TWI724829B - 一種咪唑並氮雜環化合物及其應用 - Google Patents
一種咪唑並氮雜環化合物及其應用 Download PDFInfo
- Publication number
- TWI724829B TWI724829B TW109109688A TW109109688A TWI724829B TW I724829 B TWI724829 B TW I724829B TW 109109688 A TW109109688 A TW 109109688A TW 109109688 A TW109109688 A TW 109109688A TW I724829 B TWI724829 B TW I724829B
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- Prior art keywords
- unsubstituted
- substituted
- heteroaryl
- alkyl
- aryl
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- -1 nitrogen heterocyclic compound Chemical class 0.000 title claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title abstract 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 111
- 239000000463 material Substances 0.000 claims abstract description 44
- 238000000605 extraction Methods 0.000 claims abstract description 16
- 230000000903 blocking effect Effects 0.000 claims abstract description 8
- 125000003118 aryl group Chemical group 0.000 claims description 47
- 125000001072 heteroaryl group Chemical group 0.000 claims description 36
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 claims description 32
- 125000004404 heteroalkyl group Chemical group 0.000 claims description 26
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 21
- 125000006753 (C1-C60) heteroaryl group Chemical group 0.000 claims description 20
- 125000006749 (C6-C60) aryl group Chemical group 0.000 claims description 20
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical group [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 18
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 18
- 229910052805 deuterium Inorganic materials 0.000 claims description 18
- 229910052736 halogen Inorganic materials 0.000 claims description 18
- 150000002367 halogens Chemical group 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 150000002431 hydrogen Chemical group 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 125000002950 monocyclic group Chemical group 0.000 claims description 14
- 125000003367 polycyclic group Chemical group 0.000 claims description 14
- 150000002527 isonitriles Chemical group 0.000 claims description 12
- 150000002825 nitriles Chemical group 0.000 claims description 12
- FVZVCSNXTFCBQU-UHFFFAOYSA-N phosphanyl Chemical group [PH2] FVZVCSNXTFCBQU-UHFFFAOYSA-N 0.000 claims description 10
- 238000006467 substitution reaction Methods 0.000 claims description 9
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 125000004104 aryloxy group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- 125000002883 imidazolyl group Chemical group 0.000 claims 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims 2
- 125000000623 heterocyclic group Chemical group 0.000 claims 1
- 125000004433 nitrogen atom Chemical group N* 0.000 claims 1
- 125000004430 oxygen atom Chemical group O* 0.000 claims 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims 1
- 125000004434 sulfur atom Chemical group 0.000 claims 1
- 238000000859 sublimation Methods 0.000 abstract description 8
- 230000008022 sublimation Effects 0.000 abstract description 8
- 229920001621 AMOLED Polymers 0.000 abstract description 4
- 230000003287 optical effect Effects 0.000 abstract description 4
- 230000005923 long-lasting effect Effects 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 26
- 238000003786 synthesis reaction Methods 0.000 description 25
- 239000007787 solid Substances 0.000 description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 101100457453 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) MNL1 gene Proteins 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- SFHYNDMGZXWXBU-LIMNOBDPSA-N 6-amino-2-[[(e)-(3-formylphenyl)methylideneamino]carbamoylamino]-1,3-dioxobenzo[de]isoquinoline-5,8-disulfonic acid Chemical compound O=C1C(C2=3)=CC(S(O)(=O)=O)=CC=3C(N)=C(S(O)(=O)=O)C=C2C(=O)N1NC(=O)N\N=C\C1=CC=CC(C=O)=C1 SFHYNDMGZXWXBU-LIMNOBDPSA-N 0.000 description 7
- 238000001819 mass spectrum Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 229940125904 compound 1 Drugs 0.000 description 4
- 229940125782 compound 2 Drugs 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 150000002391 heterocyclic compounds Chemical class 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000010549 co-Evaporation Methods 0.000 description 2
- 229940125773 compound 10 Drugs 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 1
- UVNPEUJXKZFWSJ-LMTQTHQJSA-N (R)-N-[(4S)-8-[6-amino-5-[(3,3-difluoro-2-oxo-1H-pyrrolo[2,3-b]pyridin-4-yl)sulfanyl]pyrazin-2-yl]-2-oxa-8-azaspiro[4.5]decan-4-yl]-2-methylpropane-2-sulfinamide Chemical compound CC(C)(C)[S@@](=O)N[C@@H]1COCC11CCN(CC1)c1cnc(Sc2ccnc3NC(=O)C(F)(F)c23)c(N)n1 UVNPEUJXKZFWSJ-LMTQTHQJSA-N 0.000 description 1
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 1
- GAMYYCRTACQSBR-UHFFFAOYSA-N 4-azabenzimidazole Chemical compound C1=CC=C2NC=NC2=N1 GAMYYCRTACQSBR-UHFFFAOYSA-N 0.000 description 1
- QRXMUCSWCMTJGU-UHFFFAOYSA-N 5-bromo-4-chloro-3-indolyl phosphate Chemical compound C1=C(Br)C(Cl)=C2C(OP(O)(=O)O)=CNC2=C1 QRXMUCSWCMTJGU-UHFFFAOYSA-N 0.000 description 1
- 235000007119 Ananas comosus Nutrition 0.000 description 1
- 244000099147 Ananas comosus Species 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- IVDFJHOHABJVEH-UHFFFAOYSA-N HOCMe2CMe2OH Natural products CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000005577 anthracene group Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- PBAYDYUZOSNJGU-UHFFFAOYSA-N chelidonic acid Natural products OC(=O)C1=CC(=O)C=C(C(O)=O)O1 PBAYDYUZOSNJGU-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229940125797 compound 12 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000005232 imidazopyridines Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 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
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- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
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- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
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- C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
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Abstract
本發明涉及一種咪唑並氮雜環化合物及其應用。本發明化合物具有式(I)所示結構。本發明咪唑並氮雜環化合物具有昇華溫度低,光、電、熱穩定性好,折射率高、可見光區折射率差異小等優點,該化合物製備的器件具有電壓低、壽命長,發光效率高等優點,可用於有機發光器件中。特別是作為電子傳輸材料、空穴阻隔層材料、光提取層材料,具有應用於AMOLED產業的可能。
Description
本發明涉及有機電致發光材料技術領域,特別涉及咪唑並氮雜環化合物及其在有機電致發光器件上的應用。
目前,作為新一代顯示技術的有機電致發光器件(OLED)在顯示和照明技術方面都獲得了越來越多的關注,應用前景十分廣泛。但是,和市場應用要求相比,OLED器件的發光效率、驅動電壓、使用壽命等性能還需要繼續加強和改進。
一般來說,OLED器件基本結構為在金屬電極中間夾雜各種不同功能的有機功能材料薄膜,猶如一個三明治的結構,在電流的驅動下,從陰陽兩極分別注入空穴和電子,空穴和電子在移動一段距離後,在發光層得到複合,並以光或熱的形式進行釋放,從而產生了OLED的發光。然而,有機功能材料是有機電致發光器件的核心組成部分,材料的熱穩定性、光化學穩定性、電化學穩定性、量子產率、成膜穩定性、結晶性、色飽和度等都是影響器件性能表現的主要因素。
一方面,如何縮小OLED器件內外量子效率之間的巨大差距,如何減少器件中的全發射效應、提高光耦合提取比例引起人們的廣泛關注。現行的光提取層的材料的折射率都比較低,尤其是在紅光波段,通常折射率小於1.85,極少數大於1.90,更少數大於2.0。另外,現有的光提取材料在紅綠藍光波段區域的折射率差別較大,造成三種顏色光的最佳厚度差別大,未能充分體現光提取材料的性能。對於頂發射器件來說,光提取層材料的折射率越大,相應的外量子效率就越高,器件的發光效率就越高。所以,開發高折射率的光提取層材料尤為重要。CN103828485和TW201506128公開了以多聯苯二胺為核心的光提取層材料,但是折射率還是稍微偏低,尤其是在紅光方面更需要進一步提升。
另一方面,如何降低器件工作電壓、降低產品功耗、提高器件壽命、提高發光效率,也是OLED器件不斷提升的方向。CN101186608公開了一例以咪唑並吡啶和蒽環鍵接的化合物,這類化合物三線態能級、玻璃化轉變溫度和器件壽命都需要得到改善。邱等在CN103709180、CN103709181、CN103788087、CN103788116公開了一系列以咪唑並吡啶和稠合芳環鍵接的化合物,這類化合物的三線態能級、玻璃化轉變溫度和器件壽命也需要進一步改善。
針對上述領域中的缺陷,本發明提供一種咪唑並氮雜環化合物,所述化合物具有式I所示結構。該類化合物具有昇華溫度低,光、電、熱穩定性好,折射率高、可見光區折射率差異小等優點,可用於有機發光器件中。
本發明還提供該咪唑並氮雜環化合物在OLED中的應用,特別是作為電子傳輸材料、空穴阻隔層材料、光提取層材料,使器件具有發光效率高,電壓低、壽命長的特點,具有應用於AMOLED產業的可能。
一種化合物,其結構式如式(I)所示:(I)
其中R1為單鍵、烷基、雜烷基、環烷基、取代或未取代的C6-C30的非稠環芳基、取代或未取代的C3-C27的非稠環雜芳基;
其中R2、R3、R4獨立的選自氫、氘、鹵素、烷基、雜烷基、環烷基、烷氧基、芳氧基、氨基、矽烷基、腈、異腈、膦基、取代或未取代的C6-C60的芳基、取代或未取代的C1-C60的雜芳基、經取代或未經取代的單環或多環C3-C60脂肪族環或芳香族環且R3、R4中至少有一個為取代或未取代的C6-C60的芳基、取代或未取代的C1-C60的雜芳基、經取代或未經取代的單環或多環C3-C60脂肪族環或芳香族環,其中雜烷基或雜芳基中的一個或多個碳原子可由選自O、S、N、Se、Si、Ge中的至少一個雜原子替換;所述取代為被氘、鹵素、C1-C30烷基、C1-C30雜烷基、C3-C30環烷基、氨基、矽烷基、腈、異腈、、膦基、C6-C60的芳基、C1-C60的雜芳基取代;
其中X1、X2、X3獨立的表示為CH或者N; X4、X5、X6獨立的表示為CR0或者N,R0獨立的選自氫、氘、鹵素、烷基、雜烷基、芳烷基、烷氧基、芳氧基、氨基、矽烷基、芳基、雜芳基、腈、異腈、膦基,且相鄰的R0能鍵接成並環。
優選:其中R1為單鍵、C1-C30烷基、C1-C30雜烷基、C3-C30環烷基、取代或未取代的C6-C30的非稠環芳基、取代或未取代的C3-C27的非稠環雜芳基;
其中R2、R3、R4獨立的選自氫、氘、鹵素、C1-C30烷基、C1-C30雜烷基、C3-C30環烷基、氨基、矽烷基、腈、異腈、膦基、取代或未取代的C6-C60的芳基、取代或未取代的C1-C60的雜芳基、經取代或未經取代的單環或多環C3-C60脂肪族環或芳香族環且R3、R4中至少有一個為取代或未取代的C6-C60的芳基、取代或未取代的C1-C60的雜芳基、經取代或未經取代的單環或多環C3-C60脂肪族環或芳香族環,其中雜烷基或雜芳基中的一個或多個碳原子由選自O、S、N中的至少一個雜原子替換;所述取代為被氘、鹵素、C1-C30烷基、C1-C30雜烷基、C3-C30環烷基、氨基、矽烷基、腈、異腈、、膦基、C6-C60的芳基、C1-C60的雜芳基取代;
其中X1、X2、X3獨立的表示為CH或者N; X4、X5、X6獨立的表示為CR0或者N,R0獨立的選自氫、氘、鹵素、C1-C30烷基、C1-C30雜烷基、芳烷基、氨基、矽烷基、芳基、雜芳基、腈、異腈、膦基,且相鄰的R0能鍵接成並環。
進一步優選: 其中X1、X2、X3至少一個是N。
再優選:其中R3或R4至少之一含有以下結構式(II),其中R1為單鍵、烷基、雜烷基、環烷基、C1-C30烷基取代或未取代的C6-C30的非稠環芳基、C1-C30烷基取代或未取代的C3-C27的非稠環雜芳基;其中R2為氫、氘、鹵素、烷基、雜烷基、環烷基、C1-C30烷基取代或未取代的C6-C60的芳基、C1-C30烷基取代或未取代的C1-C60的雜芳基
式(II ) 。
更優選:其中R3、R4中一個為式(II)結構,另一個為C1-C4烷基取代或未取代的C6-C18的芳基、C1-C4烷基取代或未取代的C3-C15的雜芳基;R1為C1-C4烷基取代或未取代的C6-C18的非稠環芳基、C1-C4烷基取代或未取代的C3-C15的非稠環雜芳基;R2為C1-C4烷基取代或未取代的C6-C18的芳基、C1-C4烷基取代或未取代的C3-C15的雜芳基。
優選:根據權利要求5所述的化合物,其中R1為C6-C18的非稠環芳基或C5-C15的非稠環雜芳基;R2為C6-C18的芳基或C5-C15的雜芳基。
作為優選的化合物為以下化合物:
A 1 | A 2 | A 3 |
A 4 | A 5 | A 6 |
A 7 | A 8 | A 9 |
A 10 | A 11 | A 12 |
A 13 | A 14 | A 15 |
A 16 | A 17 | A 18 |
A 19 | A 20 | A 21 |
A 22 | A 23 | A 24 |
A 25 | A 26 | A 27 |
A 28 | A 29 | A 30 |
A 31 | A 32 | A 33 |
A 34 | A 35 | A 36 |
A 37 | A 38 | A 39 |
A 40 | A 41 | A 42 |
A 43 | A 44 | A 45 |
A 46 | A 47 | A 48 |
A 49 | A 50 | A 51 |
A 52 | A 53 | A 54 |
A 55 | A 56 | A 57 |
A 58 | A 59 | A 60 |
A 61 | A 62 | A 63 |
A 64 | A 65 | A 66 |
A 67 | A 68 | A 69 |
A 70 | A 71 | A 72 |
A 73 | A 74 | A 75 |
A 76 | A 77 | A 78 |
A 79 | A 80 | A 81 |
A 82 | A 83 | A 84 |
A 85 | A 86 | A 87 |
A 88 | A 89 | A 90 |
A 91 | A 92 | A 93 |
A 94 | A 95 | A 96 |
A 97 | A 98 | A 99 |
。 |
優選:式(I)所述化合物,其中X1、X2、X3表示為CH。
進一步優選:其中R1為單鍵、C1-C30烷基取代或未取代的C6-C30的非稠環芳基、C1-C30烷基取代或未取代的C3-C27的非稠環雜芳基;其中R2為C1-C30烷基取代或未取代的C6-C60的芳基、C1-C30烷基取代或未取代的C1-C60的雜芳基;R3、R4為氫、氘、鹵素、烷基、雜烷基、環烷基、C1-C30烷基取代或未取代的C6-C60的芳基、C1-C30烷基取代或未取代的C1-C60的雜芳基、經取代或未經取代的單環或多環C3-C60脂肪族環或芳香族環且R3、R4中至少有一個為C1-C30烷基取代或未取代的C6-C60的芳基、C1-C30烷基取代或未取代的C1-C60的雜芳基、經取代或未經取代的單環或多環C3-C60脂肪族環或芳香族環。
再優選:其中R1為單鍵、C1-C4烷基取代或未取代的C6-C18的非稠環芳基、C1-C4烷基取代或未取代的C3-C15的非稠環雜芳基;R2為C1-C4烷基取代或未取代的C6-C18的芳基、C1-C4烷基取代或未取代的C3-C15的雜芳基;R3、R4為氫、氘、鹵素、烷基、C1-C4烷基取代或未取代的C6-C18的芳基、C1-C4烷基取代或未取代的C3-C15的雜芳基、經取代或未經取代的單環或多環C3-C18脂肪族環或芳香族環且R3、R4不同。
更優選:其中R1為單鍵、C6-C18的非稠環芳基或C3-C15的非稠環雜芳基;R2為C6-C18的芳基或C3-C15的雜芳基。
作為優選的化合物為以下化合物:
B 1 | B 2 | B 3 |
B 4 | B 5 | B 6 |
B 7 | B 8 | B 9 |
B 10 | B 11 | B 12 |
B 13 | B 14 | B 15 |
B 16 | B 17 | B 18 |
B 19 | B 20 | B 21 |
B 22 | B 23 | B 24 |
B 25 | B 26 | B 27 |
B 28 | B 29 | B 30 |
B 31 | B 32 | B 33 |
B 34 | B 35 | B 36 |
B 37 | B 38 | B 39 |
B 40 | B 41 | B 42 |
B 43 | B 44 | B 45 |
B 46 | B 47 | B 48 |
B 49 | B 50 | B 51 |
B 52 | B 53 | B 54 |
B 55 | B 56 | B 57 |
B 58 | B 59 | B 60 |
B 61 | B 62 | B 63 |
B 64 | B 65 | B 66 |
B 67 | B 68 | B 69 |
B 70 | B 71 | B 72 |
B 73 | B 74 | B 75 |
B 76 | B 77 | B 78 |
B 79 | B 80 | B 81 |
B 82 | B 83 | B 84 |
B 85 | B 86 | B 87 |
B 88 | B 89 | B 90 |
B 91 | B 92 | B 93 |
B 94 | B 95 | B 96 |
B 97 | B 98 | B 99 |
B 100 | B 101 | B 102 |
B 103 | B 104 | B 105 |
B 106 | B 107 | B 108 |
B 109 | B 110 | B 111 |
B 112 | B 113 | B 114 |
B 115 | B 116 | B 117 |
B 118 | B 119 | B 120 |
B 121 | B 122 | B 123 |
B 124 | B 125 | B 126 |
B 127 | B 128 | B 129 |
B 130 | B 131 | B 132 |
B 133 | B 134 | B 135 |
B 136 | B 137 | B 138 |
B 139 | B 140 | B 141 |
B 142 | B 143 | B 144 |
B 145 | B 146 | B 147 |
B 148 | B 149 | B 150 |
B 151 | B 152 | B 153 |
B 154 | B 155 | B 156 |
B 157 | B 158 | B 159 |
B 160 | B 161 | B 162 |
B 163 | B 164 | B 165 |
B 166 | B 167 | B 168 |
B 169 | B 170 | B 171 |
B 172 | B 173 | B 174 |
B 175 | B 176 | B 177 |
B 178 | B 179 | B 180 |
B 181 | B 182 | B 183 |
B 184 | B 185 | B 186 |
B 187 | B 188 | B 189 |
B 190 | B 191 | B 192 |
B 193 | B 194 | B 195 |
B 196 | B 197 | B 198 |
B 199 | B 200 | B 201 |
B 202 | B 203 | B 204 |
B 205 | B 206 | B 207 |
B 208 | B 209 | B 210 |
B 211 | B 212 | B 213 |
B 214 | B 215 | B 216 |
B 217 | B 218 | B 219 |
B 220 | B 221 | B 222 |
B 223 | B 224 | B 225 |
B 226 | B 227 | B 228 |
B 229 | B 230 | B 231 |
B 232 | B 233 | B 234 |
B 235 | B 236 | B 237 |
B 238 | B 239 | B 240 |
B 241 | B 242 | B 243 |
B 244 | B 245 | B 246 |
B 247 | B 248 | B 249 |
B 250 | B 251 | B 252 |
B 253 | B 254 | B 255 |
B 256 | B 257 | B 258 |
B 259 | B 260 | B 261 |
B 262 | B 263 | B 264 |
B 265 | B 266 | B 267 |
B 268 | B 269 | B 270 |
B 271 | B 272 | B 273 |
B 274 | B 275 | B 276 |
B 277 | B 278 | B 279 |
B 280 | B 281 | B 282 |
B 283 | B 284 | B 285 |
B 286 | B 287 | B 288 |
B 289 | B 290 | B 291 |
B 292 | B 293 | B 294 |
B 295 | B 296 | B 297 |
B 298 | B 299 | B 300 |
B 301 | B 302 | B 303 |
B 304 | B 305 | B 306 |
B 307 | B 308 | B 309 |
B 310 | B 311 | B 312 |
B 313 | B 314 | B 315 |
B 316 | B 317 | B 318 |
B 319 | B 320 | B 321 |
B 322 | B 323 | B 324 |
B 325 | B 326 | B 327 |
B 328 | B 329 | B 330 |
B 331 | B 332 | B 333 |
B 334 | B 335 | B 336 |
B 337 | B 338 | B 339 |
B 340 | B 341 | B 342 |
B 343 | B 344 | B 345 |
B 346 | B 347 | B 348 |
B 349 | B 350 | B 351 |
B 352 | B 353 | B 354 |
B 355 | B 356 | B 357 |
B 358 | B 359 | B 360 |
B 361 | B 362 | |
。 |
上述化合物在OLED器件中的應用。
所述應用為化合物作為OLED器件的電子傳輸層材料、空穴阻隔層材料和/或光提取層材料。
本發明的化合物材料具有昇華溫度低,光、電、熱穩定性好,發光效率高,電壓低、壽命長,折射率高、可見光區折射率差異小等優點,可用於有機發光器件中,特別是作為電子傳輸材料、空穴阻隔層材料、光提取層材料,該器件具有驅動電壓低、發光效率高、器件壽命長的優點,具有應用於AMOLED產業的可能。
下述實施例僅僅是為了便於理解技術發明,不應視為本發明的具體限制。
本發明中的化合物合成中涉及的原物料和溶劑等均購自於Alfa、Acros等本領域技術人員熟知的供應商。
實施例:
化合物03的合成:向一個2L單口瓶,依次將化合物01(53.17g,0.57mol,1.0eq)、化合物02(200g,0.57mol,1.0eq),NaHCO3(94.9g,1.14mol,2.0eq)、異丙醇(1000ml)投入到燒瓶中,油浴加熱到80度左右,保溫攪拌回流7h,取樣點板原料反應完。降溫,滴加去離子水,攪拌4h左右,抽濾。固體用乙醇打漿,抽濾烘乾。得到157g白色固體化合物03,收率79.6%。質譜:349.03(M+H)。
化合物04的合成:向一個1L單口瓶,依次加入化合物03(60g,171.81mmol,1.0eq)、雙聯頻呐硼酸酯(56.72g,223.35mmol,1.3eq)、Pd(dppf)Cl2(1.26g,1.72mmol,0.01eq)、CH3COOK(33.72g,343.62mmol,2.0eq),600ml二氧六環,攪拌下N2置換3次,加熱,回流3h。TLC監測反應完全(EA/Hex=1:8)。反應液降至室溫,真空濃縮二氧六環至無溶劑餾出,加入600mlDCM將固體溶解,用水200ml洗一次,將水相用200ml DCM提一次,合併有機相,並用水洗兩次(每次200ml),將有機相有無水MgSO4乾燥。過矽膠濾,並用DCM 300ml淋洗,濃縮有機相至僅剩150ml左右,加入正己烷500ml降至室溫結晶2h。過濾,濾餅用正己烷100ml,淋洗,抽乾得到59g,真空乾燥過夜,得到54g類白色固體化合物04,收率78.2%。質譜:397.30(M+H)。
化合物A1的合成:向一個1L單口瓶,依次加入化合物04(45.06g,113.73mmol,2.1eq)、化合物05(12.62g,54.16mmol,1.0eq),Pd132(383.5mg,0.5416mmol,0.01eq),K2
CO3
(15.69g,113.73mmol,2.1eq),甲苯450ml,乙醇150ml,水150ml攪拌下N2置換3次,加熱,回流20h。TLC監測反應完全,降至室溫後過濾,濾餅分別依次用水200ml,甲醇100ml,甲苯100ml,甲醇100ml淋洗,抽乾,得到灰白色固體37g。將所得固體用THF重結晶,得到28g白色固體化合物A1。得到的化合物經過昇華純化得到21克米白色固體化合物A1,收率75%。質譜:692.28(M+H);1H NMR (400 MHz, CDCl3) δ 8.13 (d, J = 8.4 Hz, 4H), 7.98 (d, J = 6.9 Hz, 2H), 7.87 (s, 2H), 7.81 (d, J = 8.3 Hz, 4H), 7.72 (t, J = 8.4 Hz, 4H), 7.58 – 7.43 (m, 13H), 7.24 – 7.19 (m, 2H), 6.75 (t, J = 6.8 Hz, 2H)。
化合物08的合成:參照化合物A1合成過程中,化合物04的合成方式和處理方法,只需要將對應的原物料變更即可。質譜:397.30(M+H)。
化合物10的合成:將化合物08(22g,55.53mmol,2.1eq)、化合物09(22.5g,53.44mmol,1.04eq)、K2
CO3
(11g,79.71mmol,1.5eq)、Pd(PPh3
)4
(1.2g,1.04mmol,0.02eq)、甲苯(400ml)、乙醇(50ml)、水(50ml)依次加入到1L的四口燒瓶中,置換N2三次,升溫至80℃,攪拌6小時,TLC顯示反應完全。反應液降溫後,過濾,濾渣用乙醇/水打漿,抽濾得25g灰色固體化合物10,收率75%。質譜:612.19(M+H)。
化合物11的合成:將化合物10(25g,40.90mmol,1.0eq)、雙聯頻呐硼酸酯(15.5g,61mmol,1.5eq)、X-Phos(0.8g,1.68mmol,0.04eq)、CH3
COOK(8g,81.52mmol,2.0eq)、dioxane(400ml)、Pd(OAc)2
(183mg,0.81mmol,0.02eq)依次加入至1L的四口燒瓶中,置換N2三次,升溫至105℃,攪拌3小時,TLC顯示反應完全。反應液降溫後,加DCM(200ml),矽膠過濾,母液水洗後旋乾, 得到的殘渣用甲苯/正己烷重結晶得26g白色固體化合物11,收率91%。質譜:704.31(M+H)。
化合物B283的合成:將化合物11(26g,36.97mmol,1.0eq)、化合物12(10.3g,55.67mmol,1.5eq)、K2
CO3
(10.2g,73.91mmol,2.0eq)、Pd-132(0.5g,0.7061mmol,0.02eq)、甲苯(300ml)、乙醇(50ml)、水(50ml)依次加入至1L的四口燒瓶中,置換N2三次,開始升溫體系至85℃,攪拌5小時,反應完全。降溫後反應液加DCM稀釋(500ml),濾矽膠,母液水洗後旋乾得25g粗品,殘渣用Tol/hex重結晶得12g白色固體化合物B283,收率48%。得到的化合物經過昇華純化得到7.56克米白色固體化合物B283,收率63%。質譜:683.28(M+H);1H NMR (400 MHz, CDCl3) δ 8.99 (s, 1H), 8.77-8.73 (m, 5H), 8.13-8.11 (d, 2H), 7.99-7.87 (m, 2H), 7.78-7.69 (m, 5H), 7.64 – 7.52 (m, 8H), 7.34 – 7.29 (t, 2H), 7.24 – 7.21 (t, 2H), 7.14 – 7.12 (d, 1H),2.64 (s, 3H) ,2.60 (s, 3H)。
選取對應的材料,用同樣類似的方法可以用於合成、昇華得到其他化合物。
應用例:
(1)化合物性能對比:本發明的化合物在OLED器件中可作為光提取層材料,具有較高的玻璃化轉變溫度、較高的折射率、可見光區較小的折射率差值。基本性能列於下表1
表1:折射率對比:
玻璃化溫度 | 折射率 | 折射率差值 | |||||
@450nm | @520nm | @630nm | ΔB-G | ΔB-R | ΔG-R | ||
化合物A1 | 150 | 2.14 | 2.05 | 2.00 | 0.09 | 0.14 | 0.05 |
化合物B283 | 128 | 2.02 | 1.96 | 1.94 | 0.06 | 0.08 | 0.02 |
化合物A3 | 156 | 2.21 | 2.16 | 2.06 | 0.05 | 0.15 | 0.1 |
化合物B19 | 134 | 2.09 | 2.03 | 1.98 | 0.06 | 0.11 | 0.05 |
化合物B23 | 133 | 2.06 | 1.99 | 1.94 | 0.07 | 0.12 | 0.05 |
化合物A46 | 158 | 2.03 | 1.95 | 1.91 | 0.08 | 0.12 | 0.04 |
化合物A2 | 155 | 2.24 | 2.12 | 2.06 | 0.12 | 0.18 | 0.06 |
HTM1 | 134 | 1.99 | 1.91 | 1.85 | 0.08 | 0.14 | 0.06 |
對比化合物3 | 132 | 1.99 | 1.89 | 1.84 | 0.1 | 0.15 | 0.05 |
(2)有機電致發光器件的製作
將50mm*50mm*1.0mm的具有ITO(100nm)透明電極的玻璃基板在乙醇中超聲清洗10分鐘,再150度烘乾後經過N2 Plasma處理30分鐘。將洗滌後的玻璃基板安裝在真空蒸鍍裝置的基板支架上,首先在有透明電極線一側的面上按照覆蓋透明電極的方式蒸鍍化合物HATCN,形成膜厚為5nm的薄膜,緊接著蒸鍍一層HTM1形成膜厚為60nm的薄膜,再在HTM1薄膜上蒸鍍一層HTM2形成膜厚為10nm的薄膜,然後,在HTM2膜層上再採用共蒸鍍的模式蒸鍍主體材料CBP和摻雜材料,膜厚為30nm,主體材料和摻雜材料比例為90%:10%。在發光層上再依次按照下表的搭配蒸鍍HBL(5nm)作為空穴阻隔層材料、ETL(30nm)作為電子傳輸材料,接著在電子傳輸材料層之上蒸鍍LiF(1nm) 作為電子注入材料,接著再採用共蒸鍍的模式蒸鍍Mg/Ag(18nm,1:9)作為陰極材料,最後在陰極材料之上按照下表的搭配蒸鍍CPL(50nm)作為光提取層材料。
器件性能評價
將上述器件進行器件性能測試,在各實施例和比較例中,使用恒定電流電源(Keithley 2400),使用固定的電流密度流過發光元件,使用分光輻射倆都系(CS 2000)測試發光波譜。同時測定電壓值以及測試亮度為初始亮度的90%的時間(LT90)。結果如下表2:
表2:
HBL | ETL | CPL | 啟動電壓V @3000nits | 電流效率Cd/A @3000nits | LT90@ 3000nits | |
實施例1 | 化合物A1 | 化合物A1 | HTM1 | 4.6 | 61 | 186 |
實施例2 | 化合物B283 | 化合物B283 | HTM1 | 4.5 | 63 | 175 |
實施例3 | 化合物A3 | 化合物A3 | HTM1 | 4.6 | 64 | 192 |
實施例4 | 化合物B19 | 化合物B19 | HTM1 | 4.4 | 62 | 169 |
實施例5 | 化合物B23 | 化合物B23 | HTM1 | 4.3 | 63 | 173 |
實施例6 | 化合物A46 | 化合物A46 | HTM1 | 4.5 | 61 | 181 |
實施例7 | 化合物A2 | 化合物A2 | HTM1 | 4.5 | 60 | 156 |
實施例8 | 化合物B340 | 化合物B283 | 化合物A3 | 4.2 | 68 | 216 |
實施例9 | 對比化合物1 | 對比化合物1 | 化合物A3 | 4.7 | 53 | 96 |
實施例10 | 對比化合物2 | 對比化合物2 | 化合物A3 | 4.7 | 55 | 130 |
實施例11 | 化合物B340 | 化合物B23 | 化合物A3 | 4.6 | 69 | 256 |
實施例12 | 化合物B340 | 化合物B9 | 化合物A2 | 4.7 | 67 | 234 |
對比例1 | 對比化合物1 | 對比化合物1 | HTM1 | 5.2 | 48 | 92 |
對比例2 | 對比化合物2 | 對比化合物2 | HTM1 | 4.9 | 50 | 125 |
由上面表格中的資料對比可知,使用本發明的化合物應用於有機電致發光器件作為空穴阻隔層或電子傳輸層或光提取層材料,相較於對比化合物在驅動電壓、發光效率、器件壽命都表現出更加優越的性能。
上述結果表明本發明的化合物具有昇華溫度低,光、電、熱穩定性好,折射率高、可見光區折射率差異小等優點,該化合物製備的器件具有電壓低、壽命長,發光效率高等優點,可用於有機發光器件中。特別是作為電子傳輸材料、空穴阻隔層材料、光提取層材料,具有應用於AMOLED產業的可能。
Claims (14)
- 一種化合物,其結構式如式(I)所示:
- 如請求項1所述的化合物,其中,R1為單鍵、C1-C30烷基、C1-C30雜烷基、C3-C30環烷基、取代或未取代的C6-C30的非稠環芳基、取代或未取代的C3-C27的非稠環雜芳基;其中,R2、R3、R4獨立的選自氫、氘、鹵素、C1-C30烷基、C1-C30雜烷基、C3-C30環烷基、氨基、矽烷基、腈、異腈、膦基、取代或未取代的C6-C60的芳基、取代或未取代的C1-C60的雜芳基、經取代或未經取代的單環或多環C3-C60脂肪族環或芳香族環且R3、R4中至少有一個為取代或未取代的C6-C60的芳基、取代或未取代的C1-C60的雜芳基、經取代或未經取代的單環或多環C3-C60脂肪族環或芳香族環,其中雜烷基或雜芳基中的一個或多個碳原子由選自O、S、N中的至少一個雜原子替換;所述取代為被氘、鹵素、C1-C30烷基、C1-C30雜烷基、C3-C30環烷基、氨基、矽烷基、腈、異腈、、膦基、C6-C60的芳基、C1-C60的雜芳基取代;其中,X1、X2、X3獨立的表示為CH或者N;X4、X5、X6獨立的表示為CR0或者N,R0獨立的選自氫、氘、鹵素、C1-C30烷基、C1-C30雜烷基、芳烷基、氨基、矽烷基、芳基、雜芳基、腈、異腈、膦基,且相鄰的R0能鍵接成並環。
- 如請求項1或2中任一項所述的化合物,其中,X1、X2、X3至少一個是N。
- 如請求項4所述的化合物,其中,R3、R4中一個為式(II)結構,另一個為C1-C4烷基取代或未取代的C6-C18的芳基、C1-C4烷基取代或未取代的C3-C15的雜芳基;R1為C1-C4烷基取代或未取代的C6-C18的非稠環芳基、C1-C4烷基取代或未取代的C3-C15的非稠環雜芳基;R2為C1-C4烷基取代或未取代的C6-C18的芳基、C1-C4烷基取代或未取代的C3-C15的雜芳基。
- 如請求項5所述的化合物,其中,R1為C6-C18的非稠環芳基或C5-C15的非稠環雜芳基;R2為C6-C18的芳基或C5-C15的雜芳基。
- 請求項1至2中任一項所述的化合物,其中,X1、X2、X3表示為CH。
- 如請求項8所述的化合物,其中,R1為單鍵、C1-C30烷基取代或未取代的C6-C30的非稠環芳基、C1-C30烷基取代或未取代的C3-C27的非稠環雜芳基;其中,R2為C1-C30烷基取代或未取代的C6-C60的芳基、C1-C30烷基取代或未取代的C1-C60的雜芳基;R3、R4為氫、氘、鹵素、烷基、雜烷基、環烷基、C1-C30烷基取代或未取代的C6-C60的芳基、C1-C30烷基取代或未取代的C1-C60的雜芳基、經取代或未經取代的單環或多環C3-C60脂肪族環或芳香族環且R3、R4中至少有一個為C1-C30烷基取代或未取代的C6-C60的芳基、C1-C30烷基取代或未取代的C1-C60的雜芳基、經取代或未經取代的單環或多環C3-C60脂肪族環或芳香族環,且R4不為取代或未取代的咪唑基。
- 如請求項9所述的化合物,其中,R1為單鍵、C1-C4烷基取代或未取代的C6-C18的非稠環芳基、C1-C4烷基取代或未取代的C3-C15的非稠環雜芳基;R2為C1-C4烷基取代或未取代的C6-C18的芳基、C1-C4烷基取代或未取代的C3-C15的雜芳基;R3、R4為氫、氘、鹵素、烷基、C1-C4烷基取代或未取代的C6-C18的芳基、C1-C4烷基取代或未取代的C3-C15的雜芳基、經取代或未經取代的單環或多環C3-C18脂肪族環或芳香族環且R3、R4不同,且R4不為取代或未取代的咪唑基。
- 如請求項10所述的化合物,其中,R1為單鍵、C6-C18的非稠環芳基或C3-C15的非稠環雜芳基;R2為C6-C18的芳基或C3-C15的雜芳基。
- 一種如請求項1至12中任一項所述的化合物在OLED器件中的應用。
- 如請求項13所述的應用,其特徵在於作為OLED器件的電子傳輸層材料、空穴阻隔層材料和/或光提取層材料。
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1626531A (zh) * | 2003-10-13 | 2005-06-15 | 三星Sdi株式会社 | 含咪唑环的化合物和有机电致发光显示器 |
TW200846348A (en) * | 2006-11-24 | 2008-12-01 | Samsung Sdi Co Ltd | Imidazopyridine-based compound and organic light emitting diode including organic layer comprising the imidazopyridine-based compound |
KR20090079134A (ko) * | 2008-01-16 | 2009-07-21 | 주식회사 엘지화학 | 새로운 이미다졸 유도체 및 이를 이용한 유기전자소자 |
US7763882B2 (en) * | 1999-12-31 | 2010-07-27 | Lg Chem, Ltd. | Organic light-emitting device comprising buffer layer and method for fabricating the same |
JP5351124B2 (ja) * | 1999-07-22 | 2013-11-27 | ユー・ディー・シー アイルランド リミテッド | 新規ヘテロ環化合物、発光素子材料及び発光素子 |
CN104882555A (zh) * | 2008-05-16 | 2015-09-02 | Lg化学株式会社 | 层叠式有机发光二极管 |
CN105968100A (zh) * | 2016-07-16 | 2016-09-28 | 吉林奥来德光电材料股份有限公司 | 一种咪唑类衍生物化合物及其制备方法和发光器件 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4290858B2 (ja) * | 2000-06-12 | 2009-07-08 | 富士フイルム株式会社 | 有機電界発光素子 |
US7196095B2 (en) | 2001-06-25 | 2007-03-27 | Merck & Co., Inc. | (Pyrimidinyl) (phenyl) substituted fused heteroaryl p38 inhibiting and PKG kinase inhibiting compounds |
JP5006606B2 (ja) * | 2006-09-13 | 2012-08-22 | 双葉電子工業株式会社 | 有機el素子用化合物及び有機el素子 |
JP5640006B2 (ja) | 2008-07-14 | 2014-12-10 | ギリアード サイエンシーズ, インコーポレイテッド | ヒストン脱アセチル化酵素および/またはサイクリン依存性キナーゼの縮合複素環式阻害剤 |
US20120190666A1 (en) | 2009-05-13 | 2012-07-26 | Amgen Inc. | Heteroaryl Compounds as PIKK Inhibitors |
CN102070632B (zh) * | 2009-11-20 | 2013-09-11 | 中国科学院理化技术研究所 | 吡啶并咪唑衍生物及其在有机电致发光器件中的应用 |
JP5898950B2 (ja) * | 2010-12-27 | 2016-04-06 | 東ソー株式会社 | 1,3,5−トリアジン化合物とその製造方法、及びそれらを構成成分とする有機電界発光素子 |
CN104650117B (zh) * | 2013-12-26 | 2017-08-01 | 北京鼎材科技有限公司 | 一种有机化合物及其在有机电致发光器件中的应用 |
CN104650116B (zh) * | 2013-12-26 | 2017-12-05 | 北京鼎材科技有限公司 | 一种有机化合物及其在有机电致发光器件中的应用 |
US10292970B2 (en) | 2014-12-02 | 2019-05-21 | Bayer Pharma Aktiengesellschaft | Heteroaryl-substituted imidazo[1,2-A]pyridines and their use |
KR102510282B1 (ko) * | 2015-12-24 | 2023-03-16 | 솔루스첨단소재 주식회사 | 유기 발광 화합물 및 이를 이용한 유기 전계 발광 소자 |
CN108864079B (zh) | 2017-05-15 | 2021-04-09 | 深圳福沃药业有限公司 | 一种三嗪化合物及其药学上可接受的盐 |
-
2019
- 2019-05-13 CN CN201910393579.5A patent/CN111925366B/zh active Active
-
2020
- 2020-03-23 TW TW109109688A patent/TWI724829B/zh active
- 2020-03-28 KR KR1020217028611A patent/KR102615337B1/ko active IP Right Grant
- 2020-03-28 US US17/432,335 patent/US20220169661A1/en active Pending
- 2020-03-28 WO PCT/CN2020/081895 patent/WO2020228430A1/zh active Application Filing
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5351124B2 (ja) * | 1999-07-22 | 2013-11-27 | ユー・ディー・シー アイルランド リミテッド | 新規ヘテロ環化合物、発光素子材料及び発光素子 |
US7763882B2 (en) * | 1999-12-31 | 2010-07-27 | Lg Chem, Ltd. | Organic light-emitting device comprising buffer layer and method for fabricating the same |
CN1626531A (zh) * | 2003-10-13 | 2005-06-15 | 三星Sdi株式会社 | 含咪唑环的化合物和有机电致发光显示器 |
TW200846348A (en) * | 2006-11-24 | 2008-12-01 | Samsung Sdi Co Ltd | Imidazopyridine-based compound and organic light emitting diode including organic layer comprising the imidazopyridine-based compound |
KR20090079134A (ko) * | 2008-01-16 | 2009-07-21 | 주식회사 엘지화학 | 새로운 이미다졸 유도체 및 이를 이용한 유기전자소자 |
CN104882555A (zh) * | 2008-05-16 | 2015-09-02 | Lg化学株式会社 | 层叠式有机发光二极管 |
CN105968100A (zh) * | 2016-07-16 | 2016-09-28 | 吉林奥来德光电材料股份有限公司 | 一种咪唑类衍生物化合物及其制备方法和发光器件 |
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KR102615337B1 (ko) | 2023-12-19 |
CN111925366B (zh) | 2024-04-09 |
WO2020228430A1 (zh) | 2020-11-19 |
TW202041506A (zh) | 2020-11-16 |
US20220169661A1 (en) | 2022-06-02 |
KR20210126065A (ko) | 2021-10-19 |
CN111925366A (zh) | 2020-11-13 |
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