CN109134347A - 一种具有tadf特性的双受体型多取代咔唑类化合物及其制备方法和应用 - Google Patents
一种具有tadf特性的双受体型多取代咔唑类化合物及其制备方法和应用 Download PDFInfo
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- -1 polysubstituted carbazole compound Chemical class 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 150000001875 compounds Chemical group 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 25
- 239000003513 alkali Substances 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 25
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 9
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 8
- 238000002347 injection Methods 0.000 claims description 6
- 239000007924 injection Substances 0.000 claims description 6
- 230000005540 biological transmission Effects 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 4
- 235000011009 potassium phosphates Nutrition 0.000 claims description 4
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000005401 electroluminescence Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 claims 1
- 239000000758 substrate Substances 0.000 claims 1
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 abstract description 12
- 239000002585 base Substances 0.000 abstract description 2
- 239000012299 nitrogen atmosphere Substances 0.000 abstract description 2
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000012467 final product Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 150000001716 carbazoles Chemical class 0.000 description 4
- 238000011097 chromatography purification Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000003111 delayed effect Effects 0.000 description 3
- 239000007850 fluorescent dye Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- ZEOMRHKTIYBETG-UHFFFAOYSA-N 2-phenyl-1,3,4-oxadiazole Chemical class O1C=NN=C1C1=CC=CC=C1 ZEOMRHKTIYBETG-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 2
- 150000004866 oxadiazoles Chemical class 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- ZQWJZVCRQDBHBQ-UHFFFAOYSA-N 1-butyl-9h-carbazole Chemical compound C12=CC=CC=C2NC2=C1C=CC=C2CCCC ZQWJZVCRQDBHBQ-UHFFFAOYSA-N 0.000 description 1
- BKPDQETYXNGMRE-UHFFFAOYSA-N 1-tert-butyl-9h-carbazole Chemical compound N1C2=CC=CC=C2C2=C1C(C(C)(C)C)=CC=C2 BKPDQETYXNGMRE-UHFFFAOYSA-N 0.000 description 1
- PRWATGACIORDEL-UHFFFAOYSA-N 2,4,5,6-tetra(carbazol-9-yl)benzene-1,3-dicarbonitrile Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=C(C#N)C(N2C3=CC=CC=C3C3=CC=CC=C32)=C(N2C3=CC=CC=C3C3=CC=CC=C32)C(N2C3=CC=CC=C3C3=CC=CC=C32)=C1C#N PRWATGACIORDEL-UHFFFAOYSA-N 0.000 description 1
- CRGSMSNUTNRNQM-UHFFFAOYSA-N 2-(4-tert-butylphenyl)-1,3,4-oxadiazole Chemical class C1=CC(C(C)(C)C)=CC=C1C1=NN=CO1 CRGSMSNUTNRNQM-UHFFFAOYSA-N 0.000 description 1
- CINYXYWQPZSTOT-UHFFFAOYSA-N 3-[3-[3,5-bis(3-pyridin-3-ylphenyl)phenyl]phenyl]pyridine Chemical compound C1=CN=CC(C=2C=C(C=CC=2)C=2C=C(C=C(C=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)=C1 CINYXYWQPZSTOT-UHFFFAOYSA-N 0.000 description 1
- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical group C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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- 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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Abstract
本发明公开了一种具有TADF特性的双受体型多取代咔唑类化合物及其制备方法和应用,所述化合物结构如式I所示。所述化合物的制备方法包括如下步骤:以多氟取代的1,4‑双(5‑苯基‑1,3,4‑噁二唑‑2‑基)苯衍生物或全氟取代的4,4′‑二甲基‑1,1′‑联苯为原料,加入咔唑,碱和有机溶剂,在氮气氛围下反应即得。本发明提供的TADF材料在纯固态下具有非常高的PLQY,将其作为发光客体应用在OLEDs中具有较高的电致发光效率。
Description
技术领域
本发明涉及一种热激活延迟荧光材料,特别涉及一种具有TADF特性的双受体型多取代咔唑类化合物及其制备方法和应用。
背景技术
有机发光二极管(OLED)具有重量轻、视角宽、驱动电压低、响应快、可实现柔性显示等优点,被认为是替代液晶显示的下一代显示技术。目前已经商业化应用在OLEDs中的材料主要是贵金属配合物的磷光材料,但由于其资源稀缺、价格昂贵,限制了其大规模的应用。热激活延迟荧光(TADF)可以实现三线态(T1)到单线态(S1)的反系间窜越过程,其三线态也能被有效利用有效发光,能够实现100%的最大内量子效率。用该类材料制备的OLEDs器件,能够实现较高的发光效率,可以和商业化的磷光OLEDs器件相媲美。例如,Adachi等报导的绿光TADF发光材料4CzIPN,器件外量子效率超过20%。[Uoyama,H.et al.Nature 492,234-238(2012).;Lin,T.A.et al.Adv.Mater.28,6976-6983(2016).]
TADF发光材料通常为纯有机小分子,可通过优选合成路线实现廉价绿色的制备流程,进一步降低成本。为了提高TADF-OLEDs的器件效率,对TADF荧光材料要求提出以下几个要求:1、分子的应具有较小的ΔEST(单线态S1与其三线态T1的能级差),以有效实现三线态激子到单线态激子的反系间窜越;2,具有较高的辐射跃迁速率,从而实现激子的高效发光;3,良好的载流子迁移能力、成膜性和热稳定性;4,具有较弱的分子间作用力,防止与主体分子间的强相互作用而引起的聚集淬灭。通常平面类TADF荧光染料由于其分子间具有较强的相互作用可以有效促进载流子传输,但也会促进分子的聚集,从而引起发射淬灭,降低器件的效率。
咔唑是有机光电材料中常用的供体单元,在单一苯环上引入多个咔唑取代基,能够利用空间位阻效应,形成空间扭曲的分子构型。这样既可以满足TADF材料要求的HOMO/LUMO空间离域的要求,同时又能实现较弱的分子间作用力,降低了分子间聚集引起的淬灭。另外,噁二唑和三氟甲基是TADF材料中较为罕见的电子受体单元,可以被用来构建TADF荧光染料。但是早期的报导以单一受体为主,器件外量子效率不超过10%。[Di Zhang,etal.J.Mater.Chem.C,2018,6,3675-3682(2018).;Ling Mei,et al.Chem.Commun.,2015,51,13024-13027(2015)]
发明内容
本发明的目的是提供一种具有TADF特性的双受体型多取代咔唑类化合物,以解决现有的以噁二唑和三氟甲基为单一电子受体的TADF荧光染料在纯固体条件下荧光量子效率不高,制备的器件效率低的问题。
本发明的另一个目的是提供所述具有TADF特性的双受体型多取代咔唑类化合物的制备方法。
本发明的另一个目的是提供所述具有TADF特性的双受体型多取代咔唑类化合物的应用。
本发明的最后一个目的是提供包含所述的具有TADF特性的双受体型多取代咔唑类化合物的有机电致发光器件。
为实现上述目的,本发明技术方案如下:
一种具有TADF特性的双受体型多取代咔唑类化合物,其结构如式I所示:
其中,R1选自:
或CF3;
R2选自:
R3选自H或叔丁基。
优选地,所述的具有TADF特性的双受体型多取代咔唑类化合物选自:
本发明所述具有TADF特性的双受体型多取代咔唑类化合物的制备方法,
当R2选自时,所述方法包括以下步骤:式II化合物与式III化合物在惰性气体保护下,在碱和有机溶剂的存在下反应,得到式I化合物,
其中,R1选自:
或CF3;
R3选自H或叔丁基。
所述的碱为碳酸钾、磷酸钾或叔丁醇钾,所述的有机溶剂为二甲基亚砜或N,N-二甲基甲酰胺,优选为二甲基亚砜,式II化合物、式III化合物和碱的摩尔比为1∶(5-7)∶(15-20),优选1∶(5.5-6)∶(16-18),反应温度为135-160℃,优选140-150℃,更优选150℃,反应时间为8-16h,优选12-15h,更优选12h。
本发明所述具有TADF特性的双受体型多取代咔唑类化合物的制备方法,
当R2选自时,所述方法包括以下步骤:式IV化合物与式III化合物在惰性气体保护下,在碱和有机溶剂的存在下反应,得到式I化合物,
其中,R1选自:
或CF3;
R3选自H。
所述的碱为碳酸钾、磷酸钾或叔丁醇钾,所述的有机溶剂为二甲基亚砜或N,N-二甲基甲酰胺,优选为二甲基亚砜,式IV化合物、式III化合物和碱的摩尔比为1∶(8-12)∶(20-40),优选1∶10∶30,反应温度为135-160℃,优选140-150℃,更优选140℃,反应时间为8-16h,优选12-15h,更优选12h。
本发明所述惰性气体优选为氮气。
更优选地,所述具有TADF特性的双受体型多取代咔唑类化合物的制备方法,包括如下步骤:以多氟取代的1,4-双(5-苯基-1,3,4-噁二唑-2-基)苯衍生物或全氟取代的4,4′-二甲基-1,1′-联苯为原料,加入咔唑(或叔丁基咔唑),碱(K2CO3等),有机溶剂(DMSO或DMF),在氮气氛围下反应12h-15h,再用柱层析提纯得到纯品产物。
所述的具有TADF特性的双受体型多取代咔唑类化合物作为TADF荧光材料的应用。具有电子传输性能的噁二唑单元或三氟甲基单元和具有空穴传输性能的咔唑单元的双受体型化合物作为TADF荧光材料的应用。
所述的具有TADF特性的双受体型多取代咔唑类化合物作为TADF荧光材料在制备电致发光器件中的应用。所述的双受体型多咔唑取代的热激活延迟荧光材料,作为发光材料应用在有机电致发光的器件中。
所述的具有TADF特性的双受体型多取代咔唑类化合物的电致发光器件,由下至上依次包括玻璃、附着在玻璃上的导电玻璃衬底层,与导电玻璃衬底层贴合的空穴注入层,与空穴注入层贴合的空穴传输层,与空穴传输层贴合的发光层,与发光层贴合的电子传输层,与电子传输层贴合的阴极层,所述的发光层包含本发明所述的化合物。
所述发光层的掺杂主体材料为CBP,掺杂客体材料为本发明所述的化合物。
有益效果:
1、本发明提供的TADF材料在纯固态下具有非常高的PLQY,将其作为发光客体应用在OLEDs中具有较高的电致发光效率。
2、本发明方法在无贵金属催化剂的条件下直接形成碳氮单键,操作简便、高效、条件温和,适于工业化生产。
附图说明
图1为本发明四种化合物在DCM溶液中的吸收光谱图和光致发光光谱图。
图2为本发明四种化合物充当OLED器件掺杂客体的电致发光光谱图。
具体实施方式
为了更好地理解本发明,下面通过具体的实施例来具体说明本发明的技术方案。
实施例1:4Cz-DOXD的合成
5,5′-(全氟-1,4-亚苯基)双(2-苯基-1,3,4-噁二唑)(0.5g,1.14mmol),咔唑(1.14g,6.84mmol),K2CO3(2.84g,20.53mmol),DMSO 20ml,氮气保护下,150℃加热反应12h。冷却至室温后倒入200ml饱和食盐水中搅拌,析出大量黄色固体,抽滤,经柱层析提纯后得到黄色固体产物1g,产率85%。1H NMR(CDCl3,303k,500Hz):δ=7.736-7.685(d,8H),7.351-7.315(d,10H),7.160-7.088(t,12H),7.083-7.017(t,8H),6.805-6.754(d,4H)。
实施例2:4TCz-DOXD的合成
5,5′-(全氟-1,4-亚苯基)双(2-苯基-1,3,4-噁二唑)(0.5g,1.14mmol),3,6-二叔丁基咔唑(1.91g,6.84mmol),K2CO3(2.84g,20.53mmol),DMSO 20ml,氮气保护下,150℃加热反应12h。冷却至室温后倒入200ml饱和食盐水中搅拌,析出大量黄色固体,抽滤,经柱层析提纯后得到黄色固体产物1.45g,产率85%。1H NMR(CDCl3,303k,500Hz):δ=7.60(s,8H),7.351-7.315(d,2H),7.182-7.129(d,12H),7.129-7.076(d,8H),6.988-6.937(d,4H),1.31(s,72H)。
实施例3:4Cz-tBu的合成
5,5′-(全氟-1,4-亚苯基)双(2-(4-(叔丁基)苯基)-1,3,4-噁二唑)(0.5g,0.98mmol),咔唑(0.911g,5.45mmol),K2CO3(2.26g,16.35mmol),DMSO 20ml,氮气保护下,150℃加热反应12h。冷却至室温后倒入200ml饱和食盐水中搅拌,析出大量黄色固体,抽滤,经柱层析提纯后得到黄色固体产物0.96g,产率约85%。1H NMR(CDCl3,303k,500Hz):δ=7.742-7.690(s,8H),7.340-7.034(d,8H),7.149-7.086(t,12H),7.086-7.020(t,8H),6.738-6.685(d,4H),1.27(s,18H)。
实施例4:7Cz2Ph2CF3的合成
八氟-4,4′-双(三氟甲基)-1,1′-联苯(0.2g,.461mmol),咔唑(0.766g,4.61mmol),K2CO3(1.91g,13.82mmol),DMSO 20ml,氮气保护下,140℃加热反应12h。冷却至室温后倒入200ml饱和食盐水中搅拌,析出大量黄色固体,抽滤,经柱层析提纯后得到黄色固体产物0.43g,产率约64%。1H NMR(CDCl3,303k,500Hz):δ=8.191-8.128(2H),7.663-7.580(2H),7.543-7.440(4H),7.445-7.310(10H),7.176-7.057(4H),7.005-6.803(10H),6.803-6.643(6H),6.653-6.503(8H),6.223-6.109(4H),5.954-5.845(4H),5.592-5.514(2H)。
实施例5
一种电致发光器件,由下层至上层,依次为ITO导电玻璃衬底、空穴注入层、空穴传输层、发光层、电子传输层、电子注入层、阴极层。其中,采用MoO3为空穴注入层;采用TAPC为空穴传输层;采用CBP掺杂实施例1-4制备得到的TADF荧光染料为发光层;采用TmPyPB为电子传输层;采用LiF/A1为阴极层。
采用上述的器件结构,制备的OLEDs的电致发光光谱图如图2所示。
采用上述的器件结构,制备的OLEDs效率性能如下表1所示:
表1
Claims (10)
1.一种具有TADF特性的双受体型多取代咔唑类化合物,其特征在于,其结构如式I所示:
其中,R1选自:
或CF3;
R2选自:
R3选自H或叔丁基。
2.根据权利要求1所述的具有TADF特性的双受体型多取代咔唑类化合物,其特征在于,所述化合物选自:
3.权利要求1所述具有TADF特性的双受体型多取代咔唑类化合物的制备方法,其特征在于:
当R2选自时,所述方法包括以下步骤:式II化合物与式III化合物在惰性气体保护下,在碱和有机溶剂的存在下反应,得到式I化合物,
其中,R1选自:
或CF3;
R3选自H或叔丁基。
4.根据权利要求3所述的方法,其特征在于,所述的碱为碳酸钾、磷酸钾或叔丁醇钾,所述的有机溶剂为二甲基亚砜或N,N-二甲基甲酰胺,式II化合物、式III化合物和碱的摩尔比为1∶(5-7)∶(15-20),反应温度为135-160℃,反应时间为8-16h。
5.权利要求1所述具有TADF特性的双受体型多取代咔唑类化合物的制备方法,其特征在于:
当R2选自时,所述方法包括以下步骤:式IV化合物与式III化合物在惰性气体保护下,在碱和有机溶剂的存在下反应,得到式I化合物,
其中,R1选自:
或CF3;
R3选自H。
6.根据权利要求5所述的方法,其特征在于,所述的碱为碳酸钾、磷酸钾或叔丁醇钾,所述的有机溶剂为二甲基亚砜或N,N-二甲基甲酰胺,式IV化合物、式III化合物和碱的摩尔比为1∶(8-12)∶(20-40),反应温度为135-160℃,反应时间为8-16h。
7.权利要求1或2所述的具有TADF特性的双受体型多取代咔唑类化合物作为TADF荧光材料的应用。
8.权利要求1或2所述的具有TADF特性的双受体型多取代咔唑类化合物作为TADF荧光材料在制备电致发光器件中的应用。
9.包含权利要求1或2所述的具有TADF特性的双受体型多取代咔唑类化合物的电致发光器件,其特征在于,所述有机电致发光器件由下至上依次包括玻璃、附着在玻璃上的导电玻璃衬底层,与导电玻璃衬底层贴合的空穴注入层,与空穴注入层贴合的空穴传输层,与空穴传输层贴合的发光层,与发光层贴合的电子传输层,与电子传输层贴合的阴极层,所述的发光层包含权利要求1或2所述的化合物。
10.根据权利要求9所述的电致发光器件,其特征在于,所述发光层的掺杂主体材料为CBP,掺杂客体材料为权利要求1或2所述的化合物。
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109503508A (zh) * | 2018-11-15 | 2019-03-22 | 武汉华星光电半导体显示技术有限公司 | 绿光热活化延迟荧光材料及其合成方法、电致发光器件 |
CN113248487A (zh) * | 2021-05-14 | 2021-08-13 | 南京工业大学 | 一种基于咔唑/噁二唑的热激活延迟荧光材料及其制备方法和应用 |
US11985893B2 (en) | 2019-11-08 | 2024-05-14 | Samsung Display Co., Ltd. | Organic electroluminescence device and aromatic compound for organic electroluminescence device |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104693185A (zh) * | 2015-03-31 | 2015-06-10 | 南京工业大学 | 一类三氟甲基衍生物的合成及其在有机电致发光中应用 |
WO2015195837A1 (en) * | 2014-06-17 | 2015-12-23 | Nitto Denko Corporation | Emissive material for organic emitting diodes |
WO2016174377A1 (en) * | 2015-04-29 | 2016-11-03 | University Court Of The University Of St Andrews | Light emitting devices and compounds |
CN107011243A (zh) * | 2017-04-21 | 2017-08-04 | 瑞声光电科技(常州)有限公司 | 芳香族化合物及发光器件 |
US20180151808A1 (en) * | 2016-11-30 | 2018-05-31 | Yuan Ze University | Carbazole derivatives and organic light-emitting diodes by using the same |
-
2018
- 2018-09-19 CN CN201811098421.7A patent/CN109134347B/zh active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015195837A1 (en) * | 2014-06-17 | 2015-12-23 | Nitto Denko Corporation | Emissive material for organic emitting diodes |
CN104693185A (zh) * | 2015-03-31 | 2015-06-10 | 南京工业大学 | 一类三氟甲基衍生物的合成及其在有机电致发光中应用 |
WO2016174377A1 (en) * | 2015-04-29 | 2016-11-03 | University Court Of The University Of St Andrews | Light emitting devices and compounds |
US20180151808A1 (en) * | 2016-11-30 | 2018-05-31 | Yuan Ze University | Carbazole derivatives and organic light-emitting diodes by using the same |
CN107011243A (zh) * | 2017-04-21 | 2017-08-04 | 瑞声光电科技(常州)有限公司 | 芳香族化合物及发光器件 |
Non-Patent Citations (5)
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109503508A (zh) * | 2018-11-15 | 2019-03-22 | 武汉华星光电半导体显示技术有限公司 | 绿光热活化延迟荧光材料及其合成方法、电致发光器件 |
US11485905B2 (en) | 2018-11-15 | 2022-11-01 | Wuhan China Star Optoelectronics Semiconductor Display Technology Co., Ltd. | Green light thermally activated delayed fluorescent material and synthesizing method thereof, and electroluminescent device |
US11985893B2 (en) | 2019-11-08 | 2024-05-14 | Samsung Display Co., Ltd. | Organic electroluminescence device and aromatic compound for organic electroluminescence device |
CN113248487A (zh) * | 2021-05-14 | 2021-08-13 | 南京工业大学 | 一种基于咔唑/噁二唑的热激活延迟荧光材料及其制备方法和应用 |
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