟荧光发光材料是继有机荧光材料和有机磷光材料之后发展的第三代有机发光材料。该类材料一般具有小的单线态-三线态能级差(ΔEst)，三线态激子可以通过反系间穿越转变成单线 态激子发光。这可以充分利用电激发下形成的单线态激子和三线态激子。器件内量子效率可达到100％。同时材料结构可控，性质稳定，价格便宜无需要贵金属，在OLED领域的应用前景广阔。
TADF材料需要具有较小的单线态-三线态能级差，较好是ΔEst<0.3eV，次好是ΔEst<0.25eV，更好是ΔEst<0.20eV，最好是ΔEst<0.1eV。在一个优先的实施方案中，TADF材料有比较小的ΔEst，在另一个优先的实施方案中,TADF有较好的荧光量子效率。一些TADF发光的材料可在下述专利文件中找到:CN103483332(A)，TW201309696(A)，TW201309778(A)，TW201343874(A)，TW201350558(A)，US20120217869(A1)，WO2013133359(A1)，WO2013154064(A1)，Adachi,et.al.Adv.Mater.,21,2009,4802，Adachi,et.al.Appl.Phys.Lett.,98,2011,083302，Adachi,et.al.Appl.Phys.Lett.,101,2012,093306，Adachi,et.al.Chem.Commun.,48,2012,11392，Adachi,et.al.Nature Photonics,6,2012,253，Adachi,et.al.Nature,492,2012,234，Adachi,et.al.J.Am.Chem.Soc,134,2012,14706，Adachi,et.al.Angew.Chem.Int.Ed,51,2012,11311，Adachi,et.al.Chem.Commun.,48,2012,9580，Adachi,et.al.Chem.Commun.,48,2013,10385，Adachi,et.al.Adv.Mater.,25,2013,3319，Adachi,et.al.Adv.Mater.,25,2013,3707，Adachi,et.al.Chem.Mater.,25,2013,3038，Adachi,et.al.Chem.Mater.,25,2013,3766，Adachi,et.al.J.Mater.Chem.C.,1,2013,4599，Adachi,et.al.J.Phys.Chem.A.,117,2013,5607，特此将上述列出的专利或文章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TADF发光材料的例子:
Figure PCTCN2018122488-appb-000032
Figure PCTCN2018122488-appb-000033
5.三重态发光体(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 PCTCN2018122488-appb-000034
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:WO200070655,WO 200141512,WO 200202714,WO 200215645,EP 1191613,EP 1191612,EP1191614,WO 2005033244,WO 2005019373,US 2005/0258742,WO 2009146770,WO2010015307,WO 2010031485,WO 2010054731,WO 2010054728,WO 2010086089,WO2010099852,WO 2010102709,US 20070087219A1,US 20090061681A1,US 20010053462A1,Baldo,Thompson et al.Nature 403,(2000),750-753,US 20090061681A1,US 20090061681A1,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 2007/0252517A1,Johnson et al.,JACS 105,1983,1795,Wrighton,JACS 96,1974,998,Ma et al.,Synth.Metals 94,1998,245,US 6824895,US7029766,US 6835469,US 6830828,US 20010053462A1,WO 2007095118A1,US2012004407A1,WO 2012007088A1,WO2012007087A1,WO 2012007086A1,US 2008027220A1,WO 2011157339A1,CN 102282150A,WO 2009118087A1,WO 2013107487A1,WO2013094620A1,WO 2013174471A1,WO 2014031977A1,WO 2014112450A1,WO2014007565A1,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 PCTCN2018122488-appb-000035
Figure PCTCN2018122488-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，按照本发明的有机化合物，其分子量≤1100g/mol，优选≤1000g/mol，很优选≤950g/mol，更优选≤900g/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，按照本发明的有机化合物，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。
本发明的另一个目的是为印刷OLED提供材料的解决方案。
本发明还提供一种组合物，包含有一种如上所述的有机化合物或高聚物，或一种如上所述有机混合物，及至少一种有机溶剂。
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0.01wt％至20wt％的有机化合物，较好的是0.1wt％ 至15wt％，更好的是0.2wt％至10wt％，最好的是0.25wt％至5wt％的有机化合物。
在一些优先的实施方案中，按照本发明的一种组合物，其中所述的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，或硼酸酯或磷酸酯等无机酯类化合物，或两种及两种以上溶剂的混合物。
在另一些优先的实施方案中，按照本发明的一种组合物，其中包含至少50wt％的芳族或杂芳族溶剂；优选至少80wt％的芳族或杂芳族溶剂；特别优选至少90wt％的的芳族或杂芳族溶剂。
按照本发明的基于芳族或杂芳族溶剂的例子有，但不限于：1-四氢萘酮、3-苯氧基甲苯、苯乙酮、1-甲氧基萘、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、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、1-甲基萘、1,2,4-三氯苯、1,3-二丙氧基苯、4,4-二氟二苯甲烷、二苯醚、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、2-苯氧基甲醚、2-苯氧基四氢呋喃、乙基-2-萘基醚、N-甲基二苯胺、4-异丙基联苯、αα-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、二苄醚等。
在另一些实施例中，适当的和优选的溶剂是脂肪族、脂环族或芳烃族，胺，硫醇，酰胺，腈，酯，醚，聚醚，醇，二醇或多元醇。
在另一些实施例中，醇代表适当类别的溶剂。优选的醇包括烷基环己醇，特别是甲基化的脂肪族醇，萘酚等。
所述的溶剂可以是环烷烃，例如十氢化萘。
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。
在某些实施例中，按照本发明的组合物，包含有一种如上所述的有机功能化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。
在一些优先的实施方案中，按照本发明的一种组合物，
1)其粘度@25℃，在1cPs到100cPs范围，和/或
2)其表面张力@25℃，在19dyne/cm到50dyne/cm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表面张力参数。合适的油墨表面张力参数适合于特定的基板和特定的印刷方法。例如对喷墨印刷，在一个优选的实施例中，所述的有机溶剂在25℃下的表面张力约在19dyne/cm到50dyne/cm范围；更优为在22dyne/cm到35dyne/cm范围；最优为在25dyne/cm到33dyne/cm范围。
在一个优选的实施例中，按照本发明的油墨在25℃下的表面张力约在19dyne/cm到50dyne/cm范围；更好是在22dyne/cm到35dyne/cm范围；最好是在25dyne/cm到33dyne/cm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油墨的粘度参数。粘度可以通过 不同的方法调节，如通过合适的有机溶剂的选取和油墨中功能材料的浓度。在一个优选的实施例中，所述的有机溶剂的粘度低于100cps；更优为低于50cps；最优为为1.5到20cps。这里的粘度是指在印刷时的环境温度下的粘度，一般在15-30℃，较好的是18-28℃，更好是20-25℃，最好是23-25℃。如此配制的组合物将特别适合于喷墨印刷。
在一个优选的实施例中，按照本发明的组合物，在25℃下的粘度约在1cps到100cps范围；更好是在1cps到50cps范围；最好是在1.5cps到20cps范围。
满足上述沸点及表面张力参数及粘度参数的有机溶剂获得的油墨能够形成具有均匀厚度及组成性质的功能材料薄膜。
本发明还提供一种有机电子器件，包含一种如上所述的有机化合物或高聚物，或一种如上所述有机混合物。
如上所述的有机电子器件，所述有机电子器件可选于有机发光二极管(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)。
如上所述的有机电子器件是一有机电致发光器件，至少包含有一发光层，所述的发光层包含有一种如上所述的有机化合物或高聚物，或一种如上所述有机混合物。
本发明的另一目的是提供上述电子器件的制备方法。
具体技术方案如下：
一种制备方法，将上述化合物或混合物以蒸镀的方法于一基板上形成一功能层，或以共蒸镀的方法与至少一种另一有机功能材料一起于一基板上形成一功能层，或将上述的组合物用印刷或涂布的方法涂布于一基板上形成一功能层，其中印刷或涂布的方法可选于(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。
本发明还涉及所述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，所述的形成的一功能层，其厚度在5nm-1000nm。
本发明进一步涉及一种有机电子器件，至少包含一种按照本发明的有机化合物或高聚物，或至少包含一功能层，其是使用按照本发明的组合物制备而成。一般的，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。
在一个更为优选的实施例中，以上所述的有机电子器件是电致发光器件，特别是OLED(如图1所示)，其中包括一基片(101)，一阳极(102)，至少一发光层(104)，一阴极(106)。
基片(101)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(102)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(106)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)或空穴传输层(HTL)(103)、电子阻挡层(EBL)、电子注入层(EIL)或电子传输层(ETL)(105)、空穴阻挡层(HBL)。适合用于这些功能层中的材料在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。
在一个优选的实施例中，按照本发明的发光器件中，其发光层(104)是通过真空蒸镀，其蒸镀源包含有一按照本发明的化合物或混合物。
在另一个优选的实施例中，按照本发明的发光器件中，其发光层(104)是通过打印按照本发明的组合物制备而成。
按照本发明的电致发光器件，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有机电子器件在各种电子设备中的应用，包括，但不限于，显示设备，照明设备，光源，传感器等等。
本发明还涉及包含有按照本发明的有机电子器件的电子设备，包括，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
合成例1：化合物1的合成
Figure PCTCN2018122488-appb-000037
化合物1.1的合成：
将Mg(4.6g,182.3mmol)与碘粒加入干燥的三口烧瓶中并加入THF 30 ml，在氮气保护条件下，将溶于30 mlTHF的溴苯(10g,64.1mmol)溶液通过恒压漏斗缓慢滴加适量，并使格式引发，然后缓慢滴加溴苯溶液使格式保持适度反应状态，当溶液滴加完毕，加热至70℃恒温搅拌反应2 h，待格式反应完全，将格氏试剂在氮气保护下缓慢滴加入4-溴芴酮(14.5g,57.69mmol)的THF溶液中，并加热至70℃搅拌反应5 h，反应完全后旋去溶剂，得到中间体A；将A(10.0g,29.8mmol)与二苯并呋喃(5.0g,29.8mmol)置于三口烧瓶中，以甲磺酸(200ml)为溶剂，升温至70℃，恒温搅拌反应过夜，TLC和MS显示反应完全，主要为目标产物,冷却，将反应液用5％的Na溶液中和至PH为9左右后，以二氯甲烷和水分液，水相萃取三次，合并有机相，饱和食盐水洗涤，干燥，浓缩，残余物用DCM/PE(1:10)过柱子纯化，得到白色固体化合物1.1(12.3g，收率43％)。
化合物1的合成：
将化合物1.1(12.3g,25.3mmol)、N-(3-联苯基)咔唑-3-硼酸(9.2g,25.3mmol)和2.00 mol/L的碳酸钠(5.4g，50.6mmol)溶液加入三口烧瓶中，用300ml甲苯搅拌溶解，氮气保护，然后加入Pd(pph 3) 4(71.3mg,0.76mmol)，将反应液搅拌回流反应12小时，TLC和MS显示反应完全，主要为目标产物,冷却，将反应液用150ml的饱和食盐水洗涤三次，无水硫酸钠干燥，然后蒸发除去溶剂，残余物用DCM/PE(1:5)过柱子纯化，得到白色固体化合物1(13.7g，收率75％)。
合成例2：化合物2的合成
Figure PCTCN2018122488-appb-000038
化合物2.1的合成：
将Mg(4.6g,182.3mmol)与碘粒加入干燥的三口烧瓶中并加入THF 30 ml，在氮气保护条件下，将溶于30 mlTHF的溴苯(10g,64.1mmol)溶液通过恒压漏斗缓慢滴加适量，并使格式引发，然后缓慢滴加溴苯溶液使格式保持适度反应状态，当溶液滴加完毕，加热至70℃恒温搅拌反应2 h，待格式反应完全，将格氏试剂在氮气保护下缓慢滴加入3-溴芴酮(14.5g,57.69mmol)的THF溶液中，并加热至70℃搅拌反应5 h，反应完全后旋去溶剂，得到中间体B；将B(10.0g,29.8mmol)与二苯并噻吩(5.5g,29.8mmol)置于三口烧瓶中，以甲磺酸(200ml)为溶剂，升温至70℃，恒温搅拌反应过夜，TLC和MS显示反应完全，主要为目标产物,冷却，将反应液用5％的Na溶液中和至PH为9左右后，以二氯甲烷和水分液，水相萃取三次，合并有机相，饱和食盐水洗涤，干燥，浓缩，残余物用DCM/PE(1:10)过柱子纯化，得到白色固体化合物2.1(12.0g，收率40％)。
化合物2的合成：
将化合物2.1(12.0g,23.9mmol)、N-(3-联苯基)咔唑-3-硼酸(8.7g,23.9mmol)和2.00 mol/L的碳酸钠(5.1g，47.8mmol)溶液加入三口烧瓶中，用300ml甲苯搅拌溶解，氮气保护，然后加入Pd(pph 3) 4(69mg,0.72mmol)，将反应液搅拌回流反应12小时，TLC和MS显示反应完全，主要为目标产物,冷却，将反应液用150ml的饱和食盐水洗涤三次，无水硫酸钠干燥，然后蒸发除去溶剂，残余物用DCM/PE(1:5)过柱子纯化，得到白色固体化合物2(13g，收率75％)。
合成例3：化合物3的合成
Figure PCTCN2018122488-appb-000039
化合物3.1的合成：
将Mg(4.6g,182.3mmol)与碘粒加入干燥的三口烧瓶中并加入THF 30ml，在氮气保护条件下，将溶于30mlTHF的溴苯(10g,64.1mmol)溶液通过恒压漏斗缓慢滴加适量，并使格式引发，然后缓慢滴加溴苯溶液使格式保持适度反应状态，当溶液滴加完毕，加热至70℃恒温搅拌反应2h，待格式反应完全，将格氏试剂在氮气保护下缓慢滴加入2-溴芴酮(14.5g,57.69mmol)的THF溶液中，并加热至70℃搅拌反应5h，反应完全后旋去溶剂，得到中间体C；将C(10.0g,29.8mmol)与二苯并呋喃(5.0g,29.8mmol)置于三口烧瓶中，以甲磺酸(200ml)为溶剂，升温至70℃，恒温搅拌反应过夜，TLC和MS显示反应完全，主要为目标产物,冷却，将反应液用5％的Na溶液中和至PH为9左右后，以二氯甲烷和水分液，水相萃取三次，合并有机相，饱和食盐水洗涤，干燥，浓缩，残余物用DCM/PE(1:10)过柱子纯化，得到白色固体化合物3.1(12.3g，收率43％)。
化合物3的合成：
将化合物3.1(12.3g,25.3mmol)、N-(3-联苯基)咔唑-3-硼酸(9.2g,25.3mmol)和2.00mol/L的碳酸钠(5.4g，50.6mmol)溶液加入三口烧瓶中，用300ml甲苯搅拌溶解，氮气保护，然后加入Pd(pph 3) 4(71.3mg,0.76mmol)，将反应液搅拌回流反应12小时，TLC和MS显示反应完全，主要为目标产物,冷却，将反应液用150ml的饱和食盐水洗涤三次，无水硫酸钠干燥，然后蒸发除去溶剂，残余物用DCM/PE(1:5)过柱子纯化，得到白色固体化合物3(12.8g，收率70％)。
合成例4：化合物4的合成
Figure PCTCN2018122488-appb-000040
化合物4.1的合成：
将Mg(4.6g,182.3mmol)与碘粒加入干燥的三口烧瓶中并加入THF 30ml，在氮气保护条件下，将溶于30mlTHF的溴苯(10g,64.1mmol)溶液通过恒压漏斗缓慢滴加适量，并使格式引发，然后缓慢滴加溴苯溶液使格式保持适度反应状态，当溶液滴加完毕，加热至70℃恒温搅拌反应2h，待格式反应完全，将格氏试剂在氮气保护下缓慢滴加入4-溴芴酮(14.5g,57.69mmol)的THF溶液中，并加热至70℃搅拌反应5h，反应完全后旋去溶剂，得到中间体D；将D(10.0g,29.8mmol)与二苯并噻吩(5.5g,29.8mmol)置于三口烧瓶中，以甲磺酸(200 ml)为溶剂，升温至70℃，恒温搅拌反应过夜，TLC和MS显示反应完全，主要为目标产物,冷却，将反应液用5％的Na溶液中和至PH为9左右后，以二氯甲烷和水分液，水相萃取三次，合并有机相，饱和食盐水洗涤，干燥，浓缩，残余物用DCM/PE(1:10)过柱子纯化，得到白色固体化合物4.1(12.0g，收率40％)。
化合物4.2的合成：
将化合物4.1(12.0g,23.9mmol)、咔唑-3-硼酸(5.1g,23.9mmol)和2.00mol/L的碳酸钠(5.1g，47.8mmol)溶液加入三口烧瓶中，用300ml甲苯搅拌溶解，氮气保护，然后加入Pd(pph 3) 4(69mg,0.72mmol)，将反应液搅拌回流反应12小时，TLC和MS显示反应完全，主要为目标产物,冷却，将反应液用150ml的饱和食盐水洗涤三次，无水硫酸钠干燥，然后蒸发除去溶剂，残余物用DCM/PE(1:5)过柱子纯化，得到白色固体化合物4.2(9.9g，收率70％)。
化合物4的合成：
将化合物4.2(9.9g,16.8mmol)和4-溴-二苯并噻吩(4.4g,16.8mmol)加入三口烧瓶中，用200ml甲苯搅拌溶解，氮气保护，然后加入Pd(dba) 2(0.29g,0.5mmol)和叔丁醇钠(4.8g，50.4mmol)，随后加入10％的三叔丁基膦甲苯溶液3.1ml.将反应液搅拌回流12小时，冷却，用100ml水洗涤三次反应液，无水硫酸钠干燥，然后蒸发除去溶剂，残余物用DCM/PE(1:4)过柱子纯化，得到白色固体化合物4(8.4g，收率65％)。
合成例5：化合物5的合成
Figure PCTCN2018122488-appb-000041
化合物5.1的合成：
将化合物1.1(10g,20.6mmol)和3-溴咔唑(5g,20.6mmol)加入三口烧瓶中，用200ml甲苯搅拌溶解，氮气保护，然后加入Pd(dba) 2(0.35g,0.62mmol)和叔丁醇钠(5.9g，61.8mmol)，随后加入10％的三叔丁基膦甲苯溶液3.7ml.将反应液搅拌回流12小时，冷却，用100ml水洗涤三次反应液，无水硫酸钠干燥，然后蒸发除去溶剂，残余物用DCM/PE(1:4)过柱子纯化，得到白色固体化合物5.1(8g，收率60％)。
化合物5的合成：
将化合物5.1(8g,12.3mmol)和咔唑(2g,12.3mmol)加入三口烧瓶中，用150ml甲苯搅拌溶解，氮气保护，然后加入Pd(dba) 2(0.21g,0.37mmol)和叔丁醇钠(3.5g，36.9mmol)，随后加入10％的三叔丁基膦甲苯溶液2.2ml.将反应液搅拌回流12小时，冷却，用100ml水洗涤三次反应液，无水硫酸钠干燥，然后蒸发除去溶剂，残余物用DCM/PE(1:4)过柱子纯化，得到白色固体化合物5(4.5g，收率50％)。
合成例6：化合物6的合成
Figure PCTCN2018122488-appb-000042
化合物6.1的合成：
将化合物N-苯基咔唑-1-硼酸(10.0g,34.8mmol)、邻溴硝基苯(7.0g,34.8mmol)和2.00mol/L的碳酸钠(7.4g，69.6mmol)溶液加入三口烧瓶中，用300ml甲苯搅拌溶解，氮气保护，然后加入Pd(pph 3) 4(1.2g,1.04mmol)，将反应液搅拌回流反应12小时，TLC和MS显示反应完全，主要为目标产物,冷却，将反应液用150ml的饱和食盐水洗涤三次，无水硫酸钠干燥，然后蒸发除去溶剂，残余物用DCM/PE(1:8)过柱子纯化，得到白色固体化合物6.1(10.0g，收率80％)。
化合物6.2的合成：
将化合物6.1(10.0g,27.5mmol)加入三口烧瓶中，用150ml亚磷酸三乙酯作溶剂，氮气保护，将升温至143℃恒温搅拌反应12小时，TLC和MS显示反应完全，主要为目标产物,冷却，减压蒸馏除去溶剂，将残余物用足量DCM溶解，并用150ml的饱和食盐水洗涤三次，无水硫酸钠干燥，然后蒸发除去溶剂，残余物用DCM/PE(1:4)过柱子纯化，得到白色固体化合物6.2(8.2g，收率90％)。
化合物6的合成：
将化合物6.2(8.2g,24.7mmol)和化合物4.1(12.4g,24.7mmol)加入三口烧瓶中，用300ml甲苯搅拌溶解，氮气保护，然后加入Pd(dba) 2(0.43g,0.74mmol)和叔丁醇钠(7.1g，74.1mmol)，随后加入10％的三叔丁基膦甲苯溶液4.5ml.将反应液搅拌回流12小时，冷却，用100ml水洗涤三次反应液，无水硫酸钠干燥，然后蒸发除去溶剂，残余物用DCM/PE(1:3)过柱子纯化，得到白色固体化合物6(13.6g，收率73％)。
合成例7：化合物7的合成
Figure PCTCN2018122488-appb-000043
化合物7.1的合成：
将Mg(4.6g,182.3mmol)与碘粒加入干燥的三口烧瓶中并加入THF 30ml，在氮气保护条件下，将溶于30mlTHF的溴苯(10g,64.1mmol)溶液通过恒压漏斗缓慢滴加适量，并使格式引发，然后缓慢滴加溴苯溶液使格式保持适度反应状态，当溶液滴加完毕，加热至70℃恒温搅拌反应2h，待格式反应完全，将格氏试剂在氮气保护下缓慢滴加入3-溴芴酮(14.5g,57.69mmol)的THF溶液中，并加热至70℃搅拌反应5h，反应完全后旋去溶剂，得到中间体E；将E(10.0g,29.8mmol)与二苯并呋喃(5.0g,29.8mmol)置于三口烧瓶中，以甲磺酸(200ml)为溶剂，升温至70℃，恒温搅拌反应过夜，TLC和MS显示反应完全，主要为目标产物,冷却，将反应液用5％的Na溶液中和至PH为9左右后，以二氯甲烷和水分液，水相萃取三次，合并有机相，饱和食盐水洗涤，干燥，浓缩，残余物用DCM/PE(1:10)过柱子纯化，得到白色固体化合物7.1(12.6g，收率44％)。
化合物7的合成：
将化合物7.1(12.6g,25.9mmol)和化合物F(10.6g,25.9mmol)加入三口烧瓶中，用300ml甲苯搅拌溶解，氮气保护，然后加入Pd(dba) 2(0.45g,0.78mmol)和叔丁醇钠(7.4g，77.7mmol)，随后加入10％的三叔丁基膦甲苯溶液4.7ml.将反应液搅拌回流12小时，冷却，用100ml水洗涤三次反应液，无水硫酸钠干燥，然后蒸发除去溶剂，残余物用DCM/PE(1:3)过柱子纯化，得到白色固体化合物7(14.1g，收率67％)。
合成例8：化合物8的合成
Figure PCTCN2018122488-appb-000044
化合物8的合成：
将化合物G(10.0g,20.6mmol)、H(7.5g,20.6mmol)和2.00mol/L的碳酸钠(4.4g，41.2mmol)溶液加入三口烧瓶中，用200ml甲苯搅拌溶解，氮气保护，然后加入Pd(pph 3) 4(0.7g,0.62mmol)，将反应液搅拌回流反应12小时，TLC和MS显示反应完全，主要为目标产物,冷却，将反应液用150ml的饱和食盐水洗涤三次，无水硫酸钠干燥，然后蒸发除去溶剂，残余物用DCM/PE(1:4)过柱子纯化，得到白色固体化合物8(11.3g，收率76％)。
合成例9：化合物9的合成
Figure PCTCN2018122488-appb-000045
化合物将9化的合物合I成(：10.0g,19.9mmol)和化合物G(5.4g,19.9mmol)加入三口烧瓶中，用200ml甲苯搅拌溶解，氮气保护，然后加入Pd(dba) 2(0.34g,0.6mmol)和叔丁醇钠(5.7g，59.7mmol)，随后加入10％的三叔丁基膦甲苯溶液3.6ml.将反应液搅拌回流12小时，冷却，用100ml水洗涤三次反应液，无水硫酸钠干燥，然后蒸发除去溶剂，残余物用DCM/PE(1:3)过柱子纯化，得到白色固体化合物9(9.4g，收率68％)。
合成例10：化合物10的合成
Figure PCTCN2018122488-appb-000046
化合物10的合成：
将化合物I(10.0g,19.9mmol)和化合物K(6.6g,19.9mmol)加入三口烧瓶中，用200ml甲苯搅拌溶解，氮气保护，然后加入Pd(dba) 2(0.34g,0.6mmol)和叔丁醇钠(5.7g，59.7mmol)，随后加入10％的三叔丁基膦甲苯溶液3.6ml.将反应液搅拌回流12小时，冷却，用100ml水洗涤三次反应液，无水硫酸钠干燥，然后蒸发除去溶剂，残余物用DCM/PE(1:3)过柱子纯化，得到白色固体化合物10(10.7g，收率71％)。
合成例11：化合物11的合成
Figure PCTCN2018122488-appb-000047
在氮气流下装有冷凝管的250mL三口烧瓶中，将化合物11-1(6.49g,10mmol)和4-溴-二苯并呋喃(2.47g,10mmol)加入三口烧瓶中，用100ml无水甲苯搅拌溶解，然后加入Pd(dba) 2(665g,0.5mmol),NatB(1.92g，20mmol)和2ml的TTBP甲苯溶液。将反应液搅拌回流12小 时，冷却，用100ml水洗涤三次反应液，无水硫酸钠干燥，然后蒸发除去溶剂，残余物用DCM/PE(1:5)过柱子纯化，得到白色固体化合物11(4.24g，收率52％)。
合成例12：化合物12的合成
Figure PCTCN2018122488-appb-000048
在氮气流下装有冷凝管的250mL三口烧瓶中，将化合物12-1(4.87,10ml)和螺二芴-4-硼酸(3.61g,10mmol)加入三口烧瓶中，用100ml甲苯和20ml水搅拌溶解，然后加入Pd(PPh 3) 4(665mg,0.05mmol)和K 2CO 3(2.76g，20mmol)。将反应液搅拌回流12小时，冷却，分液，有机相用100ml水洗涤反应液3次，无水硫酸钠干燥，然后蒸发除去溶剂，残余物用DCM/PE(1:10)过柱子纯化，得到白色固体化合物12(5.05g，收率70％).
合成例13：化合物13的合成
Figure PCTCN2018122488-appb-000049
在氮气流下装有冷凝管的250mL三口烧瓶中，将化合物13-1(6.75g,10mmol)和中间体A(2.47g,10mmol)加入三口烧瓶中，用100ml无水甲苯搅拌溶解，然后加入Pd(dba) 2(665g,0.5mmol),NatB(1.92g，20mmol)和2ml的TTBP甲苯溶液。将反应液搅拌回流12小时，冷却，用100ml水洗涤三次反应液，无水硫酸钠干燥，然后蒸发除去溶剂，残余物用DCM/PE(1:5)过柱子纯化，得到白色固体化合物13(4.43g，收率57％)。
对比合成例1：对比化合物1的合成
Figure PCTCN2018122488-appb-000050
对比化合物1的合成：
将化合物9-苯基-3.3-联咔唑(12.24g,30mmol)和(7.41g,30mmol)加入三口烧瓶中，用300ml甲苯搅拌溶解，氮气保护，然后加入Pd(dba) 2 862.5mg,1.5mmol)和叔丁醇钠(5.76g，60mmol)，随后加入10％的三叔丁基膦甲苯溶液10ml.将反应液搅拌回流12小时，冷却，用100ml水洗涤三次反应液，无水硫酸钠干燥，然后蒸发除去溶剂，残余物用DCM/PE(1:10)过柱子纯化，得到白色固体(10.67g，收率62％)。
实施例1-实施例15、对比实施例1：OLED器件的制备与表征：
OLED器件结构及各层所使用材料：
ITO/HIL(5nm)/HTL(50nm)/Host：10％Dopant(40nm)/ETL：Liq(2：1)(40nm)/阴极
HIL：MoO 3；HTL：一种三芳胺衍生物；具体为NPD；
Host:化合物1-15、对比化合物1作为第一主体；化合物A-化合物C作为第二主体；摩尔比为1:1；Dopant：Ir(ppy) 3。
ETL：TPBi；阴极：Liq(1nm)/Al(100nm)。
Figure PCTCN2018122488-appb-000051
作为第二主体使用具有以下结构的化合物A或化合物B或化合物C：
Figure PCTCN2018122488-appb-000052
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，S1，T1和谐振因子f(S1)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。结果如下表所示：
材料 HOMO[eV] LUMO[eV] T 1[eV] S 1[eV]
化合物1 -5.73 -2.20 2.92 3.11
化合物2 -5.63 -2.21 2.84 3.24
化合物3 -5.56 -2.23 2.72 3.24
化合物4 -5.72 -2.22 2.90 3.10
化合物5 -5.51 -2.20 2.89 3.18
化合物6 -5.50 -2.22 2.90 3.20
化合物7 -5.60 -2.23 2.89 3.22
化合物8 -5.71 -2.24 2.92 3.27
化合物9 -5.56 -2.20 2.90 3.24
化合物10 -5.57 -2.21 2.92 3.19
化合物11 -5.50 -2.21 2.89 3.11
化合物12 -5.54 -2.23 2.89 3.17
化合物13 -5.60 -2.23 2.87 3.17
对比化合物1 -5.42 -2.22 2.98 3.19
化合物A -6.09 -2.84 2.71 3.28
化合物B -6.06 -2.86 2.79 3.19
化合物C -5.67 -2.91 2.75 2.82
实施例 第一主体 第二主体
实施例1 化合物1 化合物A
实施例2 化合物2 化合物A
实施例3 化合物3 化合物B
实施例4 化合物4 化合物B
实施例5 化合物5 化合物B
实施例6 化合物6 化合物B
实施例7 化合物7 化合物C
实施例8 化合物8 化合物C
实施例9 化合物9 化合物C
实施例10 化合物10 化合物C
实施例11 化合物11 化合物C
实施例12 化合物12 化合物C
实施例13 化合物13 化合物C
对比实施例1 对比化合物1 化合物A
所采用的器件结构如下：
具有ITO/HIL(5nm)/HTL(50nm)/Host：10％Dopant(40 nm)/ETL：Liq(2:1)(40nm)//阴极的OLED器件的制备步骤如下:
a、导电玻璃基片的清洗:首次使用时，可用多种溶剂进行清洗，例如氯仿、酮、异丙醇进行清洗，然后进行紫外臭氧等离子处理；
b、HIL(5nm)，HTL(50nm)，Host:10％Dopant(40nm)，ETL(40m)：在高真空(1×10 -6毫巴，mbar)中热蒸镀而成。
c、阴极:Liq/Al(1nm/150nm)在高真空(1×10 -6毫巴)中热蒸镀而成；
d、封装:器件在氮气手套箱中用紫外线硬化树脂封装。
各OLED器件的电流电压(J-V)特性通过表征设备来表征，同时记录重要的参数如效率，寿命及外部量子效率。经检测，采用化合物1-化合物10作为第一主体，与具有电子传输性质的第二主体形成共主体，所得到器件的效率和寿命都优于对比实施例。
实施例 电压(V) 效率(cd/A) 寿命(LT95，h)@1000cd/m 2
实施例1 3.5 71 12180
实施例2 3.6 73 12080
实施例3 3.6 73 12000
实施例4 3.6 70 12120
实施例5 3.7 75 11080
实施例6 3.6 73 11000
实施例7 3.6 78 12110
实施例8 3.6 71 12050
实施例9 3.6 71 11990
实施例10 3.6 75 12090
实施例11 3.6 70 12010
实施例12 3.7 70 12100
实施例13 3.6 73 12110
对比实施例1 3.9 59 6180
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (16)

  1. 一种如通式(I)所示的有机化合物：
    A——(L 1)s——B   (I)
    其中，
    L 1选自具有5至40个环原子的取代或未取代的芳族或杂芳族环系，或是具有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。
    S为0或1。
    A为具有通式(II)所示的结构，B为具有通式(III)所示的结构：
    Figure PCTCN2018122488-appb-100001
    其中，
    X 1选自O、S、CR 105R 106、SiR 108R 109。
    X 2选自NR 110、CR 111R 112、SiR 113R 114。
    R 101-R 114是取代基，相互独立地选自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，或者是取代或无取代的甲硅烷基，或具有1至20个C原子的取代的酮基，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。
    m为0-8的整数；n为0-5的整数；p为0-8的整数；t为0-8的整数。
  2. 根据权利要求1所述的有机化合物，其特征在于，具有以下任一通式所示的结构：
    Figure PCTCN2018122488-appb-100002
    其中，
    X 1选自O、S、CR 105R 106。
    Ar 1选自具有5至40个环原子的取代或未取代的芳族或杂芳族环系，或是具有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。
  3. 根据权利要求1-2任一项所述的有机化合物，其特征在于，所述的L 1或Ar 1分别独立地选自如下结构基团中的一种或多种组合：
    Figure PCTCN2018122488-appb-100003
    其中，
    A 1、A 2、A 3、A 4、A 5、A 6、A 7、A 8分别独立表示CR 501或N；
    Y 1选自CR 502R 503、SiR 504R 505、NR 506、C(＝O)、S或O；
    R 501-R 505是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 3，R 4，R 5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。
  4. 根据权利要求1-3任一项所述的有机化合物，其特征在于，通式(I)中所述的A选自以下所示的结构：
    Figure PCTCN2018122488-appb-100004
    其中，虚线为所示结构与L 1相连接的单键。
  5. 根据权利要求1-4任一项所述的有机化合物，其特征在于，通式(I)中所述的B选自以下所示的结构：
    Figure PCTCN2018122488-appb-100005
    Figure PCTCN2018122488-appb-100006
    其中，虚线为所示结构与L 1相连接的单键。
  6. 根据权利要求1-5任一项所述的有机化合物，其中至少一个H原子被D原子所取代。
  7. 一种高聚物，包含一重复单元，所述重复单元包含如通式(I)所示的结构。
  8. 一种有机混合物，包含至少一种第一有机化合物(H1)和第二有机化合物(H2)，所述第一有机化合物(H1)为如权利要求1-6任一项所述的有机化合物，所述的第二有机化合物(H2)具有电子传输特性，且所述第一有机化合物(H1)与所述第二有机化合物(H2)的摩尔比范围为1:9至9:1。
  9. 根据权利要求8所述的有机混合物，所述的第二有机化合物(H2)包含有氟基、或氰基或包含有以下通式中的任一基团：
    Figure PCTCN2018122488-appb-100007
    其中，
    a是1-3的整数；
    X 1–X 8选自于CR 801或N，并且至少有一个是N；
    Z 1-Z 3为单键或C(R 801) 2或O或S。
    R 801可选自于如下的基团：氢、氘、烷基、烷氧基、氨基、烯、炔、芳烷基、杂烷基、芳基和杂芳基。
  10. 根据权利要求8-9任一项所述的有机混合物，其特征在于，所述的第二有机化合物(H2)具有通式(IV)所示的结构，
    Figure PCTCN2018122488-appb-100008
    其中，
    Z 4，Z 5，Z 6选自于N或CR 901，且Z 4，Z 5，Z 6中至少一个为N原子。
    Ar 13～Ar 15相同或不同的是具有5至40个环原子的芳族或杂芳族环系，或是具有5至40个环原子的芳氧基或杂芳氧基基团，或是具有5至40个环原子的非芳香族基团，或这些体系的组合，其中一个或多个基团可进一步被R 902取代，或R 902可以进一步与所取代的基团形成环系。
    R 901、R 902在每一次出现时，相同或不同的是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。
    b、u、v独立地为1或2或3。
  11. 根据权利8-10中任一所述的有机混合物，其特征在于，通式(IV)中的Ar 13-Ar 15在多次出现时，可相同或不同地选自如下结构基团中的一种或它们的组合：
    Figure PCTCN2018122488-appb-100009
    其中，d是1或2或3或4。
  12. 根据权利8-11中任一所述的有机混合物，其特征在于，所述的第一有机化合物(H1)和第二有机化合物(H2)的升华温度差别不超过30K。
  13. 一种组合物，包含有一种如权利要求1-6任一项所述的有机化合物，或一种如权利要求7所述的高聚物，或一种如权利要求8-12任一项所述有机混合物，及至少一种有机溶剂。
  14. 一种有机电子器件，包含一种如权利要求1-6任一项所述的有机化合物，或一种如权利要求7所述的高聚物，或一种如权利要求8-12任一项所述有机混合物，及至少一种有机溶剂。
  15. 根据权利要求14所述的有机电子器件，其特征在于，所述有机电子器件可选于有机发光二极管、有机光伏电池、有机发光电池、有机场效应管、有机发光场效应管、有机激光器、有机自旋电子器件、有机传感器及有机等离激元发射二极管。
  16. 根据权利要求14-15任一项所述的有机电子器件是一有机电致发光器件，其中至少包含有一发光层，所述的发光层包含有一种如权利要求1-6任一项所述的有机化合物，或一种如权利要求7所述的高聚物，或一种如权利要求8-12任一项所述有机混合物。
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