CN111303174B - 一种有机电致发光材料及其应用 - Google Patents
一种有机电致发光材料及其应用 Download PDFInfo
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- CN111303174B CN111303174B CN201811510544.7A CN201811510544A CN111303174B CN 111303174 B CN111303174 B CN 111303174B CN 201811510544 A CN201811510544 A CN 201811510544A CN 111303174 B CN111303174 B CN 111303174B
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- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 4
- 239000012044 organic layer Substances 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 3
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- 125000001072 heteroaryl group Chemical group 0.000 abstract description 10
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- 125000000217 alkyl group Chemical group 0.000 abstract description 6
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- 101000930898 Cryphonectria parasitica Glyceraldehyde-3-phosphate dehydrogenase Proteins 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
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- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 2
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- 125000004988 dibenzothienyl group Chemical group C1(=CC=CC=2SC3=C(C21)C=CC=C3)* 0.000 description 2
- 238000005401 electroluminescence Methods 0.000 description 2
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- 125000001624 naphthyl group Chemical group 0.000 description 2
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
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- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 2
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- 125000004076 pyridyl group Chemical group 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
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- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 2
- GBXQPDCOMJJCMJ-UHFFFAOYSA-M trimethyl-[6-(trimethylazaniumyl)hexyl]azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCCCCC[N+](C)(C)C GBXQPDCOMJJCMJ-UHFFFAOYSA-M 0.000 description 2
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 2
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 1
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 1
- IOPQERQQZZREDR-UHFFFAOYSA-N 1-bromo-3,5-diphenylbenzene Chemical compound C=1C(Br)=CC(C=2C=CC=CC=2)=CC=1C1=CC=CC=C1 IOPQERQQZZREDR-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
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- NUQHGLAGHWFIMW-UHFFFAOYSA-N 2-chloro-3-naphthalen-2-ylquinoxaline Chemical compound C1=CC=CC2=CC(C3=NC4=CC=CC=C4N=C3Cl)=CC=C21 NUQHGLAGHWFIMW-UHFFFAOYSA-N 0.000 description 1
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- NSGDYZCDUPSTQT-UHFFFAOYSA-N N-[5-bromo-1-[(4-fluorophenyl)methyl]-4-methyl-2-oxopyridin-3-yl]cycloheptanecarboxamide Chemical compound Cc1c(Br)cn(Cc2ccc(F)cc2)c(=O)c1NC(=O)C1CCCCCC1 NSGDYZCDUPSTQT-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 241000235648 Pichia Species 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- SLGBZMMZGDRARJ-UHFFFAOYSA-N Triphenylene Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- JHYLKGDXMUDNEO-UHFFFAOYSA-N [Mg].[In] Chemical compound [Mg].[In] JHYLKGDXMUDNEO-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 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
- 238000004458 analytical method Methods 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- LPTWEDZIPSKWDG-UHFFFAOYSA-N benzenesulfonic acid;dodecane Chemical compound OS(=O)(=O)C1=CC=CC=C1.CCCCCCCCCCCC LPTWEDZIPSKWDG-UHFFFAOYSA-N 0.000 description 1
- 125000004618 benzofuryl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010549 co-Evaporation Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
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- 125000004987 dibenzofuryl group Chemical group C1(=CC=CC=2OC3=C(C21)C=CC=C3)* 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
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- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
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- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- HRRMKZWYKMIUEI-UHFFFAOYSA-N sodium 2-methylpropan-2-olate toluene Chemical compound [Na+].CC(C)(C)[O-].CC1=CC=CC=C1 HRRMKZWYKMIUEI-UHFFFAOYSA-N 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- VNFWTIYUKDMAOP-UHFFFAOYSA-N sphos Chemical compound COC1=CC=CC(OC)=C1C1=CC=CC=C1P(C1CCCCC1)C1CCCCC1 VNFWTIYUKDMAOP-UHFFFAOYSA-N 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 125000005580 triphenylene group Chemical group 0.000 description 1
- 125000003960 triphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C3=CC=CC=C3C12)* 0.000 description 1
- 238000007738 vacuum evaporation 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
-
- 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
- C07D495/12—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 three hetero rings
- C07D495/14—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/12—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains three hetero rings
- C07D491/14—Ortho-condensed systems
- C07D491/153—Ortho-condensed systems the condensed system containing two rings with oxygen as ring hetero atom and one ring with nitrogen as ring hetero atom
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Abstract
本发明公开了下式(1)的通式化合物:其中:X1和X2分别独立的选自S或O;L1选自单键、取代或未取代的C6~C30的亚芳基、取代或未取代C3~C30亚杂芳基中的一种;Ar1选自取代或未取代的C6~C30芳基、取代或未取代的C3~C30杂芳基中的一种;R1和R2独立的选自氢、C1~C12烷基、C1~C12烷氧基、卤素、氰基、硝基、羟基、硅烷基、氨基、取代或未取代的C6~C30芳基氨基、取代或未取代的C3~C30杂芳基氨基、取代或未取代的C6~C30芳基、取代或未取代的C3~C30杂芳基中的一种,m、n为0~4的整数。本发明的化合物作为OLED器件中的发光材料,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
本发明涉及一种有机化合物,尤其涉及一种用于有机电致发光器件的化合物及在有机电致发光器件中的应用。
背景技术
有机电致发光显示器(以下简称OLED)具有自主发光、低电压直流驱动、全固化、视角宽、重量轻、组成和工艺简单等一系列的优点,与液晶显示器相比,有机电致发光显示器不需要背光源,视角大,功率低,其响应速度可达液晶显示器的1000倍,其制造成本却低于同等分辨率的液晶显示器,因此,有机电致发光器件具有广阔的应用前景。
随着OLED技术在照明和显示两大领域的不断推进,人们对于影响OLED器件性能的高效有机材料的研究更加关注,一个效率好寿命长的有机电致发光器件通常是器件结构与各种有机材料的优化搭配的结果。在最常见的OLED器件结构里,通常包括以下种类的有机材料:空穴注入材料、空穴传输材料、电子传输材料,以及各色的发光材料(染料或者掺杂客体材料)和相应的主体材料等。目前应用的磷光主体材料往往都是具有单一载流子传输能力,诸如空穴类传输主体以及电子类传输主体。单一的载流子传输能力会造成发光层中电子和空穴的不匹配,从而造成严重的效率滚降以及寿命缩短。目前在磷光主体的使用过程中,采用双极性材料或者是双主体材料搭配的形式来解决单主体材料载流子不平衡的问题。双极性材料是在一个化合物中实现电子和空穴的共同传输,分子结构较复杂;双主体材料是使用两种材料搭配使用来实现发光层中电子和空穴的传输与结合,其中一种材料作为电子型材料,另外一种材料作为空穴型材料,电子和空穴经过两种材料的传导后,在界面处结合,两种材料来源更加广泛,可以采取不同材料的组合方式来实现更好的器件性能。
发明内容
为了克服以上现有技术中传统主体材料的缺点,本发明提供一类有机化合物并将其应用于有机电致发光器件中。
本发明的化合物由如下通式表示:
其中,
X1和X2分别独立的选自S或O;
L1选自单键、取代或未取代的C6~C30的亚芳基、取代或未取代C3~C30亚杂芳基中的一种;
进一步的,优选L1为单键或选自取代或未取代的下述结构式中任一所示:
其中,*表示与氮原子或Ar1基团的键合位置,“—”划过的环结构的表达方式,表示连接位点位于该环结构上任意能够成键的位置。
R1和R2独立的选自以下的基团:氢、C1~C12烷基、C1~C12烷氧基、卤素、氰基、硝基、羟基、硅烷基、氨基、取代或未取代的C6~C30芳基氨基、取代或未取代的C3~C30杂芳基氨基、取代或未取代的C6~C30芳基、取代或未取代的C3~C30杂芳基中的一种;
R1和R2可以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相同或不同,且各自独立地为0~4的整数;优选m、n各自独立地为0~2的整数。
进一步优选的,R1和R2各自独立地选自下述基团:氢、甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、苯基、联苯基、三联苯基、萘基、蒽基、菲基、茚基、芴基、荧蒽基、三亚苯基、芘基、苝基、基、呋喃基、噻吩基、吡咯基、吡啶基、苯并呋喃基、苯并噻吩基、异苯并呋喃基、吲哚基、二苯并呋喃基、二苯并噻吩基、咔唑基中的一种。
当上述基团L1、Ar1、R1和R2上存在取代基时,所述取代基分别独立地选自卤素、氰基、C1~C12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。
Ar1选自取代或未取代的C6~C30芳基、取代或未取代的C3~C30杂芳基中的一种;
进一步优选的,Ar1选自取代或未取代的下列基团:苯基、萘基、联苯基、三联苯基、菲基、蒽基、芘、苝、三亚苯基、荧蒽基、咔唑基、二苯并呋喃基、二苯并噻吩基、三嗪基、嘧啶基、吡啶基、喹唑啉基、喹啉基、喹喔啉中的一种。
更进一步优选的,Ar1选自取代或未取代的如下A1-A19结构:
上述式中,*表示与L1的连接位点,R3独立地选自以下的基团:氢、C1~C12烷基、C1~C12烷氧基、取代或未取代的C6~C30芳基氨基、取代或未取代的C3~C30杂芳基氨基、取代或未取代的C6~C30芳基、取代或未取代的C3~C30杂芳基中的一种。
上述式A1-A19可以被下述基团:C1~C12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的杂芳基中的任一所取代。
再进一步的,本发明通式(1)的化合物中,可以优选出下述具体结构化合物,这些化合物仅为代表性的。
作为本发明的另一方面,本发明上述通式化合物在有机电致发光器件中作为磷光主体材料使用。本发明的化合物优选用于红光和绿光的磷光发光主体材料。
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至少包含一层发光层的有机层,其特征在于,所述有机层中含有如上所述通式(Ⅰ)表示的化合物。
研究发现,本发明的上述通式化合物成膜性好,适合用作磷光主体材料。其原理尚不明确,据推测可能是以下原因:
本发明以两个噻吩或者呋喃为中心,该结构化学稳定性强,有利于提高器件的寿命,为了更好的调节分子的能级,与其他功能材料相匹配我们引入一个5元氮杂环,这样一来一方面提高了分子的空穴传输性,另一方面我们可以将更多的取代基团引入到氮原子上,调节分子能级,匹配器件其他层材料,使器件性能得以更好的优化,相较于已报道含有两个五环氮杂环的类似化合物,本发明的化合物具有更深的HOMO能级,在器件的能级匹配上更好。。
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。
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:
更具体地,以下给出本发明的代表性化合物的合成方法(X1、X2表示O或者S;Y表示卤素Cl、Br、I)。
中间体的合成
中间体M1-1的合成:
反应瓶中,加入2-溴噻吩(163g,1mol)、邻氯苯硫酚(144g,1mol)、碳酸钾(276g,2mol)和DMF2L,120℃反应12h。反应完毕,停反应。冷却至室温,加入水过滤得中间体M1-1。
中间体M1-2的合成:
将M1-1(50g,0.22mol)、醋酸钯(2.5g)、三环己基膦8g于装有500mlN,N-二甲基乙酰胺的反应瓶中,加热至回流反应6h,TLC监控反应完成,降温后加入水及二氯甲烷萃取,有机相浓缩后柱层析分析得产品M1-2。
中间体M1-3的合成
将M1-2(38g,0.2mol)加入装有300mlDMF的反应瓶中,降温至0℃反应,开始滴加NBS(42.78g,0.24mol)/200mlDMF的溶液,HPLC监控反应完全,缓慢倒入水中,过滤得中间体M1-3。
中间体M1-4的合成:
将M1-3(20g,0.074mol)、邻氯苯胺(9.5g,0.074mol)、1%三(二亚苄基丙酮)二钯、2%三叔丁基膦1.5eq叔丁醇钠甲苯300ml加入到反应瓶中,加热至60℃反应4h,TLC监控反应完全,处理后柱层析分析的中间体D。
M1的合成
将M1-4(15g,0.047mol)、醋酸钯5%、和三环己基膦10%于装有300mlN,N-二甲基乙酰胺的反应瓶中,加热至回流反应6h,TLC监控反应完成,降温后加入水及二氯甲烷萃取,有机相浓缩后柱层析分析得产品M1。
1H NMR(500MHz,Chloroform)δ8.45(dd,J=14.9,3.0Hz,1H),8.19(td,J=7.1,4.7Hz,2H),7.86(dd,J=15.0,3.1Hz,1H),7.56(td,J=15.0,3.0Hz,1H),7.44–7.35(m,1H),7.31(td,J=15.0,3.0Hz,1H),7.25–7.11(m,2H).
中间体M2-M4的合成
中间体M2-M4的合成步骤同M,把上述原料中噻吩替换成等当量的呋喃。
合成例1:
化合物P2的合成
反应瓶中,加入M1(28g,100mmol)、溴苯(23g,100mmol)、Pd2(dba)3(0.5%eq)、S-Phos(1%eq)、甲苯200mL和叔丁醇钠20g,100℃反应5h。反应完毕,停反应。冷却至室温,加入水及乙酸乙酯萃取,有机相浓缩得到固体通过甲苯中重结晶纯化,得到白色粉末状P2。
1H NMR(500MHz,Chloroform)δ8.55(dd,J=7.3,1.6Hz,1H),8.45(dd,J=7.5,1.4Hz,1H),7.96–7.88(m,4H),7.86(dd,J=7.5,1.4Hz,1H),7.75(dd,J=7.5,1.2Hz,2H),7.59–7.44(m,4H),7.44–7.37(m,1H),7.31(td,J=7.5,1.5Hz,1H),7.13(dtd,J=26.2,7.5,1.6Hz,2H).
合成例2:
化合物P6的合成
反应同合成例1,不同在于将4-溴联苯替换成等当量的2-([1,1′-联苯]-3-基)-4-氯-6-苯基-1,3,5-三嗪,最后得产品P6。
1H NMR(500MHz,Chloroform)δ8.55(dd,J=14.2,3.7Hz,1H),8.44(dt,J=11.4,5.6Hz,1H),8.36(dddd,J=12.3,8.4,6.1,3.0Hz,4H),7.86(dd,J=15.0,3.1Hz,1H),7.80–7.65(m,3H),7.65–7.36(m,9H),7.31(td,J=15.0,3.0Hz,1H),7.13(pd,J=15.0,3.6Hz,2H).
合成例3:
化合物P21的合成
反应同合成例1,不同在于将M1替换为等当量的M2;将4-溴联苯替换成等当量的1-溴-3,5二苯基苯,最后的产品P21。
1H NMR(500MHz,Chloroform)δ8.31(d,J=3.0Hz,2H),8.11–8.01(m,1H),8.02–7.93(m,1H),7.80–7.68(m,4H),7.57–7.36(m,8H),7.36–7.23(m,2H),7.13(pd,J=15.0,3.6Hz,2H).
合成例4:
化合物P27的合成
反应同合成例1,不同在于将M1替换为等当量的M2;将4-溴联苯替换成等当量的2-氯-3-(2-萘基)喹喔啉,最后得产品P27。
1H NMR(500MHz,Chloroform)δ9.02(t,J=3.0Hz,1H),8.63–8.39(m,2H),8.15–7.88(m,4H),7.87–7.73(m,2H),7.72–7.40(m,6H),7.37–7.22(m,2H),7.13(pd,J=14.9,3.6Hz,2H).
合成例5:
化合物P51的合成
反应同合成例1,不同在于将M1替换为等当量的M4;将4-溴联苯替换成等当量的2-(萘-2-基)-4-氯-6-苯基-1,3,5-三嗪,最后得产品P51。
1H NMR(500MHz,Chloroform)δ9.03–8.89(m,1H),8.55(dd,J=14.2,3.7Hz,1H),8.45(dd,J=14.9,3.0Hz,1H),8.41–8.30(m,2H),8.06–7.90(m,2H),7.90–7.78(m,3H),7.62–7.41(m,7H),7.31(td,J=15.0,3.0Hz,1H),7.13(pd,J=15.0,3.6Hz,2H).
器件实施例
实施方式
OLED包括位于第一电极和第二电极,以及位于电极之间的有机材料层。该有机材料又可以分为多个区域。比如,该有机材料层可以包括空穴传输区、发光层、电子传输区。
在具体实施例中,在第一电极下方或者第二电极上方可以使用基板。基板均为具有机械强度、热稳定性、防水性、透明度优异的玻璃或聚合物材料。此外,作为显示器用的基板上也可以带有薄膜晶体管(TFT)。
第一电极可以通过在基板上溅射或者沉积用作第一电极的材料的方式来形成。当第一电极作为阳极时,可以采用铟锡氧(ITO)、铟锌氧(IZO)、二氧化锡(SnO2)、氧化锌(ZnO)等氧化物透明导电材料和它们的任意组合。第一电极作为阴极时,可以采用镁(Mg)、银(Ag)、铝(Al)、铝-锂(Al-Li)、钙(Ca)、镁-铟(Mg-In)、镁-银(Mg-Ag)等金属或合金以及它们之间的任意组合。
有机材料层可以通过真空热蒸镀、旋转涂敷、打印等方法形成于电极之上。用作有机材料层的化合物可以为有机小分子、有机大分子和聚合物,以及它们的组合。
空穴传输区位于阳极和发光层之间。空穴传输区可以为单层结构的空穴传输层(HTL),包括只含有一种化合物的单层空穴传输层和含有多种化合物的单层空穴传输层。空穴传输区也可以为包括空穴注入层(HIL)、空穴传输层(HTL)、电子阻挡层(EBL)中的至少一层的多层结构。
空穴传输区的材料可以选自、但不限于酞菁衍生物如CuPc、导电聚合物或含导电掺杂剂的聚合物如聚苯撑乙烯、聚苯胺/十二烷基苯磺酸(Pani/DBSA)、聚(3,4-乙撑二氧噻吩)/聚(4-苯乙烯磺酸盐)(PEDOT/PSS)、聚苯胺/樟脑磺酸(Pani/CSA)、聚苯胺/聚(4-苯乙烯磺酸盐)(Pani/PSS)、芳香胺衍生物如下面HT-1至HT-34所示的化合物;或者其任意组合。
空穴注入层位于阳极和空穴传输层之间。空穴注入层可以是单一化合物材料,也可以是多种化合物的组合。例如,空穴注入层可以采用上述HT-1至HT-34的一种或多种化合物,或者采用下述HI1-HI3中的一种或多种化合物;也可以采用HT-1至HT-34的一种或多种化合物掺杂下述HI1-HI3中的一种或多种化合物。
发光层包括可以发射不同波长光谱的的发光染料(即掺杂剂,dopant),还可以同时包括主体材料(Host)。发光层可以是发射红、绿、蓝等单一颜色的单色发光层。多种不同颜色的单色发光层可以按照像素图形进行平面排列,也可以堆叠在一起而形成彩色发光层。当不同颜色的发光层堆叠在一起时,它们可以彼此隔开,也可以彼此相连。发光层也可以是能同时发射红、绿、蓝等不同颜色的单一彩色发光层。
根据不同的技术,发光层材料可以采用荧光电致发光材料、磷光电致发光材料、热活化延迟荧光发光材料等不同的材料。在一个OLED器件中,可以采用单一的发光技术,也可以采用多种不同的发光技术的组合。这些按技术分类的不同发光材料可以发射同种颜色的光,也可以发射不同种颜色的光。
在本发明的一方面,发光层采用磷光电致发光的技术。其发光层主体材料选自、但不限于GPH-1至GPH-80中的一种或多种的组合。
在本发明的一方面,发光层采用磷光电致发光的技术。其发光层磷光掺杂剂可以选自、但不限于以下所罗列的GPD-1至GPD-47的一种或多种的组合。
OLED有机材料层还可以包括发光层与阴极之间的电子传输区。电子传输区可以为单层结构的电子传输层(ETL),包括只含有一种化合物的单层电子传输层和含有多种化合物的单层电子传输层。电子传输区也可以为包括电子注入层(EIL)、电子传输层(ETL)、空穴阻挡层(HBL)中的至少一层的多层结构。
本发明的一方面,电子传输层材料可以选自、但不限于以下所罗列的ET-1至ET-57的一种或多种的组合。
器件中还可以包括位于电子传输层与阴极之间的电子注入层,电子注入层材料包括但不限于以下罗列的一种或多种的组合:LiQ,LiF,NaCl,CsF,Li2O,Cs2CO3,BaO,Na,Li,Ca。
下面通过将本发明的化合物具体应用到有机电致发光器件中测试实际使用性能来展示和验证本发明的技术效果和优点。
为了方便比较本发明的发光材料的器件应用性能,使用下述所示的化合物C1和C2作为对比材料。
有机电致发光器件制备过程如下:
将涂布了ITO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1×10-5~9×10-3Pa,在上述阳极层膜上真空蒸镀HT-11作为空穴注入层,蒸镀速率为0.1nm/s,蒸镀膜厚为10nm;
在空穴注入层之上真空蒸镀HT-5作为器件的空穴传输层,蒸镀速率为0.1nm/s,蒸镀总膜厚为80nm;
在空穴传输层之上真空蒸镀器件的发光层,发光层包括主体材料和染料材料,利用多源共蒸的方法,调节N型主体材料GPH-28与本发明的各个化合物以及作为对比材料的化合物C1的蒸镀速率为0.1nm/s,染料GPD-1蒸镀速率3%比例设定,蒸镀总膜厚为30nm;
在发光层之上真空蒸镀器件的电子传输层材料ET42,其蒸镀速率为0.1nm/s,蒸镀总膜厚为30nm;
在电子传输层(ETL)上真空蒸镀厚度为0.5nm的LiF作为电子注入层,厚度为150nm的Al层作为器件的阴极。
按照上述的步骤方法制备以下各个实施例的OLED器件,具体每个实施例中的器件中材料方案详见下表1。
表1:
器件实施例1和实施例3的制备过程同对比实施例1,不同之处在于将现有技术中的化合物C1换成本发明的化合物P2、P21。
器件对比例2、实施例2、实施例4、实施例5的制备过程同对比实施例1,不同之处在于将发光层中双主体材料的N型主体材料由GPH28换为P型主体材料GPH46,化合物C1换成化合物C2和本发明的化合物P6、P27、P51。
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:
在同样亮度下,使用数字源表及亮度计测定实施例以及对比例制备得到的有机电致发光器件的驱动电压和电流效率以及器件的寿命。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10000cd/m2时的电压即驱动电压,同时测出此时的电流密度;亮度与电流密度的比值即为电流效率;LT95的寿命测试如下:使用亮度计在10000cd/m2亮度下,保持恒定的电流,测量有机电致发光器件的亮度降为9500cd/m2的时间,单位为小时。
有机电致发光器件性能见下表2。
表2:
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,在电压和效率方面保持一致情况下,本发明材料寿命与对比材料延长30%以上,是性能良好的主体材料。
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 (7)
1.一种通式化合物,如下式(1)所示:
式(1)中:X1和X2分别独立的选自S或O;
L1选自单键;“—”划过的环结构的表达方式,表示连接位点位于该环结构上任意能够成键的位置;
Ar1选自取代或未取代的下列基团:苯基、三联苯基、三嗪基、喹喔啉中的一种,Ar1存在取代基时,所述取代基分别独立地选自C6~C30的芳基中的一种;
m、n各自独立地为0。
2.根据权利要求1所述的通式化合物,其中式(1)中,Ar1选自取代或未取代的下述结构式:
上述式中,*表示与L1的连接位点。
3.下述具体结构化合物:
4.权利要求1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。
5.权利要求3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。
6.一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所述的通式化合物。
7.一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3所述的结构化合物。
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