CN110734440B - 一种咪唑取代螺芴类化合物及其应用 - Google Patents
一种咪唑取代螺芴类化合物及其应用 Download PDFInfo
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- CN110734440B CN110734440B CN201810794029.XA CN201810794029A CN110734440B CN 110734440 B CN110734440 B CN 110734440B CN 201810794029 A CN201810794029 A CN 201810794029A CN 110734440 B CN110734440 B CN 110734440B
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
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- 229910052698 phosphorus Inorganic materials 0.000 description 2
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- XDBHWPLGGBLUHH-UHFFFAOYSA-N (3-cyanophenyl)boronic acid Chemical compound OB(O)C1=CC=CC(C#N)=C1 XDBHWPLGGBLUHH-UHFFFAOYSA-N 0.000 description 1
- PQMFVUNERGGBPG-UHFFFAOYSA-N (6-bromopyridin-2-yl)hydrazine Chemical compound NNC1=CC=CC(Br)=N1 PQMFVUNERGGBPG-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
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- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000012863 analytical testing Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
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- 239000001045 blue dye Substances 0.000 description 1
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- 229910052796 boron Inorganic materials 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Inorganic materials [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 1
- 150000001716 carbazoles Chemical group 0.000 description 1
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
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- 239000007850 fluorescent dye Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Inorganic materials [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 1
- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/10—Spiro-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6561—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing systems of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring or ring system, with or without other non-condensed hetero rings
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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
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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Abstract
本发明保护一种咪唑取代螺芴类化合物及其应用,公开了下述通式化合物:X1~X4选自CR4或N,R4选自氢、C1‑C10烷基、取代或未取代的C6‑C15的芳基、取代或未取代的C3‑C15的杂芳基;R1~R3选自氢、C1‑C10烷基、取代或未取代的C6‑C15的芳基、取代或未取代的C3‑C15的杂芳基;R1~R3各自独立地与相连接的苯环稠合形成C9~C30芳基或杂芳基;m、n为0~4的整数,p为0~3的整数;L1、L2选自单键、取代或未取代的C6‑C30的亚芳基、取代或未取代的C3‑C30的亚杂芳基;Ar1、Ar2选自氢、取代或未取代的C6‑C30的芳基、取代或未取代的C3‑C30的杂芳基。本发明的化合物作为OLED器件中的发光材料或作为电子传输材料时,表现出优异的器件性能和稳定性。本发明同时保护采用上述通式化合物的有机电致发光器件。
Description
技术领域
本发明涉及一种新型通式化合物,具体说涉及一种咪唑取代螺芴类有机化合物,其可以用作有机电致发光器件的发光层主体材料或者电子传输材料,本发明还涉及采用该化合物的有机电致发光器件。
背景技术
自从华裔科学家邓青云教授首次报道了有机化合物的电致发光现象后,有机电致发光二极管(OLEDs)具有自发光、高对比度、低功耗等诸多优点而引起了广泛关注。
目前,在显示与照明领域的有机电致发光器件结构中,一般都采用蓝色荧光搭配红、绿色磷光材料使用。常见电致发光器件的发光层主要采用主客体掺杂方式来调节其光色、亮度与效率,进而改善器件性能。
在J.Mater.Chem.C,2015,3,9053—9056以及Organic Letters 37(2016)108-114中,报道了一系列基于螺芴的主体材料,其用作磷光染料的主体时,显示了较好的器件性能。但是在该系列报道中,螺芴单元与咔唑类基团相连,该系列材料为空穴型的主体材料,器件的外量子效率以及仍有待提高。此外专利CN106866499A里类似的螺芴衍生物被当做空穴传输材料使用。
由于大多数有机材料的空穴传输能力大于电子传输能力,具有良好电子传输与注入能力的电子传输材料目前依然比较缺少。此外,常见的主体材料由于较宽的带隙以及偏空穴单极传输性质,激子注入能垒较高且会导致高电压下激子复合区域的偏离进而造成电致发光光谱不稳定、效率滚降严重等。因此开发具有一定电子传输能力的主体以及电子传输材料,在提高注入降低开启电压、提高发光效率、降低效率滚降等方面有着重要的意义。
现有的有机电致发光材料在发光性能方面还有很大改进余地,业界亟需开发新的有机电致发光材料。
发明内容
本发明的目的是解决上述现有技术中电子传输能力较弱、载流子传输不均衡的问题,提出一种电子传输能力良好的新型通式化合物,同时提供一种采用此类新型化合物的有机电致发光器件。
本发明提供了一种通式化合物,具有如下式(1)所示的结构式:
在通式(1)中:
X1~X4分别独立选自CR4或N,R4选自氢、C1-C10烷基、取代或未取代的C6-C15的芳基、取代或未取代的C3-C15的杂芳基中的一种;
R1~R3彼此相同或不同,分别独立选自以下基团:氢、C1-C10烷基、取代或未取代的C6-C15的芳基、取代或未取代的C3-C15的杂芳基;R1~R3各自独立地与相连接的苯环稠合形成C9~C30芳基或杂芳基,所形成的芳基或杂芳基任选地被0、1、2、3、4或5个各自独立地选自取代或未取代的C1~C12烷基、卤素、氰基、硝基、羟基、硅烷基、取代或未取代的C6~C30芳基、取代或未取代的C3~C30杂芳基中的取代基所取代;
m、n彼此相同或不同,且各自独立地为0~4的整数,p为0~3的整数;
L1、L2各自独立地选自单键、取代或未取代的C6-C30的亚芳基、取代或未取代的C3-C30的亚杂芳基,L1、L2优选为亚苯基;
Ar1、Ar2各自独立地选自氢、取代或未取代的C6-C30的芳基、取代或未取代的C3-C30的杂芳基。
当上述基团存在取代基时,所述取代基分别独立地选自卤素、氰基、C1-C10的烷基或环烷基、C2-C6的烯基或环烯基、C1-C6的烷氧基或硫代烷氧基、C6-C30的芳基、C3-C30的杂芳基。
具体说,当定义上述L1、L2和Ar1、Ar2分别独立选自芳基时,是指选自具有一定数目环骨架碳原子的芳族环系,包括单环结构取代基团例如苯基等,也包括共价连接结构的芳环取代基团例如联苯基、三联苯基等。
具体说,当定义上述L1、L2和Ar1、Ar2分别独立选自杂环芳基时是指包含一个或多个选自B、N、O、S、P(=O)、Si和P的杂原子且具有环碳原子的单环或稠环芳基。
进一步的,本发明的通式(1)优选为下述通式(2-1)至式(2-12):
式(2-1)至式(2-12)中,L1和L2、Ar1和Ar2的定义与在通式(1)中定义相同;
m1、n1彼此相同或不同,且各自独立地为0~6的整数;
R4~R5彼此相同或不同,分别独立选自以下基团:氢、C1-C10烷基、取代或未取代的C6-C15的芳基、取代或未取代的C3-C15的杂芳基。
进一步的,上述通式(1)和通式(2-1)至(2-12)中,L1、L2各自独立地选自以下基团:
进一步的,上述式(1)、式(2-1)至式(2-12)中,Ar1、Ar2各自独立地选自以下基团:
更进一步的,Ar1、Ar2各自独立地优选自下述的受体基团:取代或未取代的三嗪基团、取代或未取代的嘧啶基团、取代或未取代的吡啶基团、取代或未取代的喹唑啉基团、取代或未取代的异喹唑啉基团、取代或未取代的咔唑基团、取代或未取代的咔啉基团、取代或未取代的二苯并呋喃基团、取代或未取代的二苯并噻吩基团、取代或未取代的三苯基膦氧基团、取代或未取代的螺芴基团、取代或未取代的三亚苯基团、取代或未取代的菲基团等。
再进一步地,本发明通式(1)表示的化合物最优选为下述具体化合物M1-M104:
作为本发明的另一个方面,本发明还提供了一种如上所述的化合物在有机电致发光器件中的应用。本发明的化合物优选用于有机电致发光器件中的发光主体材料或电子传输材料。
作为本发明的又一个方面,本发明还提供了一种有机电致发光器件,包括第一电极、第二电极和插入在所述第一电极和第二电极之间的若干有机层,所述有机层中含有如下述通式(1)表示的化合物:
在通式(1)中:
X1~X4分别独立选自CR4或N,R4选自氢、C1-C10烷基、取代或未取代的C6-C15的芳基、取代或未取代的C3-C15的杂芳基中的一种;;
R1~R3彼此相同或不同,分别独立选自以下基团:氢、C1-C10烷基、取代或未取代的C6-C15的芳基、取代或未取代的C3-C15的杂芳基;R1~R3各自独立地与相连接的苯环稠合形成C9~C30芳基或杂芳基,所形成的芳基或杂芳基任选地被0、1、2、3、4或5个各自独立地选自取代或未取代的C1~C12烷基、卤素、氰基、硝基、羟基、硅烷基、取代或未取代的C6~C30芳基、取代或未取代的C3~C30杂芳基中的取代基所取代;
m、n彼此相同或不同,且各自独立地为0~4的整数,p为0~3的整数;
L1、L2各自独立地选自单键、取代或未取代的C6-C30的亚芳基、取代或未取代的C3-C30的亚杂芳基,优选亚苯基;
Ar1、Ar2各自独立地选自氢、取代或未取代的C6-C30的芳基、取代或未取代的C3-C30的杂芳基。
当上述基团存在取代基时,所述取代基分别独立地选自卤素、氰基、C1-C10的烷基或环烷基、C2-C6的烯基或环烯基、C1-C6的烷氧基或硫代烷氧基、C6-C30的芳基、C3-C30的杂芳基。
研究发现,本发明的上述通式化合物成膜性好,适合用作发光主体材料和电子传输材料。其原理尚不明确,据推测可能是以下原因:本发明通式(1)所示的化合物中,由于在分子骨架中引入了受体单元,使得分子的电子传输能力增强,使得分子的载流子传输均衡。该类材料作为有机电致发光器件的发光层材料使用时,相比现有技术,能够进一步降低驱动电压、提高发光效率。
本发明的技术方案有如下优点:
(1)咪唑以及芴基团具有较高的三线态能级,二者以σ键连接时不会导致共轭程度的大幅度提升,咪唑取代螺芴基团仍具有较高的三线态能级,能够作为红、绿、蓝三种发光材料的主体材料使用。此外,该系列化合物的能隙也较窄,有利于载流子的注入,能够有效地降低器件的开启电压。
(2)咪唑基团均具有较好的电子传输能力,在发光层中使用时能够拓展其载流子的复合区域,有效地降低效率滚降。作为电子传输材料使用时能够有效地降低注入能垒,降低开启电压。
(3)芴与咪唑以σ键连接后,整个分子呈现出较大的刚性扭曲结构,能够有效地降低因聚集引起的发光淬灭,提高发光效率。
具体实施方式
为了使本领域技术人员更好地理解本发明,下面结合具体实施方式对本发明作进一步详细说明。
本发明中未提到的合成方法的化合物的都是通过商业途径获得的原料产品。本发明中所用溶剂和试剂,例如二氯甲烷、石油醚、乙醇、四氢呋喃、N,N-二甲基乙酰胺、无水硫酸镁、咔唑、苯并咪唑等等化学试剂,均可以从国内化工产品市场购买,例如购买自国药集团试剂公司、TCI公司、上海毕得医药公司、百灵威试剂公司等。另外,本领域技术人员也可以通过公知方法合成。
本发明中的中间体和化合物的分析检测使用ABSCIEX质谱仪(4000QTRAP)和赛默飞有机元素分析仪。
下面对本发明化合物的合成方法进行简要的说明。
代表性合成路径:
合成例1:M1的合成
中间体M1-1的合成:
将11.8g(100mmol)苯并咪唑以及20.2g 2-氟-4-溴苯甲醛(100mmol)加入到一新烘干的500mL双口瓶中,氮气保护下加入20.7g(150mmol)无水碳酸钾以及200mL二甲基亚砜(DMSO)。升温至120℃持续反应20h。反应结束后降至室温,将反应体系倒入到搅拌的1L冰水中,此时有大量淡黄色沉淀产生。减压抽滤,蒸馏水反复洗涤。粗品以二氯甲烷溶解,洗脱剂为乙酸乙酯:二氯甲烷=1:10进行柱层析得到米白色固体,12.5g,收率42%。质谱分析确定的分子离子质量为:298.02(计算值为:297.97);理论元素含量(%)C14H7BrN2O:C,56.21;H,2.36;Br,26.71;N,9.37;O,5.35。实测元素含量(%):C,56.23;H,2.38;N,9.35。上述分析结果表明,获得的产物为预计的产品。
中间体M1-2的合成:
取一干燥的1000mL三口瓶,氮气条件下依次加入2-溴联苯9.3g(40mmol)以及150mL干燥的四氢呋喃(THF),反应体系降温至-78℃。持续搅拌30min后逐滴加入20mL正丁基锂(2M),滴加完毕后,维持低温反应1.5h。最后将11.92g(40mmol)M1-1以500mL干燥的THF溶解,逐滴滴加到反应体系中。滴加完毕后升温至室温继续反应12h。反应结束后,加入20mL蒸馏水进行淬灭,通过减压蒸馏将反应体系的溶剂除去。在粗产品中加入300mL冰醋酸以及30mL浓盐酸,升温至100℃反应12h。反应结束后,将反应体系溶剂减压蒸馏除去。二氯甲烷:石油醚=1:1为洗脱剂进行柱层析,得到大量白色固体,13.1g,收率75%。以质谱分析确定的分子离子质量为:434.10(计算值为:434.04);理论元素含量(%)C26H15BrN2:C,71.74;H,3.47;Br,18.36;N,6.44。实测元素含量(%):C,71.76;H,3.46;N,6.42。上述分析结果表明,获得的产物为预计的产品。
化合物M1的合成:
取一干燥的500mL双口瓶,依次加入8.68g(20mmol)M1-2、4.18g(25mmol)咔唑、6.36g(30mmol)无水磷酸钾、3.8g(20mmol)碘化亚铜。氮气置换三次后加入2.4g(40mmol)乙二胺以及250mL甲苯,加热回流12h。将反应体系溶剂减压蒸馏后,以二氯甲烷萃取,大量水洗。合并有机相后,浓缩,以二氯甲烷:石油醚=1:1为洗脱剂进行柱层析,得到白色固体,7.1g,收率68%。质谱分析确定的分子离子质量为:521.16(计算值为:521.19);理论元素含量(%)C38H23N3:C,87.50;H,4.44;N,8.06。实测元素含量(%):C,87.46;H,4.41;N,8.07。上述分析结果表明,获得的产物为预计的产品。
合成例2:M2的合成:
依照M1的合成,步骤相同,用5-溴-2-氟苯甲醛代替2-氟-4-溴-苯甲醛进行反应,得到白色固体7.2g,收率69%。质谱分析确定的分子离子质量为:521.16(计算值为:521.19);理论元素含量(%)C38H23N3:C,87.50;H,4.44;N,8.06。实测元素含量(%):C,87.47;H,4.42;N,8.06。上述分析结果表明,获得的产物为预计的产品。
合成例3:M12的合成:
取一干燥的500mL双口瓶,依次加入8.68g(20mmol)M1-2、7.2g(25mmol)3-硼酸-9-苯基咔唑、4.14g(30mmol)无水碳酸钾、230mg(0.2mmol)四三苯基膦钯。氮气置换三次后加入15mL蒸馏水以及250mL1,4-二氧六环,加热回流12h。将反应体系溶剂减压蒸馏后,以二氯甲烷萃取,大量水洗。合并有机相后,浓缩,以二氯甲烷:石油醚=1:1为洗脱剂进行柱层析,得到白色固体,10.3g,收率86%。质谱分析确定的分子离子质量为:597.20(计算值为:597.22);理论元素含量(%)C44H27N3:C,88.42;H,4.55;N,7.03。实测元素含量(%):C,88.46;H,4.54;N,8.07。上述分析结果表明,获得的产物为预计的产品。
合成例4:M46的合成:
依照M12的合成,步骤相同,用3-氰基苯硼酸代替3-硼酸-9-苯基咔唑进行反应,得到米白色固体8.23g,收率90%。质谱分析确定的分子离子质量为:457.14(计算值为:457.16);理论元素含量(%)C33H19N3:C,86.63;H,4.19;N,9.18。实测元素含量(%):C,86.64;H,4.17;N,9.20。上述分析结果表明,获得的产物为预计的产品。
合成例5:M53的合成:
依照M12的合成,步骤相同,用[4-(2-苯基-1H-苯并咪唑-1-基)苯基]硼酸代替3-硼酸-9-苯基咔唑进行反应,得到米白色固体11.5g,收率92%。质谱分析确定的分子离子质量为:624.21(计算值为:624.23);理论元素含量(%)C45H28N4:C,86.51;H,4.52;N,8.97。实测元素含量(%):C,86.52;H,4.50;N,8.96。上述分析结果表明,获得的产物为预计的产品。
以下对本发明的有机电致发光器件的发光层和有机电致发光器件进行说明。
本发明的有机电致发光器件的发光层,包括主体材料和染料。本发明的化合物既可以作为主体材料来使用,也可以作为电子传输层材料来使用。
本发明的有机电致发光器件,包括基板,以及依次形成在所述基板上的阳极层、多个发光功能层和阴极层。
所述的发光功能层包括空穴注入层、空穴传输层、发光层、电子传输层,所述的空穴注入层形成在所述的阳极层上,所述的空穴传输层形成在所述的空穴注入层上,所述的阴极层形成在所述的电子传输层上,所述的空穴传输层与所述的电子传输层之间为发光层;所述的发光层为上述本发明的有机电致发光器件的发光层。
具体地,阳极材料可以采用铟锡氧(ITO)、铟锌氧(IZO)、二氧化锡(SnO2)、氧化锌(ZnO)等透明导电材料,也可以是银及其合金、铝及其合金等金属材料,也可以是PEDOT等有机导电材料,及上述材料的多层结构。
空穴注入层包括但不限于以下所罗列的HI1-HI3的一种或多种的组合。
空穴传输层可以包括但不限于以下所罗列的HT1-HT33的一种或多种。
主体材料包括GPH44-GPH80中的一种或多种的组合。
荧光染料可以但不限于以下所罗列的TDE1-TDE39的一种或多种的组合。
磷光染料可以但不限于以下所罗列的PD1-PD17的一种或多种的组合。
电子传输层可以但不限于以下所罗列的ET1-ET62的一种或多种的组合。
LiQ,LiF,NaCl,CsF,Li2O,Cs2CO3,BaO,Na,Li,Ca。
阴极为镁银混合物、LiF/Al、ITO等金属、金属混合物、氧化物。
本发明的化合物作为热活化延迟荧光型有机电致发光器件中的主体材料的实施例是实施例1-6;作为磷光电致发光器件中主体材料的实施例是实施例7-12:作为电子传输材料使用的实施例是实施例13-18。
器件实施例1:
器件结构如下所示:
ITO(150nm)/HI-2(10nm)/HT-2(40nm)/M1:TDE7(30nm,5%wt)/ET59(25nm)/LiF(0.5nm)/Al(150nm)。
有机电致发光器件制备过程如下:将涂布了ITO(厚度150nm)透明导电层的玻璃板在商用清洗剂中超声处理,在去离子水中冲洗,在丙酮:乙醇混合溶剂中超声除油,在洁净环境下烘烤至完全除去水份,用紫外光和臭氧清洗,并用低能阳离子束轰击表面;
把上述带有阳极的玻璃基片置于真空腔内,抽真空至1×10-5~1×10-4Pa,在上述阳极层膜上真空蒸镀HI-2和HT-2分别作为空穴注入层和空穴传输层,蒸镀速率为0.1nm/s,蒸镀膜厚分别为10nm和40nm;
在空穴传输层之上真空蒸镀“M1:TDE7(30nm,5%wt)”作为有机电致发光器件的发光层,蒸镀速率为0.1nm/s,蒸镀总膜厚为30nm;其中“5%wt”是指蓝光染料的掺杂比例,即主体材料与TDE7的重量份比为95:5。
在发光层之上真空蒸镀ET59作为有机电致发光器件的电子传输层,其蒸镀速率为0.1nm/s,蒸镀总膜厚为20nm;
在电子传输层上真空蒸镀0.5nm的LiF作为电子注入层和150nm的Al作为阴极。
器件实施例2-6和对比实施例1-2的制作过程同器件实施例1,区别是将主体材料换为本发明的化合物M12、M21、M25、M27、M46和现有技术中的材料GPH-77、GPH-81。
器件实施例7:
器件结构如下所示:
ITO(150nm)/HI-2(10nm)/HT-2(40nm)/M1:PD1(30nm,5%wt)/ET58(25nm)/LiF(0.5nm)/Al(150nm)。
与器件实施例1的制作过程基本相同,不同的是电子传输材料由ET59换成ET58,染料由TDE7换为PD1,主体材料仍为M1。
器件实施例8-12及对比实施例3-4的制作过程同器件是实施例7,不同之处是主体材料换为M12、M21、M22、M27、M47和GPH-77、GPH-81。
器件实施例13:
ITO(150nm)/HT32(20nm)/GPH77:TDE7(30nm,5wt%)/M29(30nm)/LiF(0.5nm)/Al(150nm)。
有机电致发光器件制备过程如下:将涂布了ITO(厚度150nm)透明导电层的玻璃板在商用清洗剂中超声处理,在去离子水中冲洗,在丙酮:乙醇混合溶剂中超声除油,在洁净环境下烘烤至完全除去水份,用紫外光和臭氧清洗,并用低能阳离子束轰击表面;
把上述带有阳极的玻璃基片置于真空腔内,抽真空至小于1×10-5,在上述阳极层膜上真空蒸镀空穴传输层HT32,蒸镀速率为0.1nm/s,蒸镀膜厚为20nm;
在空穴传输层之上真空蒸镀发光主体材料和染料,作为有机电致发光器件的发光层,蒸镀速率为0.1nm/s,蒸镀总膜厚为30nm;
在发光层之上真空蒸镀M29作为有机电致发光器件的电子传输层,其蒸镀速率为0.1nm/s,蒸镀总膜厚为20nm;
在电子传输层上真空蒸镀0.5nm的LiF,150nm的Al作为电子注入层和阴极。
器件实施例14-18以及对比例5、6的制备过程同实施例13,不同之处在于电子传输材料由M29替换为M35、M49、M53、M75、M82以及ET35、ET58。
对由上述过程制备的有机电致发光器件进行如下性能测定:
使用数字源表及亮度计测定实施例1~18以及对比例1~6中制备得到的有机电致发光器件的开启电压、最大亮度并计算出最大的外量子效率。具体而言,以每秒0.1V的速率提升电压,测定当有机电致发光器件的亮度达到1cd/m2时的电压即开启电压,同时测出此时的电流密度并依据光谱等数据计算出最大的外量子效率。具体结果见表1、表2和表3。
所制备的有机电致发光器件最大亮度、开启电压以及最大外量子效率等相关性能见表1-3。
表1
表2
表3
由上述表1-表3中的数据可以看到:
通过实施例1-6与对比例1-2的比较可见,本发明合成的化合物在OLED器件中用做TADF主体材料时,无论是最大亮度还是最大外量子效率都比已知采用现有技术材料所制备的OLED器件的性能要优异。
通过实施例6-12和对比例3-4的对比可见,采用本发明化合物做绿光的发光主体材料时所制备器件的最大亮度和最大外量子效率都要优于采用现有技术材料所制备的器件,同时开启电压相对较低。
通过实施例6-13和对比例5-6的对比可见,采用本发明化合物作为电子传输材料所制备器件的最大亮度和最大外量子效率都要优于采用现有技术材料所制备的器件,同时开启电压相对较低。
采用本发明的化合物作为TADF、磷光染料的主体以及电子传输材料时,其开启电压、最大亮度以及最大外量子效率都有所提升,表现出优异的器件性能。
以上结果表明,本发明的新型有机材料用于有机电致发光器件的主体时,可以有效的降低起降电压,提高电流效率,且具有良好的稳定性能。
尽管结合实施例对本发明进行了说明,但本发明并不局限于上述实施例,应当理解,在本发明构思的引导下,本领域技术人员可进行各种修改和改进,所附权利要求概括了本发明的范围。
Claims (10)
1.一种通式化合物,如下式(1)所示:
式(1)中:X1~X4分别独立选自CR4或N,R4选自氢、C1-C10烷基、取代或未取代的C6-C15的芳基、取代或未取代的C3-C15的杂芳基中的一种;
R1~R3彼此相同或不同,分别独立选自以下基团:氢、C1-C10烷基、取代或未取代的C6-C15的芳基、取代或未取代的C3-C15的杂芳基;R1~R3各自独立地与相连接的苯环稠合形成C9~C30芳基或杂芳基,所形成的芳基或杂芳基任选地被0、1、2、3、4或5个各自独立地选自取代或未取代的C1~C12烷基、卤素、氰基、硝基、羟基、硅烷基、取代或未取代的C6~C30芳基、取代或未取代的C3~C30杂芳基中的取代基所取代;R1~R3不同时为氢;
当X1~X4分别独立选自CR4时,R1~R3中的至少一个与相连接的苯环稠合形成C9~C30芳基或杂芳基;
m、n彼此相同或不同,且各自独立地为1~4的整数,p为1~3的整数;
L1、L2各自独立地选自单键、取代或未取代的C6-C30的亚芳基、取代或未取代的C3-C30的亚杂芳基;
Ar1、Ar2各自独立地选自氢、取代或未取代的C6-C30的芳基、取代或未取代的C3-C30的杂芳基;
当上述基团存在取代基时,所述取代基分别独立地选自卤素、氰基、C1-C10的烷基或环烷基、C2-C6的烯基或环烯基、C1-C6的烷氧基或硫代烷氧基、C6-C30的芳基、C3-C30的杂芳基。
5.根据权利要求1或2所述的通式化合物,其中式(1)、式(2-1)至式(2-12)中,Ar1、Ar2各自独立地选自下述基团:
取代或未取代的三嗪基团、取代或未取代的嘧啶基团、取代或未取代的吡啶基团、取代或未取代的喹唑啉基团、取代或未取代的异喹唑啉基团、取代或未取代的咔唑基团、取代或未取代的咔啉基团、取代或未取代的二苯并呋喃基团、取代或未取代的二苯并噻吩基团、取代或未取代的三苯基膦氧基团、取代或未取代的螺芴基团、取代或未取代的三亚苯基团、取代或未取代的菲基团。
7.权利要求1或2所述的通式化合物的应用,所述应用为在有机电致发光器件中作为发光主体材料或作为电子传输材料。
8.根据权利要求6所述的结构化合物的应用,所述应用为在有机电致发光器件中作为发光主体材料或作为电子传输材料。
9.一种有机电致发光器件,该器件包括第一电极、第二电极和插入所述第一电极和第二电极之间的一层或多层有机层,其特征在于,所述有机层中包括至少一种由权利要求1或2中任一项所述的通式化合物。
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