WO2017100967A1 - 具有电子供体-受体结构的苯并[c]菲类的衍生物、其应用及电致发光器件 - Google Patents

具有电子供体-受体结构的苯并[c]菲类的衍生物、其应用及电致发光器件 Download PDF

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WO2017100967A1
WO2017100967A1 PCT/CN2015/097225 CN2015097225W WO2017100967A1 WO 2017100967 A1 WO2017100967 A1 WO 2017100967A1 CN 2015097225 W CN2015097225 W CN 2015097225W WO 2017100967 A1 WO2017100967 A1 WO 2017100967A1
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substituted
unsubstituted
alkane
benzo
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穆广园
王磊
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武汉尚赛光电科技有限公司
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
    • C07C211/61—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton with at least one of the condensed ring systems formed by three or more rings
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
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    • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
    • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
    • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
    • C07D235/18—Benzimidazoles; Hydrogenated benzimidazoles with aryl radicals directly attached in position 2
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    • 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
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    • C07—ORGANIC CHEMISTRY
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    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials

Definitions

  • the invention belongs to the field of optoelectronic material application technology, and particularly relates to a derivative of benzo[c]phenanthrene having an electron donor-acceptor structure, an application thereof and an electroluminescent device.
  • OLED full color display requires red, blue and green primary color materials.
  • Blue light material has always been the weakest link. Although the use of phosphorescent materials can obtain high-efficiency blue light devices, the cost is high, the light color is poor, the efficiency is greatly reduced under high brightness, and the device is stable. Poor sex.
  • the blue fluorescent material has the characteristics of simple synthesis and purification, light color can be dark blue or even ultraviolet, and the efficiency roll is lowered at high current density. (Zhu M., Yang C., Blue Fluorescent Emitters: Design Tactics and Applications in Organic Light-Emitting Diodes.
  • blue-light fluorescent materials are still a bottleneck in the development of organic light-emitting diodes.
  • Traditional fluorescent materials have carrier imbalance problems, resulting in low device efficiency.
  • the use of strong electron-withdrawing electron groups leads to HOMO and LUMO. The energy level changes, resulting in a high injection barrier, a high turn-on voltage, and low efficiency.
  • the benzo[c]phenanthrene derivatives of the invention have high quantum efficiency, balance electron carrier transport, and have bipolarity, can be widely used in organic light-emitting diodes, and achieve good results.
  • the effect is a new type of material with great commercial value.
  • the present invention provides a class of electron donor-receptors Structure of benzo[c]phenanthrene derivatives, applications thereof and electroluminescent devices.
  • the derivatives are based on benzo[c]phenanthrene.
  • Luminescent material By binding different aromatic amine groups at different positions of benzo[c]phenanthrene or changing the bridge structure, high-efficiency fluorescence with bipolarity is formed.
  • a benzo[c]phenanthrene derivative of the present invention which has the structural formula (I) represented by the following compound I:
  • R 1 to R 4 each independently select a substituted or unsubstituted C 1 -C 20 alkane group, a C 1 -C 20 alkane group, a C 6 -C 65 aromatic group, C 5 -C 65 heterocyclic groups, C 6 -C 65 polycyclic group, C 6 -C 65 arylene group or C 6 -C 65 alkylene aromatic heterocyclic group, m and n are independently selected integers 0 Or 1.
  • R 1 -R 4 is selected from the 2a-2g structure of the formula (II), and R 1 -R 4 may be the same.
  • a and B are selected from the 2h structure of the formula (II).
  • X, R 21 , R 22 , R 23 represent a hydrogen, an anthracene, a halogen atom, a cyano group, a nitro group, a fluorenyl group, a hydroxyl group or a carbonyl group substituted or unsubstituted C 1 -C 20 alkane group, respectively, C 1 - C 20 alkane group, C 6 -C 65 aromatic group, C 6 -C 65 aromatic silane group, substituted or unsubstituted C 6 -C 65 heteroaryl ring group, C 6 -C 65 condensation
  • the cyclic aromatic hydrocarbon group, p represents an integer of 1-9
  • m and n are each independently selected as an integer of 0 or 1
  • * represents a substitution position.
  • the benzo[c]phenanthrene derivative of the present invention the linear or non-linear alkane and alkane of C 1 -C 20 in X, R 21 , R 22 , and R 23 are selected from the group consisting of methyl and ethyl. , propyl, isopropyl, butyl, isobutyl, tert-butyl, etc., or at least one hydrogen atom of the alkane chain is bonded to a halogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, an amine group, a fluorenyl group , substituted by a carbonyl group or the like.
  • the unsubstituted aromatic ring of C 6 -C 65 includes at least one aromatic ring, and two or more square rings are connected by a single bond or a fused ring, such as phenyl, 1-nyl, 2-nyl, 3,5-di Phenylphenyl and the like.
  • Substituted aromatic group comprising at least one hydrogen atom is above C 1 -C linear or non-linear alkanes and substituted aromatic ring of 20, such as C 1 -C 10 alkyl group substituted with (toluene, ethyl Benzene, o-, m-, p-cumyl, methylnaphthalene), halogenated (o-, m-, p-fluorobenzene, fluorinated naphthalene, trifluoromethylbenzene), cyano (cyanobenzene, cyanide) Naphthalene, cyanobiphenyl), C 1 -C 10 alkyl substituted biphenyl group, C 1 -C 10 alkoxy substituted biphenyl group, C 1 -C 10 alkyl substituted naphthalene group, C 1 -C 10 alkoxy substituted naphthalene group.
  • C 1 -C 10 alkyl substituted biphenyl group C
  • the unsubstituted heteroaromatic ring of C 6 -C 65 includes at least one five- or six-membered ring containing one, two, three or four nitrogen, oxygen, phosphorus or sulfur atoms, two or more aromatic rings Linked by a single bond or a fused ring, such as a thiophene group, a benzothienyl group, a pyridyl group, a pyrrole group, an oxazole group, a thiazole group, a thiadiazole group, a triazine group, a diphenyl group Phosphorus group, imidazole group, p-phenylbenzimidazole group, m-phenylbenzimidazole group, carbazole group, anthracene group, quinolyl group, isoquinol group, these impurities
  • the cyclic aromatic ring includes a heterocyclic aromatic ring substituted with at least one linear or non-linear alkane
  • R 1 is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthryl group or a substituted or unsubstituted fluorenyl group, and the substituent of R 1 is a phenyl group, a cyano group, a C 1 - C 5 alkylsilyl or haloalkyl, R 2 is substituted or unsubstituted fluorenyl, substituted or unsubstituted 9,9-dialkylfluorenyl, substituted or unsubstituted 9,9-diarylfluorene a substituted or unsubstituted oxonyl group, a substituted or unsubstituted thioindolyl group, a substituted or unsubstituted dibenzothiophene sulfone group, a substituted or unsubstituted
  • the rights protecting group is exemplified by the following examples, but the groups included in the rights are not limited to the examples given.
  • the organic material of the present invention is used as an electroluminescent layer in an organic electroluminescent device.
  • the present invention also proposes an organic electroluminescent device comprising an organic functional layer containing a compound of the above formula, which is used as a luminescent material in an organic functional layer.
  • the organic material of the present invention has high electroluminescence efficiency and is used as an electroluminescent layer in an organic electroluminescence display.
  • the benzo[c]phenanthrene derivative according to claim 1 which is applied to an electroluminescent layer material in an organic electroluminescence device.
  • a benzophenanthrene unit having a higher quantum yield is selected as a core unit, which has a good rigid structure, and an easily substituted active site can be used to bond with different substituents to obtain a target.
  • the compound has a deep blue color, and due to its core rigid molecular structure, it can form an effective steric hindrance effect with the peripheral modifying group. Therefore, the material has good thermal stability and can satisfy the industrialization of material thermal stability. Sexual requirements.
  • Figure 1 is a graph of luminance-current density-voltage characteristics of compounds 9, 21 and 23 as guest luminescent materials.
  • Figure 3 is an electroluminescence spectrum of compounds 9, 21 and 23 as guest luminescent materials.
  • Example 1 The 9 described in the present invention can be synthesized by the following method.
  • Example 2 9 A device was prepared as a light-emitting layer.
  • ITO (indium tin oxide) glass was ultrasonically cleaned in a cleaning agent and deionized water for 30 minutes. Then, it was vacuum dried for 2 hours (105 ° C), and then ITO (indium tin oxide) glass was placed in a plasma reactor for 5 minutes of oxygen plasma treatment, and transferred to a vacuum chamber to prepare an organic film and a metal electrode, followed by vacuum evaporation.
  • a 10 nm hole injecting material molybdenum trioxide was prepared and then an 80 nm thick hole injecting material was deposited: 4,4'-cyclohexyl bis[N,N-bis(4-methylphenyl)aniline] (TAPC) And then continue on this hole transport layer Continued by vacuum evaporation of a layer of 12nm material 9,10-bis(2-naphthyl)-2-methylindole; 2-methyl-9,10-bis(naphthalen-2-yl)anthracene (MADN) :9, finally, a layer of 1 nm of LiF and 100 nm of Al were evaporated.
  • TAPC 4,4'-cyclohexyl bis[N,N-bis(4-methylphenyl)aniline]
  • Aluminum is used as the cathode of the device.
  • the positive electrode of the direct current is applied to the ITO (indium tin oxide) layer, and the negative electrode is applied to the metal layer to obtain a bright and uniform deep blue light emitted from the ITO (indium tin oxide) layer.
  • the CIE color coordinate is (0.15, 0.07), the starting voltage is 3.2V, the maximum brightness is 22290cd/m 2 , and the maximum current efficiency is 11.94cd/A.
  • the structure of the experimental device was: ITO (indium tin oxide) / TAPC (60 nm) / MADN: wt 6% 9 (12 nm) LiF (1 nm) / Al (100 nm).
  • Example 3 21 of the present invention can be synthesized by the following method.
  • Example 4 21 A device was prepared as a light-emitting layer.
  • ITO (indium tin oxide) glass was ultrasonically cleaned in a cleaning agent and deionized water for 30 minutes. Then, it was vacuum dried for 2 hours (105 ° C), and then ITO (indium tin oxide) glass was placed in a plasma reactor for 5 minutes of oxygen plasma treatment, and transferred to a vacuum chamber to prepare an organic film and a metal electrode, followed by vacuum evaporation.
  • a 10 nm hole injecting material molybdenum trioxide was prepared and then an 80 nm thick hole injecting material was deposited: 4,4'-cyclohexyl bis[N,N-bis(4-methylphenyl)aniline] (TAPC) Then, on the hole transport layer, a 12 nm material of 9,10-bis(2-naphthyl)-2-methylindole; 2-methyl-9,10-bis (naphthalene) is continuously evaporated by vacuum evaporation. -2-yl) fluorene (MADN): 21, and finally a layer of 1 nm of LiF and 100 nm of Al were evaporated.
  • TAPC 4,4'-cyclohexyl bis[N,N-bis(4-methylphenyl)aniline]
  • Aluminum is used as the cathode of the device.
  • the positive electrode of the direct current is applied to the ITO (indium tin oxide) layer, and the negative electrode is applied to the metal layer to obtain a bright and uniform deep blue light emitted from the ITO (indium tin oxide) layer.
  • the CIE color coordinate is (0.15, 0.06), the starting voltage is 3.17V, the maximum brightness is 14680cd/m 2 , and the maximum current efficiency is 12.85cd/A.
  • the structure of the experimental device was: ITO (indium tin oxide) / TAPC (60 nm) / MADN: wt 6% 21 (12 nm) LiF (1 nm) / Al (100 nm).
  • Example 5 23 of the present invention can be synthesized by the following method.
  • Example 6 23 A device was prepared as a light-emitting layer.
  • ITO (indium tin oxide) glass was ultrasonically cleaned in a cleaning agent and deionized water for 30 minutes. Then, it was vacuum dried for 2 hours (105 ° C), and then ITO (indium tin oxide) glass was placed in a plasma reactor for 5 minutes of oxygen plasma treatment, and transferred to a vacuum chamber to prepare an organic film and a metal electrode, followed by vacuum evaporation.
  • a 10 nm hole injecting material molybdenum trioxide was prepared and then an 80 nm thick hole injecting material was deposited: 4,4'-cyclohexyl bis[N,N-bis(4-methylphenyl)aniline] (TAPC) Then, on the hole transport layer, a 12 nm material of 9,10-bis(2-naphthyl)-2-methylindole; 2-methyl-9,10-bis (naphthalene) is continuously evaporated by vacuum evaporation. -2-yl) fluorene (MADN): 23, and finally a layer of 1 nm of LiF and 100 nm of Al were evaporated.
  • TAPC 4,4'-cyclohexyl bis[N,N-bis(4-methylphenyl)aniline]
  • Aluminum is used as the cathode of the device.
  • the positive electrode of the direct current is applied to the ITO (indium tin oxide) layer, and the negative electrode is applied to the metal layer to obtain a bright and uniform deep blue light emitted from the ITO (indium tin oxide) layer.
  • the CIE color coordinate is (0.15, 0.07), the starting voltage is 3.18V, the maximum brightness is 11840cd/m 2 , and the maximum current efficiency is 7.81 cd/A.
  • the structure of the experimental device was: ITO (indium tin oxide) / TAPC (60 nm) / MADN: wt 6% 23 (12 nm) LiF (1 nm) / Al (100 nm).
  • compound 9 represents a broad class of compounds provided by the present invention:
  • R 1 is an aryl group
  • R 2 is an aryl substituted oxonium, hydrazine, thioindole, carbazole
  • R 1 is the same as R 4
  • R 2 is the same as R 3 .
  • the change in the number of R 1 aryl groups, and the change in the R 2 group, the properties of the obtained compound are close, and the fluorescence emission spectrum is between 430 and 460 nm.
  • the current efficiency of the device is between 8-12 cd/A.
  • R 1 is a substituted aryl group
  • R 2 is an aryl-substituted oxonium, anthracene, thioindole, carbazole
  • R 1 Like R 4 , R 2 is the same as R 3 , and in this type of compound, the change in the number of R 1 aryl groups, and the change in the R 2 group, the properties of the obtained compound are close, and the fluorescence emission spectrum is 435- Between 465 nm and the current efficiency of the device is between 8-12 cd/A.
  • Example 7 Structural characterization of Compound 3 provided by the present invention.
  • Example 8 Characterization of 12 structures as described herein.
  • Example 9 Structural characterization of 106 as described herein.
  • Compounds 3, 12 and 106 correspond to a broad class of compounds provided by the present invention, i.e., R 1 is a phenyl group and R 2 is a 2-3 ring fused ring aromatic hydrocarbon.
  • the synthesis method of such a compound can be obtained by substituting N-phenyl-N-naphthalene (or anthracene or phenanthrenyl)amine with 5,8-dibromobenzo[c]phenanthrene by referring to the above-mentioned synthesis method.
  • Example 10 Structural characterization of compound 107 provided by the present invention.
  • Compound 107 corresponds to a broad class of compounds provided by the present invention, i.e., R 1 is phenyl and R 2 is an alkyl substituted 2-3 benzene ring fused ring aromatic hydrocarbon.
  • the synthesis method of this type of compound can be obtained by substituting N-phenyl-N-alkylnaphthalene (or anthracene or phenanthrenyl)amine with 5,8-dibromobenzo[c]phenanthrene by referring to the above-mentioned synthesis method.
  • Example 11 Structural characterization of compound 108 provided by the present invention.
  • Compound 108 corresponds to a broad class of compounds provided by the present invention, i.e., R 1 is phenyl and R 2 is haloalkyl.
  • the synthesis method of this kind of compound can be obtained by substituting N-phenyl-N-haloalkylamine with 5,8-dibromobenzo[c]phenanthrene by referring to the above synthesis method.
  • Example 12 Structural characterization of compound 61 provided by the present invention.
  • Example 13 Structural characterization of compound 68 provided by the present invention.
  • Compounds 61, 68 correspond to a broad class of compounds provided by the present invention, i.e., R 1 is phenyl and R 2 is 9,9-dialkylfluorenyl or 9,9-diarylfluorenyl.
  • the synthesis method of this kind of compound can be obtained by substituting N-phenyl-N-mercaptoamine with 5,8-dibromobenzo[c]phenanthrene by referring to the above synthesis method.
  • Example 14 Structural characterization of compound 70 provided by the present invention.
  • Compound 70 corresponds to a broad class of compounds provided by the present invention, i.e., R 1 is a phenyl or 2-3 benzene ring fused ring aryl group, and R 2 is a thiol or aryl substituted thiol group.
  • the synthesis method of this kind of compound can be obtained by substituting N-aryl-N-thioindenyl (or arylthioindenyl)amine with 5,8-dibromobenzo[c]phenanthrene by referring to the above-mentioned synthesis method.
  • Example 15 Structural characterization of compound 79 provided by the present invention.
  • Compound 79 corresponds to a broad class of compounds provided by the present invention, that is, R 1 is a phenyl or 2-3 benzene ring fused ring aryl group, and R 2 is a dibenzothiophene sulfone group or an aryl group substituted Benzothiophene sulfone group.
  • R 1 is a phenyl or 2-3 benzene ring fused ring aryl group
  • R 2 is a dibenzothiophene sulfone group or an aryl group substituted Benzothiophene sulfone group.
  • Example 16 Structural characterization of compound 109 provided by the present invention.
  • Compound 109 corresponds to a broad class of compounds provided by the present invention, i.e., R 1 is a phenyl or 2-3 benzene ring fused ring aryl group, and R 2 is a carbazolyl or aryl substituted oxazolyl group.
  • the synthesis method of such a compound can be obtained by substituting N-aryl-N-carbazolyl (or arylcarbazolyl)amine with 5,8-dibromobenzo[c]phenanthrene by referring to the above-mentioned synthesis method.
  • Example 17 Structural characterization of 88 of the compounds provided herein.
  • Compound 88 corresponds to a broad class of compounds provided by the present invention, i.e., R 1 is a phenyl or 2-3 benzene ring fused ring aryl group and R 2 is an N-aryl carbazolyl group.
  • the synthesis method of this type of compound can be obtained by substituting N-aryl-N-(N-arylcarbazolyl)amine with 5,8-dibromobenzo[c]phenanthrene by referring to the above synthesis method.
  • Example 18 Structural characterization of compound 103 provided by the present invention.
  • Example 19 Structural characterization of compound 104 provided by the present invention.
  • Example 20 Structural characterization of compound 105 provided by the present invention.
  • Compounds 103, 104, and 105 correspond to a large class of the compounds provided by the present invention, that is, R 1 is a phenyl or 2-3 benzene ring fused ring aryl group, and R 2 is a 2- or 1-position.
  • R 1 is a phenyl or 2-3 benzene ring fused ring aryl group
  • R 2 is a 2- or 1-position.
  • the synthesis method of this kind of compound can be obtained by substituting N-aryl-N-phenylbenzimidazolylamine with 5,8-dibromobenzo[c]phenanthrene by referring to the above synthesis method.
  • Example 21 Characterization of the structure of 110 described in the present invention.
  • Example 22 Structural characterization of compound 40 provided by the present invention
  • Compound 40 embodies a broad class of compounds of the present invention is provided in that: R 1 is phenyl or phenyl substituted by phenyl, R 2 is a phenyl group substituted dibenzofuran.
  • Example 23 Structural characterization of 54 of the compounds provided by the present invention
  • Compound 54 exemplifies a broad class of compounds provided by the present invention, i.e., R 1 is a naphthyl group and R 2 is a phenyl substituted oxonyl group.
  • Example 24 Structural characterization of compound 56 provided by the present invention
  • Compound 56 embodies a broad class of compounds provided by the present invention, i.e., R 1 is a naphthyl or phenyl substituted naphthyl group, and R 2 is a diphenyl substituted oxonyl group.
  • Example 25 Structural Characterization of Compound 58 Provided by the Invention
  • Compound 58 exemplifies a broad class of compounds provided by the present invention, i.e., R 1 is a naphthyl or phenyl substituted naphthyl group, and R 2 is a phenyl substituted oxonyl group.
  • Example 26 Structural characterization of compound 59 provided by the present invention
  • Example 27 Structural characterization of compound 60 provided by the present invention

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Abstract

提供具有电子供体-受体结构的苯并[c]菲类的衍生物、其应用及电致发光器件。该类衍生物以苯并[c]菲为核心，通过在苯并[c]菲的不同位点键联不同的芳香胺基团，或改变桥联结构，形成了具有双极性的高效荧光发光材料。所述荧光发光材料利用苯并菲大芳环的稳定性及共轭性，利用外围基团来调整分子上的电子云分布，能够有效的调整发光特性。

Description

具有电子供体-受体结构的苯并[c]菲类的衍生物、其应用及电致发光器件 技术领域
本发明属于光电材料应用科技领域，具体涉及具有电子供体-受体结构的苯并[c]菲类的衍生物、其应用及电致发光器件。
背景技术
二十一世纪是以信息产业为核心的知识经济时代，其显著特点是信息的数字化和网络化及信息高速公路的建设。自1987年美国柯达公司(Pope M.,Kallmann.H.P.,Magnante.P.,Electroluminescence in Organic Crystals.The Journal of Chemical Physics 1963,38(8):2042-2043)和1990年英国剑桥大学分别推出有机和高分子电致发光材料和器件以来，在材料科学和信息技术领域引起了全世界范围内“现代平板显示技术”的国际竞争。
OLED全彩显示需要红、蓝、绿三原色材料，蓝光材料一直是最薄弱的环节，虽然应用磷光材料可以获得高效的蓝光器件，但成本高，光色差，高亮度下效率滚降严重，器件稳定性较差。蓝光荧光材料则具有合成提纯简单，光色可以到深蓝甚至紫外，高电流密度下效率滚降低等特点。(Zhu M.,Yang C.,Blue Fluorescent Emitters:Design Tactics and Applications in Organic Light-Emitting Diodes.ChemSoc Rev 2013,42(12):4963-4976；Chang Y.T.,Chang J.K.,Lee Y.T.,et al,High-Efficiency Small-Molecule-Based Organic Light Emitting Devices with Solution Processes and Oxadiazole-Based Electron Transport  Materials.ACS Appl Mater Interfaces 2013,5(21):10614-10622)。
目前应用较多的蓝光掺杂剂如苝的衍生物TBP(J.Shi,C.W.Tang,Anthracene Derivatives for Stable Blue-Emitting Organic Electroluminescence Devices.Applied Physics Letters 2002,80(17):3201-3203.)，但由于苝环坚硬和平面结构，容易导致浓度猝灭，掺杂浓度很低。二芳香胺苯乙烯类衍生物DSA-Ph(M.-T.Lee,H.-H.Chen,C.-H.Liao,et al.,Stable Styrylamine-Doped Blue Organic Electroluminescent Device Based on2-Methyl-9,10-Di(2-Naphthyl)Anthracene.Applied Physics Letters 2004,85(15):3301-3303)，掺杂器件效率达到9.7cd/A，但光色只有天蓝CIE(0.16,0.32)。2012年台湾清华大学郑建鸿报道了BCzVBi作为蓝光掺杂剂，电流效率达到了9.7cd/A，CIE(0.14,0.14)(J.-C.Kieffer,B.M.Lee,H.H.Yu,et al.,Highly Efficient Blue Organic Light-Emitting Diodes Using Dual Emissive Layers with Host-Dopant System.Proc.SPIE 2012,8412(841221):1-8)。但光色难以达到深蓝光区域。所以蓝光荧光材料依旧是有机发光二极管发展中的一个瓶颈，传统的荧光发光材料存在着载流子不平衡的问题，导致器件效率偏低，而一般采用强吸拉电子基团会导致HOMO与LUMO能级变化，导致注入势垒偏高，开启电压偏高，效率偏低。
本发明涉及的苯并[c]菲类的衍生物具有很高的量子效率，电子空穴载流子传输平衡，具有双极性，能够广泛应用于有机发光二级管中，并取得良好的效果，是一种具有很大商业价值的新型材料。
发明内容
为解决现有技术的不足，本发明提供了一类具有电子供体-受体 结构的苯并[c]菲类的衍生物、其应用及电致发光器件。该类衍生物以苯并[c]菲为核心，通过在苯并[c]菲的不同位点键联不同的芳香胺基团，或改变桥联结构，形成了具有双极性的高效荧光发光材料。
本发明的苯并[c]菲类的衍生物，其具有以下化合物I所示的结构通式(I)：
Figure PCTCN2015097225-appb-000001
其中R1-R4分别独立选择取代的或未被取代的C1-C20的烷烃基团、C1-C20的烷烃基团、C6-C65的芳香基团、C5-C65的杂环基团、C6-C65的多环基团、C6-C65的亚芳香基团或者C6-C65的亚芳香杂环基团，m和n分别独立选取整数0或者1。
更具体而言，所发明的苯并[c]菲类衍生物，R1-R4选自通式(II)的2a-2g结构，R1-R4可同可不同。A和B选自通式(II)的2h结构。X，R21，R22，R23分别代表氢、氘、卤原子、氰基、硝基、脒基、羟基或羰酰基取代或非取代的C1-C20的烷烃基团，C1-C20的烷烃基团、C6-C65芳香基团、C6-C65的芳香硅烷基团、取代或非取代的C6-C65杂芳环基团、C6-C65缩合多环芳烃基团、，p代表整数1-9，m和n分别独立选取整数0或者1，*代表取代位置。
Figure PCTCN2015097225-appb-000002
上述技术方案所对应的化合物，均在本发明的公开和保护之列。
进一步来说，本发明的苯并[c]菲类衍生物，X、R21，R22，R23中C1-C20的直链或非直链烷烃和烷烃选自甲基、乙基、丙基、异丙基、丁基、异丁基、叔丁基等，或者其烷烃链中至少有一个氢原子被氘原子、卤原子、羟基、硝基、氰基、胺基、脒基，羰酰基等取代。C6-C65的非取代芳香环至少包括一个芳香环，两个或者多个的方香环通过单键或者稠环相连，如苯基、1-奈基、2-奈基、3，5-二苯基苯基等。取代的芳香环基团包括至少有一个氢原子被如上C1-C20的直链或非直链烷烃和烷烃取代的芳香环，如C1-C10烷基取代基团(甲苯，乙基苯，邻、间、对-异丙苯基，甲基萘)，卤代物(邻、间、对-氟苯，氟化萘，三氟甲基苯)，氰基物(氰基苯，氰基萘，氰基联苯)，C1-C10烷基取代联苯基团，C1-C10烷氧基取代联苯基团，C1-C10烷基取代萘基团，C1-C10烷氧基取代萘基团。C6-C65的非取代杂芳香环至少包括一个含有一个、两个、三个或者四个的氮、氧、磷或者硫原子的五元或者六元环，两个或者多个的芳香环通过单键或者稠环相连，如噻吩基团、苯并噻吩基团、吡啶基团、吡咯基团、噁唑基团、噻唑基团、噻 二唑基团、三嗪基团、二苯基磷氧基团、咪唑基团、对苯基苯并咪唑基团、间苯基苯并咪唑基团、咔唑基团、吲哚基团、喹啉基团、异喹啉基团，这些杂环芳香环包括由至少一个氢位置被上述C1-C20的直链或非直链烷烃和硅烷烃取代的杂环芳香环。
优选的，当m+n＝0时，或者当m＝1、n＝0时、A为苯基时，或者当m＝0、n＝1时、B为苯基时：
R1为取代或未取代的苯基、取代或未取代的萘基、取代或未取代的菲基或取代或未取代的蒽基，R1的取代基为苯基、氰基、C1-C5的烷基硅烷基或者卤代烷基，R2为取代或未取代的芴基、取代或未取代的9,9-二烷基芴基、取代或未取代的9,9-二芳基芴基、取代或未取代的氧芴基、取代或未取代的硫芴基、取代或未取代的二苯并噻吩砜基、取代或未取代的咔唑基、取代或未取代的在9位上通过含有1-3个苯环的芳基(当为2或3个苯基时，为稠环芳基)与母体N桥连的9-苯基咔唑、取代或未取代的在9位上通过含有1-3个苯环的芳基与母体N桥连的9-苯基咔唑、取代或未取代的在1位或2位上通过含有1-3个苯环的芳基(当为2或3个苯基时，为稠环芳基)与母体N桥连的2-苯基苯并咪唑、1-苯基苯并咪唑或3苯基苯并咪唑，R2的取代基为1-3个苯环的芳基，其中，R1与R3相同且R2与R4相同，或者R1与R4相同且R2与R3相同。
为直观的体现本发明的技术思量，以以下例证体现权利得保护基团，但权利所包含的基团不局限于所举的实例。
Figure PCTCN2015097225-appb-000003
Figure PCTCN2015097225-appb-000004
Figure PCTCN2015097225-appb-000005
Figure PCTCN2015097225-appb-000006
Figure PCTCN2015097225-appb-000007
Figure PCTCN2015097225-appb-000008
Figure PCTCN2015097225-appb-000009
Figure PCTCN2015097225-appb-000010
本发明的有机材料在有机电致发光器件中用作电致发光层。
本发明还提出了一种有机电致发光器件，其有机功能层中包含上述通式化合物，该类化合物用作有机功能层中的发光材料。
本发明的有机材料具有较高的电致发光效率，在有机电致发光显示器中用作电致发光层。根据权利要求1所述的苯并[c]菲类衍生物的应用于有机电致发光器件中电致发光层材料。
本发明中，选取了具有较高量子产率的苯并菲单元为核心单元，其具有较好的刚性结构，利用易取代的活性位点，可以实现与不同的取代基进行键联，得到目标化合物具有深蓝光色的，同时由于其核心刚性的分子结构，可以与外围的修饰基团形成有效的空间位阻效应，因此，材料具有较好的热稳定性，能够满足产业化对材料热稳定性的要求。
附图说明
图1是化合物9、21和23作为客体发光材料的亮度-电流密度-电压特性曲线图。
图2是化合物9、21和23作为客体发光材料的电流效率-电流密度特性曲线图。
图3是化合物9、21和23作为客体发光材料的电致发光光谱。
具体实施方式
下面结合实施例对本发明做进一步说明。依据本发明的技术实质对以下实施例所作的任何简单修改、等同变化等，仍属于本发明技术方案的保护范围。本发明不限于以下实施例中所述的内容。
实施例1：本发明所述的9可通过下列方法合成。
Figure PCTCN2015097225-appb-000011
于1000ml三口瓶中加入4-溴二苯并呋喃(30g,121.5mmol),苯硼酸(15.6g,127.6mmol),四三苯基膦钯(0.7g,0.61mmol),碳酸钾(41g,297.1mmol),甲苯300ml,乙醇150ml,水150ml,氮气保护 下于80℃反应12h。TLC显示反应完全。旋掉甲苯，乙醇，用二氯甲烷(200ml X 3)萃取水相，合并有机相，无水硫酸钠干燥，浓缩，减压蒸馏得产品4-苯基二苯并呋喃(24.4g，82％收率)
Figure PCTCN2015097225-appb-000012
于500ml三口瓶中加入4-苯基二苯并呋喃(22g,90.2mmol),无水四氢呋喃300ml,置换空气,氮气保护,液氮乙醇降低温度至-78℃,缓慢滴加正丁基锂(2.5mol/L,40ml),滴加完成后升至室温，室温下搅拌2h，重新降至-78℃缓慢滴入碘(25.2g，99.2mmol)的四氢呋喃(100ml)溶液，滴加完成后升至室温搅拌12h。TLC显示反应完全，加水淬灭，旋掉四氢呋喃，加入300ml二氯甲烷溶液，饱和亚硫酸钠水溶液洗，水洗，无水硫酸钠干燥，浓缩得黄色固体产品4-溴-6-苯基二苯并呋喃(26g,78％收率)。
Figure PCTCN2015097225-appb-000013
于500ml三口瓶中加入4-溴-6-苯基二苯并呋喃(26g,70.3mmol),苯胺(16.3g,175.8mmol),Pd2(dba)3(0.32g,0.35mmol),无水甲苯(300ml)氮气保护下于110℃反应12h。TLC显示反应完全，浓缩，减压蒸馏除去过量的苯胺，浓缩液过硅胶过滤，滤液旋干，石油醚洗涤得白色固体N-6-苯基苯并呋喃-4-苯胺(17g,72％收率)。
Figure PCTCN2015097225-appb-000014
于500ml三口瓶中加入N-6-苯基苯并呋喃-4-苯胺(15.8g,46.9mmol),5，8二溴苯并[c]菲(8.0g,22.3mmol),Pd2(dba)3(1g,1.12mmol),叔丁醇钠(6.4g,66.9mmol),无水甲苯(300ml)氮气保护下于110℃反应12h。TLC显示反应完全，浓缩旋掉甲苯，加200ml水，过滤，滤饼用乙醇洗涤，热甲苯洗涤，甲苯重结晶得黄色固体9(8g,41％收率)。1H-NMR:(CDCl3,400MHz):δ(ppm)8.89(d,2H)，8.08(q,4H)，8.02(d,2H)，7.68(m,8H)，7.51(m，12H)，7.24(t,4H)，7.18(t,2H)，7.08(d,4H)，7.00(q,4H).13C-NMR(CDCl3,100MHz):150.6,145.9,145.0,139.5,136.5,135.1,131.0,129.6,129.2,128.9,128.3,127.9,127.6,127.5,126.8,126.6,125.7,124.9,124.2,123.8,122.8,122.4,119.8,118.6,115.3,114.0,113.9,106.4.MS(APCI)(m/z):[M+H+]calcd,894.32；found,894.31.
实施例2：9作为发光层制备器件。
这个实例展示了9作为客体发光材料而制备的电致发光器件的性能验证。ITO(氧化铟锡)玻璃相继在清洗剂和去离子水中以超声波清洗30分钟。然后真空干燥2小时(105℃)，再将ITO(氧化铟锡)玻璃放入等离子反应器中进行5分钟的氧等离子处理，传送到真空室内制备有机膜和金属电极，接着通过真空蒸发的方法制备一层10nm的空穴注入材料三氧化钼接着蒸镀80nm厚的空穴注入材料:4,4'-环己基二[N,N-二(4-甲基苯基)苯胺](TAPC)，然后在此空穴传输层上继 续通过真空蒸镀上一层12nm的材料9,10-二(2-萘基)-2-甲基蒽；2-甲基-9,10-双(萘-2-基)蒽(MADN):9，最后再蒸镀一层1nm的LiF和100nm的Al。
铝作为器件的阴极，将直流电的正极加于ITO(氧化铟锡)层，将负极加于金属层，即可得到从ITO(氧化铟锡)层发出的明亮均匀的深蓝光，CIE色坐标为(0.15,0.07)，启亮电压3.2V，最大亮度为22290cd/m2，最大电流效率为11.94cd/A。本实验器件结构为：ITO(氧化铟锡)/TAPC(60nm)/MADN:wt 6％9(12nm)LiF(1nm)/Al(100nm)。
实施例3：本发明所述的21可通过下列方法合成。
Figure PCTCN2015097225-appb-000015
于1000ml三口瓶中加入4-溴二苯并呋喃(30g,121.5mmol),苯硼酸(15.6g,127.6mmol),四三苯基膦钯(0.7g,0.61mmol),碳酸钾(41g,297.1mmol),甲苯300ml,乙醇150ml,水150ml,氮气保护下于80℃反应12h。TLC显示反应完全。旋掉甲苯，乙醇，用二氯甲烷(200ml X 3)萃取水相，合并有机相，无水硫酸钠干燥，浓缩，减压蒸馏得产品4-苯基二苯并呋喃(24.4g，82％收率)
Figure PCTCN2015097225-appb-000016
于500ml三口瓶中加入4-苯基二苯并呋喃(22g,90.2mmol),无水四氢呋喃300ml,置换空气,氮气保护,液氮乙醇降低温度至-78℃,缓慢滴加正丁基锂(2.5mol/L,40ml),滴加完成后升至室温，室温下搅拌2h，重新降至-78℃缓慢滴入碘(25.2g，99.2mmol)的四氢 呋喃(100ml)溶液，滴加完成后升至室温搅拌12h。TLC显示反应完全，加水淬灭，旋掉四氢呋喃，加入300ml二氯甲烷溶液，饱和亚硫酸钠水溶液洗，水洗，无水硫酸钠干燥，浓缩得黄色固体产品4-溴-6-苯基二苯并呋喃(26g,78％收率)。
Figure PCTCN2015097225-appb-000017
于500ml三口瓶中加入4-溴-6-苯基二苯并呋喃(26g,70.3mmol),间氰基苯胺(18.3g,175.8mmol),Pd2(dba)3(0.32g,0.35mmol),无水甲苯(300ml)氮气保护下于110℃反应12h。TLC显示反应完全，浓缩，减压蒸馏除去过量的苯胺，浓缩液过硅胶过滤，滤液旋干，石油醚洗涤得白色固体N-6-苯基苯并呋喃-4-(3-氰基)苯胺(19g,70％收率)。
Figure PCTCN2015097225-appb-000018
于500ml三口瓶中加入N-6-苯基苯并呋喃-4-(3-氰基)苯胺(17.8g,46.9mmol),5，8二溴苯并[c]菲(8.0g,22.3mmol),Pd2(dba)3(1g,1.12mmol),叔丁醇钠(6.4g,66.9mmol),无水甲苯(300ml)氮气保护下于110℃反应12h。TLC显示反应完全，浓缩旋掉甲苯，加200ml水，过滤，滤饼用乙醇洗涤，热甲苯洗涤，甲苯重结晶得黄色固体21(8.3g,43％收率)。1H-NMR:(CDCl3,400MHz):δ(ppm)8.98(d.2H),8.11(d, 6H),7.66(m,8H),7.49(m,20H),7.18(d,2H),6.97(d,2H)13C-NMR(CDCl3,100MHz):δ(ppm)150.6,145.0,141.6,139.5,136.5,135.1,134.9,132.2,131.0,130.3,129.3,129.2,128.9,128.3,127.9,127.6,127.5,127.4,126.6,124.9,124.2,123.8,122.8,122.4,119.8,118.6,115.3,114.0,113.9,113.5,106.4MS(APCI)(m/z):[M+H+]calcd for 945.32；found,945.32.
实施例4：21作为发光层制备器件。
这个实例展示了21作为客体发光材料而制备的电致发光器件的性能验证。ITO(氧化铟锡)玻璃相继在清洗剂和去离子水中以超声波清洗30分钟。然后真空干燥2小时(105℃)，再将ITO(氧化铟锡)玻璃放入等离子反应器中进行5分钟的氧等离子处理，传送到真空室内制备有机膜和金属电极，接着通过真空蒸发的方法制备一层10nm的空穴注入材料三氧化钼接着蒸镀80nm厚的空穴注入材料:4,4'-环己基二[N,N-二(4-甲基苯基)苯胺](TAPC)，然后在此空穴传输层上继续通过真空蒸镀上一层12nm的材料9,10-二(2-萘基)-2-甲基蒽；2-甲基-9,10-双(萘-2-基)蒽(MADN):21，最后再蒸镀一层1nm的LiF和100nm的Al。
铝作为器件的阴极，将直流电的正极加于ITO(氧化铟锡)层，将负极加于金属层，即可得到从ITO(氧化铟锡)层发出的明亮均匀的深蓝光，CIE色坐标为(0.15,0.06)，启亮电压3.17V，最大亮度为14680cd/m2，最大电流效率为12.85cd/A。本实验器件结构为：ITO(氧化铟锡)/TAPC(60nm)/MADN:wt 6％21(12nm)LiF(1nm)/Al(100nm)。
实施例5：本发明所述的23可通过下列方法合成。
Figure PCTCN2015097225-appb-000019
于500ml三口瓶中加入3-溴-6-苯基二苯并呋喃(26g,70.3mmol),苯胺(17.3g,175.8mmol),Pd2(dba)3(0.32g,0.35mmol),无水甲苯(300ml)氮气保护下于110℃反应12h。TLC显示反应完全，浓缩，减压蒸馏除去过量的苯胺，浓缩液过硅胶过滤，滤液旋干，石油醚洗涤得白色固体N-6-苯基苯并呋喃-3-苯胺(18g,70％收率)。
Figure PCTCN2015097225-appb-000020
于500ml三口瓶中加入N-6-苯基苯并呋喃-3-苯胺(17.8g,46.9mmol),5，8二溴苯并[c]菲(8.0g,22.3mmol),Pd2(dba)3(1g,1.12mmol),叔丁醇钠(6.4g,66.9mmol),无水甲苯(300ml)氮气保护下于110℃反应12h。TLC显示反应完全，浓缩旋掉甲苯，加200ml水，过滤，滤饼用乙醇洗涤，热甲苯洗涤，甲苯重结晶得黄色固体23(8.2g,45％收率)。1H NMR(400MHz,CDCl3)δ[ppm]:8.98(d,2H),8.11(m,8H),7.69(m,20H),7.24(t,4H),7.08(d,4H),7.00(t,2H),6.91(d,2H)；13C NMR(100MHz,CDCl3)δ[ppm]:164.1,145.9,141.2,139.5,137.7,136.5,135.1,131.0,129.6,129.2,128.9,128.4,128.3,127.9,127.6,127.5,126.8,126.6,125.7,123.8,122.8,122.4,121.8,119.8,117.2,114.0,113.9,106.4,103.6.MS(APCI)(m/z):[M+H+]calcd 894.32；found, 894.32.
实施例6：23作为发光层制备器件。
这个实例展示了23作为客体发光材料而制备的电致发光器件的性能验证。ITO(氧化铟锡)玻璃相继在清洗剂和去离子水中以超声波清洗30分钟。然后真空干燥2小时(105℃)，再将ITO(氧化铟锡)玻璃放入等离子反应器中进行5分钟的氧等离子处理，传送到真空室内制备有机膜和金属电极，接着通过真空蒸发的方法制备一层10nm的空穴注入材料三氧化钼接着蒸镀80nm厚的空穴注入材料:4,4'-环己基二[N,N-二(4-甲基苯基)苯胺](TAPC)，然后在此空穴传输层上继续通过真空蒸镀上一层12nm的材料9,10-二(2-萘基)-2-甲基蒽；2-甲基-9,10-双(萘-2-基)蒽(MADN):23，最后再蒸镀一层1nm的LiF和100nm的Al。
铝作为器件的阴极，将直流电的正极加于ITO(氧化铟锡)层，将负极加于金属层，即可得到从ITO(氧化铟锡)层发出的明亮均匀的深蓝光，CIE色坐标为(0.15,0.07)，启亮电压3.18V，最大亮度为11840cd/m2，最大电流效率为7.81cd/A。本实验器件结构为：ITO(氧化铟锡)/TAPC(60nm)/MADN:wt 6％23(12nm)LiF(1nm)/Al(100nm)。
代表性化合物的性能如下表
Figure PCTCN2015097225-appb-000021
Figure PCTCN2015097225-appb-000022
在上述实施例中，
以化合物9为典型，代表了本发明所提供的化合物中一大类：即R1为芳基，R2为芳基取代的氧芴、芴、硫芴、咔唑，R1与R4相同，R2与R3相同，在这一类化合物中，R1芳基的数量的改变，以及R2 基团的改变，得到的化物的性能接近，其荧光发射光谱在430-460nm之间，且器件的电流效率在8-12cd/A之间。
以化合物21、23为典型，代表了本发明所提供的化合物中一大类：即R1为取代的芳基，R2为芳基取代的氧芴、芴、硫芴、咔唑，R1与R4相同，R2与R3相同，在这一类化合物种，R1芳基的数量的改变，以及R2基团的改变，得到的化物的性能接近，其荧光发射光谱在435-465nm之间，且器件的电流效率在8-12cd/A之间。
下面给出进一步的归纳
实施例7：本发明所提供的化合物3的结构表征。
1H-NMR:(CDCl3,400MHz):δ(ppm)8.98(d,2H),8.22(d,2H),8.11(d,2H),7.84(d,2H),7.69(m,8H),7.58(m,8H),7.24(t,4H),7.08(d,4H),7.00(t,2H),13C-NMR(CDCl3,100MHz):δ(ppm)145.9,142.0，139.5，135.1，134.3，129.6，128.9，128.6，128.3，127.6，127.5，126.8，126.6，126.0，125.7，125.0，124.7，122.4，121.0，119.0，114.0，113.9，109.3.
MS(APCI)(m/z):[M+H+]calcd 663.27；found,663.27.
实施例8：本发明所述的12结构表征。
1H-NMR:(CDCl3,400MHz):δ(ppm)8.98(d,3H)，8.84(d,2H),8.64(d,1H),8.11(d,3H),7.92(m,4H),7.68(m,13H),7.49(s,2H),7.24(t,4H),7.08(d,4H)，7.00(t,2H).13C-NMR(CDCl3,100MHz):145.9,141.4,139.7,139.4,135.1,134.2,133.3,132.3,131.4,130.8,129.6,128.3,127.5,127.0,126.8,126.6,125.8,125.7,122.8,122.4,122.0,120.7,116.8,114.9,113.9,113.2.MS(APCI)(m/z):[M+H+]calcd 763.30；found, 763.30.
实施例9：本发明所述的106结构表征。
1H-NMR:(CDCl3,400MHz):δ(ppm)8.98(d,2H)，8.61(s,1H),8.49(s,1H),8.15(m,4H),8.04(m,5H),7.90(s,1H),7.71(m,6H),7.53(m,6H),7.24(t,5H),7.17(d,1H),7.08(d,4H),7.00(t,2H).13C-NMR(CDCl3,100MHz):145.9,142.1,140.2,139.7,139.4,135.1,132.3,132.1130.8,129.6,128.3,128.2,128.1,127.0,126.8,126.6,125.9,125.7,125.6,125.4,124.9,122.8,122.4,122.1,121.2,119.2,118.8,118.0,117.2,114.9,113.9,113.2,108.8.[M+H+]calcd 763.30；found,763.30.
化合物3、12和106对应了本发明所提供的化合物中的一大类，即：R1为苯基，R2为2-3个苯环的稠环芳烃。这一类化合物的合成方法可参考上述的合成方法，通过N-苯基-N-萘(或蒽或菲)基胺与5，8二溴苯并[c]菲取代得到。
实施例10：本发明所提供的化合物107的结构表征。
1H-NMR:(CDCl3,400MHz):δ(ppm)8.98(d,2H),8.11(s,2H),7.97(s,1H),7.90(s,1H),7.80(d,1H),7.68(t,1H),7.24(m,7H),6.60(m,7H),3.20(s,1H),2.83(q,2H),1.24(t,3H).13C-NMR(CDCl3,100MHz):145.9,141.5,141.0,139.7,135.9,135.1,134.2,132.3,130.8,129.6,128.3,127.9,127.4,126.8,126.7,126.6,125.7,123.4,122.8,122.7,122.4,121.9,120.2,118.4,114.0,113.2,111.3,109.0,108.2,43.1,28.6,14.5.[M+H+]calcd579.27；found,579.27.
化合物107对应了本发明所提供的化合物中的一大类，即：R1 为苯基，R2为烷基取代的2-3个苯环的稠环芳烃。这一类化合物的合成方法可参考上述的合成方法，通过N-苯基-N-烷基萘(或蒽或菲)基胺与5，8二溴苯并[c]菲取代得到。
实施例11：本发明所提供的化合物108的结构表征。
1H-NMR:(CDCl3,400MHz):δ(ppm)8.98(d,2H),8.11(d,2H),7.69(m,6H),7.40(t,4H),7.33(d,4H),7.06(t,2H),5.86(d,4H).13C-NMR(CDCl3,100MHz):149.1,141.1,135.1,129.6,128.3,127.5,126.6,125.3,122.4,121.9,119.1,115.1,110.4,104.1.[M+H+]calcd 475.19；found,475.19.
化合物108对应了本发明所提供的化合物中的一大类，即：R1为苯基，R2为卤代烷基。这一类化合物的合成方法可参考上述的合成方法，通过N-苯基-N-卤代烷基胺与5，8二溴苯并[c]菲取代得到。
实施例12：本发明所提供的化合物61的结构表征。
1H-NMR:(CDCl3,400MHz):δ(ppm)8.98(d.2H),8.11(d,2H),7.90(m,4H),7.66(m,5H),7.53(m,4H),7.35(m,3H),7.28(m,7H),7.16(d,1H),7.04(m,6H),1.69(s,12H)13C-NMR(CDCl3,100MHz):δ(ppm)148.7,147.8,145.9,142.2,141.9,141.0,140.3,139.7,139.4,138.9,135.4,135.1,132.3,130.8,129.6,128.3,127.4,127.0,126.8,126.7,126.6,125.7,123.2,122.8,122.4,122.1,121.6,121.5,121.0,120.7,114.9,113.9,113.2,45.5,30.9[M+H+]calcd 795.37；found,795.37.
实施例13：本发明所提供的化合物68的结构表征。
1H-NMR:(CDCl3,400MHz):δ(ppm)8.98(d.2H),8.11(d,2H),7.90(m,2H),7.61(m,12H),7.38(t,2H),7.20(m,34H)13C-NMR(CDCl3,100 MHz):δ(ppm)147.7,145.9,141.9,141.0,139.5,138.9,136.3,131.9,129.8,129.6,129.2,128.9,128.7,128.3,128.1,127.5,127.4,126.8,126.6,126.2,125.7,122.4,121.5,114.0,62.9[M+H+]calcd1043.43；found,1043.43.
化合物61、68对应了本发明所提供的化合物中的一大类，即：R1为苯基，R2为9,9-二烷基芴基或9,9-二芳基芴基。这一类化合物的合成方法可参考上述的合成方法，通过N-苯基-N-芴基胺与5，8二溴苯并[c]菲取代得到。
实施例14：本发明所提供的化合物70的结构表征。
1H-NMR:(CDCl3,400MHz):δ(ppm)8.98(d.2H),8.45(d,2H),7.90(m,5H),7.66(m,11H),7.25(m,8H),7.06(m,6H)13C-NMR(CDCl3,100MHz):δ(ppm)145.9,142.8,140.8,139.7,139.4,137.5,137.4,135.1,134.3,132.3,130.8,129.9,129.6,128.3,127.5,127.0,126.8,126.6,126.4,125.7,124.4,124.3,124.3,124.1,123.7,123.2,122.8,122.4,119.7,117.4,117.3,116.8,115.6,114.9,113.9,113.2.[M+H+]calcd775.22；found,775.22.
化合物70对应了本发明所提供的化合物中的一大类，即：R1为苯基或2-3苯环的稠环芳基，R2为硫芴基或芳基取代的硫芴基。这一类化合物的合成方法可参考上述的合成方法，通过N-芳基-N-硫芴基(或芳基硫芴基)胺与5，8二溴苯并[c]菲取代得到。
实施例15：本发明所提供的化合物79的结构表征。
1H-NMR:(CDCl3,400MHz):δ(ppm)8.98(d.2H),8.20(d,3H),8.11(d, 2H),7.90(m,4H),7.66(m,11H),7.35(d,1H),7.27(m,7H),7.06(m,6H)13C-NMR(CDCl3,100MHz):δ(ppm)146.8,146.4,145.9,140.8,139.7,139.4,138.5,137.6,135.1,134.2,132.3,132.0,131.6,130.8,130.7,129.8,129.7,129.6,129.3,129.2,128.6,128.3,127.0,126.8,126.6,125.7,125.1,122.8,122.6,122.4,122.0,121.7,114.9,113.9,113.2.[M+H+]calcd839.20；found,839.20.
化合物79对应了本发明所提供的化合物中的一大类，即：R1为苯基或2-3苯环的稠环芳基，R2为二苯并噻吩砜基或芳基取代的二苯并噻吩砜基。这一类化合物的合成方法可参考上述的合成方法，通过N-芳基-N-二苯并噻吩砜基(或芳基二苯并噻吩砜基)胺与5，8二溴苯并[c]菲取代得到。
实施例16：本发明所提供的化合物109的结构表征。
1H-NMR:(CDCl3,400MHz):δ(ppm)8.98(d.2H),8.20(d,3H),8.11(d,2H),7.90(s,1H),7.66(m,6H),7.49(s,1H),7.35(m,15H),7.06(m,6H)13C-NMR(CDCl3,100MHz):δ(ppm)145.9,139.7,139.4,136.4,135.7,135.1,134.8,133.9,132.7,132.3,130.8,129.6,129.4,128.3,127.0,126.8,126.6,125.7,122.8,122.4,121.7,121.4,119.8,119.7,117.7,115.8,114.9,113.9,113.7,113.5,1132,111.1,111.0,109.9,103.9,97.8.[M+H+]calcd 741.29；found,741.29.
化合物109对应了本发明所提供的化合物中的一大类，即：R1为苯基或2-3苯环的稠环芳基，R2为咔唑基或芳基取代的咔唑基。这一类化合物的合成方法可参考上述的合成方法，通过N-芳基-N-咔唑基(或芳基咔唑基)胺与5，8二溴苯并[c]菲取代得到。
实施例17：本发明所提供的化合物的88的结构表征。
1H NMR(400MHz,CDCl3)δ[ppm]:8.96(d,2H),8.19(d,2H),8.11(d,2H),8.01(s,1H),7.96(d,1H),7.90(s,1H),7.68(m,16H),7.4(d,2H),7.24(m,9H),7.08(d,4H),7.00(t,2H),6.48(d,1H),6.4(d,1H)；13C NMR(100MHz,CDCl3)δ[ppm]:146.3,145.9,139.8,139.7,139.4,136.8,135.1,134.8,134.0,132.7,132.3,131.8,130.8,129.9,129.6,129.3,128.3,127.0,126.8,126.6,125.7,125.5,122.8,122.4,121.4,119.8,119.7,115.8,114.9,113.9,113.7,113.2,112.0,111.0,110.0,109.5,103.9.[M+H+]calcd893.36；found,893.36.
化合物88对应了本发明所提供的化合物中的一大类，即：R1为苯基或2-3苯环的稠环芳基，R2为N-芳基咔唑基。这一类化合物的合成方法可参考上述的合成方法，通过N-芳基-N-(N-芳基咔唑基)胺与5，8二溴苯并[c]菲取代得到。
实施例18：本发明所提供的化合物103的结构表征。
1H NMR(400MHz,CDCl3)δ[ppm]:8.98(d,2H),8.56(d,2H),8.11(d,2H),8.01(d,4H),7.81(d,2H),7.69(m,8H),7.53(m,6H),7.38(d,4H),7.28(m,10H),7.08(d,4H),7.00(t,2H)；13C NMR(100MHz,CDCl3)δ[ppm]:149.4,145.9,144.0,139.5,138.2,137.6,135.1,129.6,128.9,128.4,128.3,128.2,127.5,126.8,126.6,125.7,123.2,123.0,122.4,122.1,120.1,114.0,113.9,112.1.[M+H+]calcd947.38；found,947.38.
实施例19：本发明所提供的化合物104的结构表征。
1H NMR(400MHz,CDCl3)δ[ppm]:8.98(d,2H),8.56(d,2H),8.11(d, 2H),7.94(d,2H),7.81(d,2H),7.69(m,16H),7.38(d,4H),7.28(m,8H),7.18(d,2H),7.08(d,4H),7.00(t,2H)；13C NMR(100MHz,CDCl3)δ[ppm]:149.4,145.9,144.0,141.4,139.5,138.2,135.1,131.5,130.6,130.1,129.6,128.9,128.3,127.5,126.8,126.6,125.7,123.0,122.4,122.1,121.9,120.6,120.1,114.0,113.9,112.1.[M+H+]calcd947.38；found,947.38.
实施例20：本发明所提供的化合物105的结构表征。
1H NMR(400MHz,CDCl3)δ[ppm]:8.98(d,2H),8.56(d,2H),8.11(d,2H),8.02(d,2H),7.81(d,2H),7.69(m,14H),7.38(m,16H),7.08(d,4H),7.00(t,2H)；13C NMR(100MHz,CDCl3)δ[ppm]:149.4,145.9,144.0,140.1,139.5,138.2,135.1,129.6,128.9,128.3,128.2,127.5,126.8,126.6,125.7,125.6,123.6,123.2,123.0,122.4,122.1,120.1,115.5,114.0,113.9,112.1.[M+H+]calcd947.38；found,947.38.
化合物103、104、105对应了本发明所提供的化合物中的一大类，即：R1为苯基或2-3苯环的稠环芳基，R2为2位或1位上通过含有1-3个苯环的芳基与母体N桥连的1-苯基苯并咪唑或2-苯基苯并咪唑。这一类化合物的合成方法可参考上述的合成方法，通过N-芳基-N-苯基苯并咪唑基胺与5，8二溴苯并[c]菲取代得到。
实施例21：本发明所述的110结构表征。
1H NMR(400MHz,CDCl3)δ[ppm]:8.98(d,2H),8.56(d,4H),8.11(d,2H),8.01(d,8H),7.81(d,4H),7.69(m,10H),7.53(m,12H),7.38(d,8H),7.28(m,12H)；13C NMR(100MHz,CDCl3)δ[ppm]:149.4,145.9,144.0,139.5,138.2,137.6,135.1,129.6,128.9,128.4,128.3,128.2, 127.5,126.6,123.2,123.0,122.4,122.1,120.1,114.0,113.9,112.1.[M+H+]calcd1332.52；found,1332.52.
实施例22：本发明所提供的化合物40的结构表征
1H NMR(400MHz,CDCl3)δ[ppm]:8.98(d,2H),8.10(m,8H),7.64(m,8H),7.51(m,22H),7.28(t,2H),7.14(m,6H),7.08(m,2H)；13C NMR(100MHz,CDCl3)δ[ppm]:150.6,145,140.5,139.7,139.5,136.5,135.1,131,129.2,128.9,128.5,128.3,127.9,127.6,127.5,126.6,125.3,124.9,124.2,123.8,123.6,123.2,122.8,122.4,119.8,118.6,115.3,114,113.9,106.4.[M+H+]calcd1047.39；found,1047.39.
化合物40体现了本发明所提供的化合物中的一大类，即：R1为苯基或苯基取代的苯基，R2为苯基取代的氧芴基。
实施例23：本发明所提供的化合物的54的结构表征
1H NMR(400MHz,CDCl3)δ[ppm]:8.98(d,2H),8.10(m,10H),7.81(m,2H),7.51(m,28H),7.28(t,2H),6.97(d,2H)；13C NMR(100MHz,CDCl3)δ[ppm]:150.6,145,142,139.5,136.5,135.1,134.3,131,129.2,128.9,128.6,128.3,127.9,127.6,127.5,126.6,126.0,125.0,124.9,124.7,124.2,123.8,122.8,122.4,121,119.8,119,118.6,115.3,114,113.9,109.3,106.4.[M+H+]calcd995.36；found,995.36.
化合物54体现了本发明所提供的化合物中的一大类，即：R1为萘基，R2为苯基取代的氧芴基。
实施例24：本发明所提供的化合物56的结构表征
1H NMR(400MHz,CDCl3)δ[ppm]:8.98(d,2H),8.32(s,2H),8.21(m, 6H),8.08(m,8H),7.51(m,40H),7.08(m,4H)；13C NMR(100MHz,CDCl3)δ[ppm]:145,141.2,140.9,139.7,139.5,137.3,136.8,136.5,135.1,133.2,131,129.2,128.9,128.8,128.6,128.3,127.9,127.6,127.5,126.6,126,125.2,125,123.8,122.8,122.4,121.5,121,119.8,119.5,118.8,116.5,114,113.9,113.5,106.4.[M+H+]calcd1300.48；found,1300.48.
化合物56体现了本发明所提供的化合物中的一大类，即：R1为萘基或苯基取代的萘基，R2为二苯基取代的氧芴基。
实施例25：本发明所提供的化合物58结构表征
1H NMR(400MHz,CDCl3)δ[ppm]:8.98(m,2H),8.20(m,2H),8.11(m,2H),8.08(m,2H),8.02(m,3H),7.90(d,1H),7.68(m,3H),7.62(m,4H),7.50(m,9H),7.46(m,4H),7.43(m,5H),7.24(m,2H),7.24(m,2H),7.08(m,4H),7(m,3H),13C NMR(100MHz,CDCl3)δ[ppm]:150.6,145.9,145.0,140.9,139.7,139.4,136.5,135.1,133.2,131.0,130.8,129.6,129.2,128.6,128.3,127.9,127.6,127.0,126.8,126.6,126.0,125.7,125.0,124.9,124.2,123.8,122.8,122.4,121.5,121.0,119.8,119.5,118.8,118.6,115.3,114.9,113.9,106.4.[M+H+]calcd1021.37；found,1021.37.
化合物58体现了本发明所提供的化合物中的一大类，即：R1为萘基或苯基取代的萘基，R2为苯基取代的氧芴基。
实施例26：本发明所提供的化合物59的结构表征
1H NMR(400MHz,CDCl3)δ[ppm]:8.98(m,2H),8.46(d,1H),8.27(m,1H),8.22(m,2H),8.15(m,2H),8.08(m,2H),8.03(m,3H),7.81(m, 1H),7.72(m,3H),7.64(m,5H),7.58(m,3H),7.52(m,10H),7.46(m,9H),7.37(m,2H),7.28(m,2H),7.08(m,2H),6.97(m,2H),13C NMR(100MHz,CDCl3)δ[ppm]:150.6,145.0,144.8,142.0,140.9,139.7,136.5,136.4,134.7,134.3,133.8,133.2,132.3,132.0,131.0,130.8,129.2,128.8,128.6,128.3,127.9,127.6,126.6,126.0,125.2,125.0,124.9,124.7,124.2,123.8,123.2,122.4,121.5,121.3,121.0,119.8,119.5,119.0,118.8,118.6,118.4,117.1,115.3,113.2,109.3,106.4.[M+H+]calcd1247.42；found,1147.42.
实施例27：本发明所提供的化合物60的结构表征
1H NMR(400MHz,CDCl3)δ[ppm]:8.98(m,3H),8.46(d,1H),8.31(m,4H),8.15(m,2H),8.08(m,2H),8.02(m,2H),7.81(m,3H),7.72(s,1H),7.68(m,2H),7.64(m,5H),7.58(m,6H),7.51(m,9H),7.41(m,4H),7.37(m,4H),7.28(m,2H),6.97(m,2H),13C NMR(100MHz,CDCl3)δ[ppm]:150.6,145.0,142.0,139.7,137.0,136.9,136.5,136.4,134.7,134.3,133.6,133.1,132,3,132.0,131.0,130.8,129.6,129.2,128.8,128.6,128.0,127.9,127.7,127.6,126.3,126.0,125.0,124.9,124.7,123.8,123.2,122.8,122.4,121.3,121.0,119.8,119.0,118.6,118.4,117.1,115.3,113.2,109.3,106.4.[M+H+]calcd1223.45；found,1223.45.
化合物59体现了本发明所提供的化合物中的一大类，即：R1为苯基取代的萘基，R3为萘基，R2和R4为苯基取代的氧芴基，m+n＝1，N与母体通过芳基桥连。
器件性能列表
Figure PCTCN2015097225-appb-000023
Figure PCTCN2015097225-appb-000024
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (7)

  1. 具有电子供体-受体结构的苯并[c]菲类的衍生物，其特征在于，具有以下所示的通式(I)的结构：
    Figure PCTCN2015097225-appb-100001
    其中，R1、R2、R3和R4分别独立的为取代的或未被取代的C1-C20的烷烃基团、C1-C20的硅烷烃基团、C6-C65的芳香基团、C5-C65的杂环基团、C6-C65的多环基团、C6-C65的亚芳香基团或者C6-C65的亚芳香杂环基团，m和n分别独立选取整数0或者1。
  2. 根据权利要求1所述的具有电子供体-受体结构的苯并[c]菲类的衍生物，其特征在于：R1、R2、R3和R4分别独立的选自通式(II)中的2a-2g中的结构，R1-R4相同或不同，A和B分别独立的为通式(II)中的2h结构，X、R21、R22和R23分别独立的为氢、氘、卤素、氰基、硝基、脒基、羟基或羰酰基取代的或非取代的C1-C20的烷烃基团、C1-C20的硅烷烃基团、取代或非取代的C6-C65芳香基团、C6-C65的芳香硅烷基团、取代或非取代的C6-C65杂芳环基团或C6-C65缩合多环芳烃基团，p选自整数1-9，m和n分别独立的选取整数0或者1，*代表取代位置，
    Figure PCTCN2015097225-appb-100002
    Figure PCTCN2015097225-appb-100003
  3. 根据权利要求2所述的具有电子供体-受体结构的苯并[c]菲类的衍生物，其特征在于，X、R21、R22和R23中：
    C1-C20的烷烃基团中的直链或非直链烷烃和C1-C20的烷烃基团分别选自甲基、乙基、丙基、异丙基、丁基、异丁基或叔丁基，或者，C1-C20的烷烃基团中的直链或非直链烷烃和C1-C20的烷烃基团中至少有一个氢原子被氘原子、卤原子、羟基、硝基、氰基、胺基、脒基或羰酰基取代；
    非取代的C6-C65芳香基团至少包括一个芳香环，当包括多个芳香环时，任意两个芳香环之间通过单键相连或直接稠合；
    取代的C6-C65芳香基团包括至少一个有至少一个氢原子被直链或非直链的C1-C20的烷烃基团或C1-C20的硅烷烃基团取代的芳香环，直链或非直链烷烃和C1-C20的硅烷烃基团分别选自甲基、乙基、丙基、异丙基、丁基、异丁基或叔丁基，或者，C1-C20的烷烃基团中的直链或非直链烷烃和C1-C20的硅烷烃基团中至少有一个氢原子被氘原子、卤原子、羟基、硝基、氰基、胺基、脒基或羰酰基取代；
    非取代的C6-C65杂芳环基团至少包括一个含有一个、两个、三个或者四个的氮、氧、磷或者硫原子的五元或者六元环，当包括多个杂芳环时，任意两个杂芳环之间通过单键相连或直接稠合；
    非取代的C6-C65杂芳环基团包括至少一个有至少一个氢被C1-C20的直链或非直链烷烃或硅烷烃取代的杂环芳香环，直链或非直链烷烃和C1-C20的硅烷烃基团分别选自甲基、乙基、丙基、异丙基、丁基、异丁基或叔丁基，或者，C1-C20的烷烃基团中的直链和非直链烷烃或C1-C20的硅烷烃基团中至少有一个氢原子被氘原子、卤原子、羟基、硝基、氰基、胺基、脒基或羰酰基取代。
  4. 根据权利要求3所述的具有电子供体-受体结构的苯并[c]菲类的衍生物，其特征在于，当m+n＝0时，或者当m＝1、n＝0时、A为苯基时，或者当m＝0、n＝1时、B为苯基时：
    R1为取代或未取代的苯基、取代或未取代的萘基、取代或未取代的菲基或取代或 未取代的蒽基，R1的取代基为苯基、氰基、C1-C5的烷基硅烷基或者卤代烷基，R2为取代或未取代的芴基、取代或未取代的9,9-二烷基芴基、取代或未取代的9,9-二芳基芴基、取代或未取代的氧芴基、取代或未取代的硫芴基、取代或未取代的二苯并噻吩砜基、取代或未取代的咔唑基、取代或未取代的在9位上通过含有1-3个苯环的芳基与母体N桥连的9-苯基咔唑、取代或未取代的在9位上通过含有1-3个苯环的芳基与母体N桥连的9-苯基咔唑、取代或未取代的在1位或2位上通过含有1-3个苯环的芳基与母体N桥连的2-苯基苯并咪唑或1-苯基苯并咪唑，R2的取代基为1-3个苯环的芳基，其中，R1与R3相同且R2与R4相同，或者R1与R4相同且R2与R3相同。
  5. 根据权利要求3或4所述的具有电子供体-受体结构的苯并[c]菲类的衍生物，其特征在于，衍生物如下所示：
    Figure PCTCN2015097225-appb-100004
    Figure PCTCN2015097225-appb-100005
    Figure PCTCN2015097225-appb-100006
    Figure PCTCN2015097225-appb-100007
    Figure PCTCN2015097225-appb-100008
    Figure PCTCN2015097225-appb-100009
    Figure PCTCN2015097225-appb-100010
    Figure PCTCN2015097225-appb-100011
  6. 一种根据权利要求1至5任一所述的具有电子供体-受体结构的苯并[c]菲类的衍生物的应用，其特征在于，用于有机电致发光器件中电致发光层材料。
  7. 一种电致发光器件，包含一对电极和设置在该对电极之间的有机发光介质，其特征在于，所述有机发光介质中至少含有一种权利要求1至5任一所述的具有电子供体受体结构的苯并[c]菲类的衍生物。
PCT/CN2015/097225 2015-12-14 2015-12-14 具有电子供体-受体结构的苯并[c]菲类的衍生物、其应用及电致发光器件 WO2017100967A1 (zh)

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