CN112390778A - 一种杂蒽衍生物及其应用和有机电致发光器件 - Google Patents
一种杂蒽衍生物及其应用和有机电致发光器件 Download PDFInfo
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- CN112390778A CN112390778A CN202011096629.2A CN202011096629A CN112390778A CN 112390778 A CN112390778 A CN 112390778A CN 202011096629 A CN202011096629 A CN 202011096629A CN 112390778 A CN112390778 A CN 112390778A
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- NXQGGXCHGDYOHB-UHFFFAOYSA-L cyclopenta-1,4-dien-1-yl(diphenyl)phosphane;dichloropalladium;iron(2+) Chemical compound [Fe+2].Cl[Pd]Cl.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 NXQGGXCHGDYOHB-UHFFFAOYSA-L 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- DSSBJZCMMKRJTF-UHFFFAOYSA-N dibenzofuran-2-ylboronic acid Chemical compound C1=CC=C2C3=CC(B(O)O)=CC=C3OC2=C1 DSSBJZCMMKRJTF-UHFFFAOYSA-N 0.000 description 1
- GOXNHPQCCUVWRO-UHFFFAOYSA-N dibenzothiophen-4-ylboronic acid Chemical compound C12=CC=CC=C2SC2=C1C=CC=C2B(O)O GOXNHPQCCUVWRO-UHFFFAOYSA-N 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- KPTRDYONBVUWPD-UHFFFAOYSA-N naphthalen-2-ylboronic acid Chemical compound C1=CC=CC2=CC(B(O)O)=CC=C21 KPTRDYONBVUWPD-UHFFFAOYSA-N 0.000 description 1
- JVJQPDTXIALXOG-UHFFFAOYSA-N nitryl fluoride Chemical group [O-][N+](F)=O JVJQPDTXIALXOG-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical group 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011593 sulfur Chemical group 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/10—1,4-Dioxanes; Hydrogenated 1,4-dioxanes
- C07D319/14—1,4-Dioxanes; Hydrogenated 1,4-dioxanes condensed with carbocyclic rings or ring systems
- C07D319/24—[b,e]-condensed with two six-membered rings
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- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/10—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing aromatic rings
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Abstract
本发明公开了一种杂蒽衍生物及其制备方法、应用和有机电致发光器件。该杂蒽衍生物利用空穴传输型基团在杂蒽基团的2,3,7进行至少一个位点的取代,具有杂蒽的母核结构,形成了具有星状空间构型的D‑A型化合物或空穴传输型化合物,多位点芳香基团的取代和星状构型使得化合物在器件制备和应用中具有更好的稳定性、平衡的电子/空穴传输速率,作为有机电致发光器件的发光主体材料或空穴传输材料,具有较高的量子复合效率,能有效解决器件中电子/空穴不平衡和易结晶的问题,发出更纯净的光色,在启动电压、电流效率、寿命以及热稳定性上具有比同类化合物和现有技术的化合物更为显著的优势。
Description
技术领域
本发明涉及光电材料领域,具体而言,本发明涉及一种杂蒽衍生物及其应用和有机电致发光器件。
背景技术
OLED,即有机发光二极管,又称为有机电激光显示。OLED具有自发光的特性,采用非常薄的有机材料涂层和玻璃基板,当电流通过时,有机材料就会发光,而且OLED显示屏幕可视角度大,并且能够显著节省电能,因此OLED被视为21世纪最具前途的产品之一。但迄今为止,OLED器件仍未能实现普及化应用,其中,器件的效率是制约其普及化的重要原因。
在OLED器件中,发光层的设计和组合对器件的性能起到了关键作用,它直接决定着器件的发光效率和寿命长短。作为OLED的发光层材料,需同时具备良好的电子与空穴传输能力,从而使得载流子能够在发光层更加平衡地复合发光。虽然,在器件制备过程中增加空穴阻挡层或者电子阻挡层,解决了载流子传输不平衡的问题,但是增加了器件制备的复杂度和成本。近年来,具有双极传输特性的发光材料和高迁移率的空穴传输材料受到了广泛关注。目前,光电材料领域对于全新的杂蒽基团,由于其兼具蒽基团的刚性结构骨架和非金属原子,初步发现了其电致发光特性,然而,由杂蒽化合物制备的电致发光器件在发光效率、寿命等方面还处于较低的水平,不能达到现有技术中对发光材料性能的要求,因此,研究杂蒽基团的光电性质,设计出性能更优的以杂蒽基团为核心的新化合物,由此制备发光效率更高、更稳定的有机电致发光器件,是光电材料领域有待解决的技术问题。
发明内容
本发明在现有技术的基础上,以产业化为目标,旨在开发一种以杂蒽基团为核心的OLED材料,解决材料层内电子/空穴迁移不匹配的问题,进而显著提高器件在发光效率、寿命、色坐标等方面的综合性能。
本发明第一个方面提供了一种杂蒽衍生物,所述杂蒽衍生物为式(I)所示结构:
其中,X选自:O、S、S=O或S(=O)2;L1、L2、L3各自独立的选自单键,未取代的或由C1-C10的烷烃基、C1-C10的烷氧基、腈基、硝基、氟基取代的亚苯基,未取代的或由C1-C10的烷烃基、C1-C10的烷氧基、腈基、硝基、氟基取代的亚联苯基;L1、L2、L3相同或不同;R1、R2、R3中的至少一个为空穴传输基团,分别独立的选自: (萘基上任意位点取代)、其余的R1、R2、R3为电子传输基团,分别独立的选自: 其中,R4-R9、R13-R15分别独立的选自:氢,C1-C10的烷烃基,未取代的或由C1-C10的烷烃基取代的苯基,未取代的或由C1-C10的烷烃基取代的联苯基;R10-R12、R16-R19分别独立的选自C1-C10的烷烃基,未取代的或由C1-C10的烷烃基、C1-C10的烷氧基、腈基、硝基、氟基取代的苯基,未取代的或由C1-C10的烷烃基、C1-C10的烷氧基、腈基、硝基、氟基取代的联苯基,未取代的或由C1-C10的烷烃基、C1-C10的烷氧基、腈基、硝基、氟基取代的三联苯基,未取代的或由C1-C10的烷烃基、C1-C10的烷氧基、腈基、硝基、氟基、苯基取代的萘基;Ar1、Ar2、Ar3分别独立的表示为不存在或为单环芳烃,所述Ar1、Ar2、Ar3与连接的萘环之间直接稠合;Y1选自:O、S、N(R20)、C(R21)(R22);Y2、Y3分别独立的选自:O、S、N(R23);R20、R23分别独立的选自:甲基,乙基,未取代的或由甲基、C1-C5的烷氧基、腈基、硝基、氟基取代的苯基,未取代的或由甲基、C1-C5的烷氧基、腈基、硝基、氟基取代的联苯基,未取代的或由甲基、C1-C5的烷氧基、腈基、硝基、氟基取代的萘基;R21与R22相同,独立的选自甲基,乙基,或者苯基,当R21、R22选自苯基时,基团之间相互独立或通过单键连接;Z各自独立的为CH、N或C(R24),且中Z为N的个数为1-3个,R24分别独立的选自苯基、甲苯基、腈基苯基、联苯基、萘基、二苯并呋喃基、二苯并噻吩基、芴基、咔唑基苯基、苯基咔唑基;T、Q各自独立的为CH或N,各基团中,Q为N的个数为1或2,T为N的个数为0或1;R1、R2、R3相同或不同;*为取代位点。
优选的,L1与L2相同,R1与R2相同。
优选的,所述杂蒽衍生物的分子量在850以下。
优选的,所述式(I)的杂蒽衍生物选自下述化合物:
进一步的,用作有机电致发光器件的空穴传输层和/或者发光层。
优选的,R1、R2、R3中1-2个选自空穴传输基团,其余选自电子传输基团时,用作机电致发光器件的发光层,R1、R2、R3均选自空穴传输基团时,用作机电致发光器件的空穴传输层。
本发明第二个方面提供了一种有机电致发光器件,主要包括阴极、阳极和两电极之间的有机层,或者主要包括出光层、阴极、阳极和两电极之间的有机层,两电极之间的有机层至少包括空穴传输层或发光层,其中,空穴传输层或发光层含有上述的杂蒽衍生物。
本申请中,利用空穴传输型基团在杂蒽基团的2,3,7进行至少一个位点的取代构建的本申请中的杂蒽衍生物表现出了优异的荧光电致发光特性,尤其是高空穴迁移率和平衡的电子/空穴传输速率。当利用1-3个空穴传输型基团对杂蒽基团的2,3,7的进行修饰,用电子传输型基团对杂蒽的2,3,7的剩余位点进行填充,形成了D-A型化合物,兼具杂蒽基团的刚性结构和氧杂原子的强吸电子特性,同时,利用各个位点的空间位阻形成了具有星状的空间构型,相对于二取代和单取代的杂蒽化合物,多位点芳香基团的取代和星状构型使得化合物在器件制备和应用中具有更好的稳定性、平衡的电子/空穴传输速率,避免缔结结晶,提高激子复合发光效率,同时,各个位点的取代基进行了进一步的限定,比如分子量在850以下,避免分子量过大不利于器件的蒸镀制备工艺,因此,将其作为发光层的发光主体材料或空穴传输材料应用至有机电致发光器件时,显著提高器件在启动电压、电流效率、寿命等方面的性能,并使得发光波长蓝移,发出更纯净的光色,是一种理想的发光层材料和空穴传输材料,另,本发明的杂蒽衍生物还有应用为发光客体材料和电子阻挡材料的潜力。
具体实施方式
下面详细描述本发明的实施例。下面描述的实施例是示例性的,仅用于解释本发明,而不能理解为对本发明的限制。实施例中未注明具体技术或条件的,按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者,均为可以通过市购获得的常规产品。
合成实施例1化合物(2)的制备
S1.在250mL三口瓶中,投入2,3-二溴-7-氯噁蒽(7.53g,20mmol)、苯硼酸(4.88g,40mmol)、碳酸钾(5.53g,40mmol),按照2,3-二溴-7-氯噁蒽的重量计,加入10倍的甲苯、5倍的乙醇和5倍的水,在氮气氛围下,加入四(三苯基膦)钯(0.23g,0.2mmol),升温至80-85℃反应一段时间,液相监测反应基本完成,冷却至室温,过滤,滤液浓缩,与滤饼一起用乙酸乙酯、乙醇或其组合打浆1-3遍,即可得到4.75g中间体1,收率64%。
S2.在100mL三口瓶中,投入上述中间体1(3.71g,10mmol),硼酸频那醇酯(3.05g,12mmol),醋酸钾(1.96g,30mmol),按中间体1的质量计,加入10倍的甲苯,在氮气氛围下,加入[1,1'-双(二苯基膦基)二茂铁]二氯化钯(0.07g,0.10mmol),升温至100-115℃反应一段时间,液相监测反应基本完成,冷却至室温,过滤,滤液浓缩,与滤饼一起用乙醇打浆1-3遍,即可得到3.46g中间体2,收率75%。
S3.在50mL三口瓶中,投入上述中间体2(2.31g,5mmol)、碳酸钾(1.38g,10mmol)、2-([1,1'-联苯]-3-基)-4-氯-6-苯基嘧啶(1.71g,5mmol),按照中间体2的质量计,加入10倍的甲苯、5倍的乙醇和5倍的水,在氮气氛围下,加入四(三苯基膦)钯(0.06g,0.05mmol),升温至80-85℃反应一段时间,液相监测反应基本完成,冷却至室温,过滤,滤液浓缩,与滤饼一起用硅胶拌样,用10:1的石油醚与二氯甲烷进行柱层析,有机相浓缩,即可得到2.15g目标化合物(2),收率67%。
质谱仪MALDI-TOF-MS(m/z)=642.7586,理论分子量:642.7580;元素分析:理论值C46H30N2(%):C 85.96,H 4.70,N 4.36;实测值:C 85.95,H 4.70,N 4.38。
合成实施例2化合物(15)的制备
S1.在250mL三口瓶中,投入2,3-二溴-7-氯噁蒽(7.53g,20mmol)、咔唑(6.69g,40mmol)、邻菲罗啉(0.36g,2mmol)、碳酸钾(5.53g,40mmol),按照2,3-二溴-7-氯噁蒽的重量计,加入10倍的N,N-二甲基甲酰胺,在氮气氛围下,加入碘化亚铜(0.38g,2mmol),升温至145-150℃反应一段时间,液相监测反应基本完成,冷却至室温,加水,过滤,滤液分液,有机相浓缩,与滤饼一起用乙酸乙酯、乙醇或其组合打浆1-3遍,即可得到6.04g中间体1,收率55%。
S2.将合成实施例1中S2的中间体1(3.71g,10mmol)替换为本实施例的中间体1(5.49g,10mmol),其他合成步骤同合成实施例1中的S2,即可得到4.48g中间体2,收率70%;
S3.将合成实施例1中S3的中间体2(2.31g,5mmol)替换为本实施例的中间体2(1.33g,5mmol),2-([1,1'-联苯]-3-基)-4-氯-6-苯基嘧啶(1.71g,5mmol)替换为4-氯-2,6-二苯基嘧啶(1.33g,5mmol),其他合成步骤同合成实施例1中的S3,即可得到2.64g目标化合物(15),收率71%;
质谱仪MALDI-TOF-MS(m/z)=744.8532,理论分子量:744.8540;元素分析:理论值C52H32N4(%):C 83.85,H 4.33,N 7.52;实测值:C 83.87,H 4.32,N 7.52。
合成实施例3化合物(23)的制备
S1.将合成实施例1中S1的苯硼酸(4.88g,40mmol)替换为萘-2-基硼酸(6.84g,40mmol),其他合成步骤同合成实施例1中的S1,即可得到5.93g中间体1,收率63%;
S2.将合成实施例1中S2的中间体1(3.71g,10mmol)替换为本实施例的中间体1(4.71g,10mmol),其他合成步骤同合成实施例1中的S2,即可得到4.16g中间体2,收率74%;
S3.将合成实施例1中S3的中间体2(2.31g,5mmol)替换为本实施例的中间体2(2.81g,5mmol),2-([1,1'-联苯]-3-基)-4-氯-6-苯基嘧啶(1.71g,5mmol)替换为2-(4-溴苯基)-4,6-二苯基-1,3,5-三嗪(1.94g,5mmol),其他合成步骤同合成实施例1中的S3,即可得到2.65g目标化合物(23),收率71%;
质谱仪MALDI-TOF-MS(m/z)=743.8667,理论分子量:743.8660;元素分析:理论值C53H33N3(%):C 85.58,H 4.47,N 5.65;实测值:C 85.60,H 4.46,N 5.64。
合成实施例4化合物(31)的制备
S1.将合成实施例1中S1的苯硼酸(4.88g,40mmol)替换为(9-苯基-9H-咔唑-2-基)硼酸(11.49g,40mmol),其他合成步骤同合成实施例1中的S1,即可得到8.13g中间体1,收率58%;
S2.在250mL三口瓶中,加入上述中间体1(7.01g,10mmol)、2,6-双氮杂咔唑(1.69g,10mmol)、邻菲罗啉(0.18g,1mmol)、碳酸钾(2.76g,20mmol),按照中间体1的重量计,加入10倍的N,N-二甲基甲酰胺,在氮气氛围下,加入碘化亚铜(0.19g,1mmol),升温至145-150℃反应一段时间,液相监测反应基本完成,冷却至室温,加水,过滤,滤液分液,有机相浓缩,与滤饼一起用乙酸乙酯、乙醇或其组合打浆1-3遍,即可得到4.42g目标化合物(31),收率53%;
质谱仪MALDI-TOF-MS(m/z)=833.9508,理论分子量:833.9510;元素分析:理论值C58H35N5(%):C 83.53,H 4.23,N 8.40;实测值:C 83.51,H 4.24,N 8.40。
合成实施例5化合物(34)的制备
S1.将合成实施例2中S1的咔唑(6.69g,40mmol)替换为二苯胺(6.77g,40mmol),其他合成过程同合成实施2的S1,即可得到5.97g中间体1,收率54%。
S2.将合成实施例4中S2的中间体1(7.01g,10mmol)替换为本实施例中S1的中间体1(5.53g,10mmol),2,6-双氮杂咔唑(1.69g,10mmol)替换为4-氮杂咔唑(1.68g,10mmol),其他合成过程同合成实施例4中的S2,即可得到3.42g目标化合物(34),收率50%;
质谱仪MALDI-TOF-MS(m/z)=684.7994,理论分子量:684.7990;元素分析:理论值C47H32N4(%):C 82.44,H 4.71,N 8.18;实测值:C 82.44,H 4.70,N 8.18。
合成实施例6化合物(41)的制备
S1.将合成实施例1中S1的苯硼酸(4.88g,40mmol)替换为二苯并噻吩-4-基硼酸(9.12g,40mmol),其他合成步骤同合成实施例1中的S1,即可得到7.00g中间体1,收率60%;
S2.将合成实施例1中S2的中间体1(3.71g,10mmol)替换为本实施例的中间体1(5.83g,10mmol),其他合成步骤同合成实施例1中的S2,即可得到4.52g中间体2,收率67%;
S3.将合成实施例1中S3的中间体2(2.31g,5mmol)替换为本实施例的中间体2(3.37g,5mmol),2-([1,1'-联苯]-3-基)-4-氯-6-苯基嘧啶(1.71g,5mmol)替换为4-溴苯基-3,6-双氮杂咔唑(1.62g,5mmol),其他合成步骤同合成实施例1中的S3,即可得到2.77g目标化合物(41),收率70%;
质谱仪MALDI-TOF-MS(m/z)=791.9437,理论分子量:791.9430;元素分析:理论值C52H29N3(%):C 78.87,H 3.69,N 5.31;实测值:C 78.88,H 3.69,N 5.30。
合成实施例7化合物(56)的制备
S1.同合成实施例2中S1;
S2.同合成实施例2中S1;
S3.将合成实施例2中S3的4-氯-2,6-二苯基嘧啶(1.33g,5mmol)替换为8-溴-5-苯基氮杂咔唑(1.62g,5mmol),其他合成步骤同合成实施例2中的S3,即可得到2.50g目标化合物(56),收率66%;
质谱仪MALDI-TOF-MS(m/z)=756.8655,理论分子量:756.8650;元素分析:理论值C53H32N4(%):C 84.11,H 4.26,N 7.40;实测值:C 84.10,H 4.25,N 7.40。
合成实施例8化合物(64)的制备
S1.将合成实施例1中S1的苯硼酸(4.88g,40mmol)替换为(9-甲基-9H-咔唑-2-基)硼酸(9.00g,40mmol),其他合成步骤同合成实施例1中的S1,即可得到6.81g中间体1,收率59%;
S2.将合成实施例1中S2的中间体1(3.71g,10mmol)替换为本实施例的中间体1(5.77g,10mmol),其他合成步骤同合成实施例1中的S2,即可得到4.61g中间体2,收率69%;
S3.将合成实施例1中S3的中间体2(2.31g,5mmol)替换为本实施例的中间体2(3.34g,5mmol),2-([1,1'-联苯]-3-基)-4-氯-6-苯基嘧啶(1.71g,5mmol)替换为2-溴-1-苯基-1H-苯并咪唑(1.36g,5mmol),其他合成步骤同合成实施例1中的S3,即可得到2.02g目标化合物(64),收率55%;
质谱仪MALDI-TOF-MS(m/z)=734.8596,理论分子量:734.8590;元素分析:理论值C51H34N4(%):C 83.36,H 4.66,N 7.62;实测值:C 83.36,H 4.65,N 7.64。
合成实施例9化合物(88)的制备
S1.将合成实施例1中S1的苯硼酸(4.88g,40mmol)替换为二苯并呋喃-2-基硼酸(8.48g,40mmol),其他合成步骤同合成实施例1中的S1,即可得到6.83g中间体1,收率62%;
S2.将合成实施例1中S2的中间体1(3.71g,10mmol)替换为本实施例的中间体1(5.51g,10mmol),其他合成步骤同合成实施例1中的S2,即可得到4.56g中间体2,收率71%;
S3.将合成实施例1中S3的中间体2(2.31g,5mmol)替换为本实施例的中间体2(3.21g,5mmol),2-([1,1'-联苯]-3-基)-4-氯-6-苯基嘧啶(1.71g,5mmol)替换为2-(4-溴苯基)苯并噁唑(1.37g,5mmol),其他合成步骤同合成实施例1中的S3,即可得到2.24g目标化合物(88),收率63%;
质谱仪MALDI-TOF-MS(m/z)=709.7568,理论分子量:709.7570;元素分析:理论值C49H27N(%):C 82.92,H 3.83,N 1.97;实测值:C 82.92,H 3.84,N 1.95。
合成实施例10化合物(102)的制备
S1.将合成实施例1中S1的苯硼酸(4.88g,40mmol)替换为(9,9-二甲基-9H-芴-2-基)硼酸(9.52g,40mmol),其他合成步骤同合成实施例1中的S1,即可得到7.24g中间体1,收率60%;
S2.将合成实施例1中S2的中间体1(3.71g,10mmol)替换为本实施例的中间体1(6.03g,10mmol),其他合成步骤同合成实施例1中的S2,即可得到4.65g中间体2,收率67%;
S3.将合成实施例1中S3的中间体2(2.31g,5mmol)替换为本实施例的中间体2(3.47g,5mmol),2-([1,1'-联苯]-3-基)-4-氯-6-苯基嘧啶(1.71g,5mmol)替换为6-氯-2-苯基苯并噁唑(1.15g,5mmol),其他合成步骤同合成实施例1中的S3,即可得到2.36g目标化合物(102),收率62%;
质谱仪MALDI-TOF-MS(m/z)=761.9217,理论分子量:761.9210;元素分析:理论值C55H39N(%):C 86.70,H 5.16,N 1.84;实测值:C 86.70,H 5.15,N 1.86。
合成实施例12化合物(138)的制备
S1.同合成实施例2中S1;
S2.同合成实施例2中S1;
S3.将合成实施例2中S3的4-氯-2,6-二苯基嘧啶(1.33g,5mmol)替换为2-溴-三唑并吡啶(1.0g,5mmol),其他合成步骤同合成实施例2中的S3,即可得到1.64g目标化合物(56),收率52%;
质谱仪MALDI-TOF-MS(m/z)=631.6954,理论分子量:631.6950;元素分析:理论值C42H25N5(%):C 79.86,H 3.99,N 11.09;实测值:C 79.86,H 4.01,N 11.08。
合成实施例13化合物(153)的制备
S1.将合成实施例1中S1的苯硼酸(4.88g,40mmol)替换为[1,1'-联苯]-3-基硼酸(7.92g,40mmol),其他合成步骤同合成实施例1中的S1,即可得到6.69g中间体1,收率64%;
S2.在250mL三口瓶中,将上述中间体1(5.23g,10mmol)溶解于5-10倍(以中间体1的物质的量计)体积的四氢呋喃中,冷却至-78℃,加入正丁基锂(0.70g,11mmol),反应1-2h后,加入二苯基氯化磷(2.65g,12mmol),升至室温反应8-12小时,加入甲醇猝灭反应,同时加入5倍(以中间体1的物质的量计)质量分数为30%的双氧水溶液氧化2-4h,液相监测反应完成,冷却至室温,萃取,有机相浓缩,用乙酸乙酯、乙醇或其组合打浆1-3遍,即可得到3.10g目标化合物(153),收率45%。
质谱仪MALDI-TOF-MS(m/z)=688.7625,理论分子量:688.7628;元素分析:理论值C48H33(%):C 83.70,H 4.83;实测值:C 83.72,H 4.82。
合成实施例14化合物(186)的制备
S1.在250mL三口瓶中,投入7-溴-2,3-二氯噁蒽(6.64g,20mmol)、二甲苯基胺(7.89g,40mmol)、邻菲罗啉(0.36g,2mmol)、碳酸钾(5.53g,40mmol),按照7-溴-2,3-二氯噁蒽的重量计,加入10倍的N,N-二甲基甲酰胺,在氮气氛围下,加入碘化亚铜(0.38g,2mmol),升温至145-150℃反应一段时间,液相监测反应基本完成,冷却至室温,加水,过滤,滤液分液,有机相浓缩,与滤饼一起用乙酸乙酯、乙醇或其组合打浆1-3遍,即可得到5.29g中间体1,收率59%。
S2.在100mL三口瓶中,投入上述中间体1(4.48g,10mmol)、正丁基锂(3.20g,50mmol)和四氢呋喃50mL,在-78℃下搅拌1-3h,然后按中间体1的质量计,加入1-1.5倍的N,N-二甲基甲酰胺并升温至室温,反应1-2h,液相监测反应完成后,加水猝灭,分液,有机相使用无水硫酸镁干燥后浓缩,再使用乙酸乙酯打浆,即可得到3.70g中间体2,收率85%;
S3.在100mL三口瓶中,投入上述中间体2(2.18g,5mmol),苄脒盐酸盐(3.13g,20mmol,)、碳酸钾(2.76g,20mmol,)、一水合醋酸铜(1.00g,5mmol,)及10倍(按中间体2的质量计)的甲苯,105℃回流8-16h,液相监测反应完成,冷却至室温,水洗,分液出有机相,用硫酸镁干燥后过滤,滤液真空旋蒸除去溶剂,最后用1:10(按体积计)的二氯甲烷/石油醚的淋洗剂进行柱层析,即可得到2.69g目标化合物(186),收率64%。
质谱仪MALDI-TOF-MS(m/z)=841.9752,理论分子量:841.9750;元素分析:理论值C56H39N7(%):C 79.89,H 4.67,N 11.65;实测值:C 79.89,H 4.68,N 11.63。
合成实施例15化合物(192)的制备
S1.将合成实施例2中S1的咔唑(6.69g,40mmol)替换为1,5-双氮杂咔唑(6.77g,40mmol),其他合成过程同合成实施例1中的S1,即可得到5.75g中间体1,收率52%;
S2.将合成实施例2中S2的中间体1(5.49g,10mmol)替换为本实施例的中间体1(5.53g,10mmol),其他合成过程同合成实施例2中的S2,即可得到4.38g中间体1,收率68%;
S3.将合成实施例2中S3的中间体2(1.33g,5mmol)替换为本实施例的中间体2(3.22g,5mmol),4-氯-2,6-二苯基嘧啶(1.33g,5mmol)替换为9-溴-10-苯基蒽(1.67g,5mmol),其他合成步骤同合成实施例1中的S3,即可得到2.31g目标化合物(192),收率60%;
质谱仪MALDI-TOF-MS(m/z)=770.8513,理论分子量:770.8520;元素分析:理论值C52H30N6(%):C 81.02,H 3.92,N 10.90;实测值:C 81.00,H 3.93,N 10.90。
合成实施例16化合物(228)的制备
S1.将合成实施例1中S1的苯硼酸(4.88g,40mmol)替换为(9-甲基-9H-氮杂咔唑-7-基)硼酸(9.04g,40mmol),其他合成步骤同合成实施例1中的S1,即可得到6.72g中间体1,收率58%;
S2.将合成实施例1中S2的中间体1(3.71g,10mmol)替换为本实施例的中间体1(5.79g,10mmol),其他合成步骤同合成实施例1中的S2,即可得到4.69g中间体2,收率70%;
S3.将合成实施例1中S3的中间体2(2.31g,5mmol)替换为本实施例的中间体2(3.35g,5mmol),2-([1,1'-联苯]-3-基)-4-氯-6-苯基嘧啶(1.71g,5mmol)替换为2-溴-9,9-二甲基-9H-芴(1.37g,5mmol),其他合成步骤同合成实施例1中的S3,即可得到2.47g目标化合物(228),收率67%;
质谱仪MALDI-TOF-MS(m/z)=736.8752,理论分子量:736.8750;元素分析:理论值C51H36N4(%):C 83.13,H 4.92,N 7.60;实测值:C 83.12,H 4.94,N 7.58。
合成实施例17化合物(240)的制备
S1.将合成实施例1中S1的苯硼酸(4.88g,40mmol)替换为(9-甲基-9H-氮杂咔唑-7-基)硼酸(9.52g,40mmol),其他合成步骤同合成实施例1中的S1,即可得到6.27g中间体1,收率52%;
S2.将合成实施例1中S2的中间体1(3.71g,10mmol)替换为本实施例的中间体1(6.03g,10mmol),其他合成步骤同合成实施例1中的S2,即可得到4.58g中间体2,收率66%;
S3.将合成实施例1中S3的中间体2(2.31g,5mmol)替换为本实施例的中间体2(3.47g,5mmol),2-([1,1'-联苯]-3-基)-4-氯-6-苯基嘧啶(1.71g,5mmol)替换为2-溴-9-苯基-9H-咔唑(1.61g,5mmol),其他合成步骤同合成实施例1中的S3,即可得到2.59g目标化合物(240),收率64%;
质谱仪MALDI-TOF-MS(m/z)=809.9284,理论分子量:809.9290;元素分析:理论值C56H35N5(%):C 83.05,H 4.36,N 8.65;实测值:C 83.06,H 4.35,N 8.64。
合成实施例18化合物(293)的制备
S1.将合成实施例1中S1的苯硼酸(4.88g,40mmol)替换为苯并噁唑-6-基硼酸(6.52g,40mmol),其他合成步骤同合成实施例1中的S1,即可得到4.98g中间体1,收率55%;
S2.将合成实施例1中S2的中间体1(3.71g,10mmol)替换为本实施例的中间体1(4.53g,10mmol),其他合成步骤同合成实施例1中的S2,即可得到3.70g中间体2,收率68%;
S3.将合成实施例1中S3的中间体2(2.31g,5mmol)替换为本实施例的中间体2(2.72g,5mmol),2-([1,1'-联苯]-3-基)-4-氯-6-苯基嘧啶(1.71g,5mmol)替换为2-溴-9-苯基-9H-咔唑(1.61g,5mmol),其他合成步骤同合成实施例1中的S3,即可得到2.14g目标化合物(293),收率65%;
质谱仪MALDI-TOF-MS(m/z)=659.7005,理论分子量:659.7010;元素分析:理论值C44H25N3(%):C 80.11,H 3.82,N 6.37;实测值:C 80.10,H 3.82,N 6.38。
合成实施例19化合物(302)的制备
S1.将合成实施例2中S1的咔唑(6.69g,40mmol)替换为2-苯基l-1H-苯并咪唑(7.77g,40mmol),其他合成过程同合成实施2的S1,即可得到6.15g中间体1,收率51%。
S2.将合成实施例4中S2的中间体1(7.01g,10mmol)替换为本实施例中S1的中间体1(6.03g,10mmol),2,6-双氮杂咔唑(1.69g,10mmol)替换为二苯胺(1.69g,10mmol),其他合成过程同合成实施例4中的S2,即可得到4.42g目标化合物(302),收率60%;
质谱仪MALDI-TOF-MS(m/z)=735.8477,理论分子量:735.8470;元素分析:理论值C50H33N5(%):C 81.61,H 4.52,N 9.52;实测值:C 81.60,H 4.52,N 9.54。
合成实施例20化合物(306)的制备
S1.将合成实施例1中S1的苯硼酸(4.88g,40mmol)替换为三唑并吡啶-2-基硼酸(6.52g,40mmol),其他合成步骤同合成实施例1中的S1,即可得到4.89g中间体1,收率54%;
S2.将合成实施例1中S2的中间体1(3.71g,10mmol)替换为本实施例的中间体1(4.53g,10mmol),其他合成步骤同合成实施例1中的S2,即可得到3.54g中间体2,收率65%;
S3.将合成实施例1中S3的中间体2(2.31g,5mmol)替换为本实施例的中间体2(2.72g,5mmol),2-([1,1'-联苯]-3-基)-4-氯-6-苯基嘧啶(1.71g,5mmol)替换为9-溴-10-苯基蒽(1.67g,5mmol),其他合成步骤同合成实施例1中的S3,即可得到2.05g目标化合物(306),收率61%;
质谱仪MALDI-TOF-MS(m/z)=670.7325,理论分子量:670.7320;元素分析:理论值C44H26N6(%):C 78.79,H 3.91,N 12.53;实测值:C 78.80,H 3.90,N 12.52。
合成实施例21化合物(323)的制备
S1.在250mL三口瓶中,投入7-溴-2,3-二氯噁蒽(6.64g,20mmol)、咔唑(3.34g,20mmol)、邻菲罗啉(0.36g,2mmol)、碳酸钾(5.53g,40mmol),按照2,3-二溴-7-氯噁蒽的重量计,加入10倍的N,N-二甲基甲酰胺,在氮气氛围下,加入碘化亚铜(0.38g,2mmol),升温至145-150℃反应一段时间,液相监测反应基本完成,冷却至室温,加水,过滤,滤液分液,有机相浓缩,与滤饼一起用乙酸乙酯、乙醇或其组合打浆1-3遍,即可得到5.60g中间体1,收率67%。
S2.在250mL三口瓶中,将上述中间体1(4.18g,10mmol)溶解于5-10倍(以中间体1的物质的量计)体积的四氢呋喃中,冷却至-78℃,加入正丁基锂(1.40g,22mmol),反应1-2h后,加入二苯基氯化磷(5.30g,24mmol),升至室温反应8-12小时,加入甲醇猝灭反应,同时加入5倍(以中间体1的物质的量计)质量分数为30%的双氧水溶液氧化2-4h,液相监测反应完成,冷却至室温,萃取,有机相浓缩,用乙酸乙酯、乙醇或其组合打浆1-3遍,即可得到2.92g目标化合物(323),收率39%。
质谱仪MALDI-TOF-MS(m/z)=749.7422,理论分子量:749.7425;元素分析:理论值C48H33N(%):C 76.90,H 4.44,N 1.87;实测值:C 76.90,H 4.45,N 1.85。
合成实施例22化合物(374)的制备
在250mL三口瓶中,投入2,3,7-三溴噁蒽(2.10g,5mmol)、二苯并呋喃-3-基硼酸(4.24g,20mmol)、碳酸钾(1.38g,10mmol),按照2,3,7-三溴噁蒽的重量计,加入10倍的甲苯、5倍的乙醇和5倍的水,在氮气氛围下,加入四(三苯基膦)钯(0.11g,0.1mmol),升温至80-85℃反应一段时间,液相监测反应基本完成,冷却至室温,过滤,滤液浓缩,与滤饼一起用乙酸乙酯、乙醇或其组合打浆1-3遍,即可得到1.70g中间体1,收率50%。
质谱仪MALDI-TOF-MS(m/z)=682.7316,理论分子量:682.7310;元素分析:理论值C48H26(%):C 84.44,H 3.84;实测值:C 84.45,H 3.82。
合成实施例23化合物(389)的制备
S1.将合成实施例4中S1的(9-苯基-9H-咔唑-2-基)硼酸(11.49g,40mmol)替换为(9,9-二甲基-9H-芴-3-基)硼酸(9.52g,40mmol),其他合成步骤同合成实施例1中的S1,即可得到6.87g中间体1,收率57%;
S2将合成实施例4中S2的中间体1(7.01g,10mmol)替换为本实施例中的中间体1(6.03g,10mmol),2,6-双氮杂咔唑(1.69g,10mmol)替换为咔唑(1.67g,10mmol),其他合成步骤同合成实施例4中的S2,即可得到4.77g中间体1,收率65%;
质谱仪MALDI-TOF-MS(m/z)=733.9104,理论分子量:733.9110;元素分析:理论值C54H39N(%):C 88.38,H 5.36,N 1.91;实测值:C 88.37,H 5.38,N 1.90。
合成实施例24化合物(399)的制备
在250mL三口瓶中,投入2,3,7-三溴噁蒽(2.10g,5mmol)、咔唑(3.34g,20mmol)、邻菲罗啉(0.09g,0.5mmol)、碳酸钾(1.38g,10mmol),按照2,3,7-三溴噁蒽的重量计,加入10倍的N,N-二甲基甲酰胺,在氮气氛围下,加入碘化亚铜(0.10g,0.5mmol),升温至145-150℃反应一段时间,液相监测反应基本完成,冷却至室温,加水,过滤,滤液分液,有机相浓缩,与滤饼一起用乙酸乙酯、乙醇或其组合打浆1-3遍,即可得到1.84g中间体1,收率54%。
质谱仪MALDI-TOF-MS(m/z)=679.7784,理论分子量:679.7790;元素分析:理论值C48H29N3(%):C 84.81,H 4.30,N 6.18;实测值:C 84.80,H 4.32,N 6.18。
合成实施例25化合物(410)的制备
S1.将合成实施例2中S1的咔唑(6.69g,40mmol)替换为二苯胺(6.77g,40mmol),其他合成过程同合成实施2的S1,即可得到5.97g中间体1,收率54%。
S2.将合成实施例4中S2的中间体1(7.01g,10mmol)替换为本实施例中S1的中间体1(5.53g,10mmol),2,6-双氮杂咔唑(1.69g,10mmol)替换为咔唑(1.67g,10mmol),其他合成过程同合成实施例4中的S2,即可得到4.10g目标化合物(410),收率60%;
质谱仪MALDI-TOF-MS(m/z)=683.8107,理论分子量:683.8110;元素分析:理论值C48H33N3(%):C 84.31,H 4.86,N 6.15;实测值:C 84.30,H 4.86,N 6.17。
合成实施例26化合物(417)的制备
S1.将合成实施例1中S1的苯硼酸(4.88g,40mmol)替换为三唑并吡啶-2-基硼酸(11.57g,40mmol),其他合成步骤同合成实施例1中的S1,即可得到7.33g中间体1,收率52%;
S2.在250mL三口瓶中,投入上述中间体1(7.05g,10mmol)、苯硼酸(1.22g,40mmol)、碳酸钾(2.76g,20mmol),按照中间体1的重量计,加入10倍的甲苯、5倍的乙醇和5倍的水,在氮气氛围下,加入四(三苯基膦)钯(0.11g,0.1mmol),升温至80-85℃反应一段时间,液相监测反应基本完成,冷却至室温,过滤,滤液浓缩,与滤饼一起用乙酸乙酯、乙醇或其组合打浆1-3遍,即可得到5.30g目标化合物(417),收率71%。
质谱仪MALDI-TOF-MS(m/z)=746.9102,理论分子量:746.9100;元素分析:理论值C54H38N2(%):C 86.84,H 5.13,N 3.75;实测值:C 86.85,H 5.13,N 3.76。
按照合成实施例1至合成实施例26基本相同的实验操作方法,即可得到化合物(1)至(420)。
以上详细描述的本发明的实施例是示例性的,仅用于解释本发明,而不能理解为对本发明的限制。实施例中未注明具体技术或条件的,按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。
器件实施例1
本发明所提供的杂蒽衍生物作为发光层主体材料进行的器件制备可按照本方法制备。
在高真空条件下,在相继经过清洗剂和去离子水超声波清洗的氧化铟锡(ITO)玻璃衬底上进行蒸镀。首先蒸镀一层10nm的三氧化钼(MoO3)作为空穴注入层,其次,蒸镀一层60nm的4,4'-环己基二[N,N-二(4-甲基苯基)苯胺(NPB)作为空穴传输层,再在上述空穴传输层上,真空蒸镀4,4',4”-三(咔唑-9-基)三苯胺(TCTA),以形成10nm的电子阻挡层,接着混合蒸镀30nm本发明所提供的杂蒽衍生物与4,4'-双(9-乙基-3-咔唑乙烯基)-1,1'-联苯(BCzVBi),作为发光层材料,其中,BCzVBi掺杂浓度为10%(以质量分数计),随后蒸镀20nm的3,3'-[5'-[3-(3-吡啶基)苯基][1,1':3',1”-三联苯]-3,3”-二基]二吡啶(TmPyPB)作为电子传输层,最后在电子传输层上真空蒸镀一层1nm的氟化锂(LiF)和100nm的镁银合金(Mg/Ag)分别作为电子注入层和阴极。具体结构为:ITO/MoO3(10nm)/NPB(60nm)/TCTA(10nm)/本发明提供的杂蒽衍生物:10%wt BCzVBi(30nm)/TmPyPB(20nm)/LiF(1nm)/Mg:Ag(100nm)。
分别采用本发明所提供的杂蒽衍生物中的化合物1、2、15、23、31、34、41、56、64、78、88、102、111、117、126、138、149、153、168、173、174、186、192、203、217、228、236、240、245、251、293、302、306、317、323、324、410以及下列结构式的对比物1-3及9,10-二(2-萘基)蒽(ADN)作为发光主体材料完成有机发光器件1-1至1-41的制备,并对制备的发光器件进行性能检测。
具体检测数据见表1:
表1有机电致发光器件性能表征
检测结果表明,利用空穴传输型基团在杂蒽基团的2,3,7进行至少一个位点的取代构建的本申请中的杂蒽衍生物表现出了优异的荧光电致发光特性。具体表现为,将本申请的杂蒽衍生物作为发光层主体材料制备得到的有机电致发光器件,相比于具有同样器件结构的以现有技术中常用的ADN、电子传输型基团对杂蒽三取代形成的化合物以及对杂蒽二取代形成的化合物分别作为发光主体材料制备的器件,在启动电压、电流效率、光色及寿命等方面的综合性能上具有显著的优势,增大幅度达到29%以上,尤其是强电子传输型基团和强空穴传输型基团分别对杂蒽基团的两侧进行不对称取代,电致发光特性更为优良。本申请中的杂蒽衍生物在杂蒽的2,3,7位利用至少一个空穴传输型基团对杂蒽基团进行特定修饰,形成了D-A型化合物,兼具杂蒽基团的刚性结构和氧杂原子的强吸电子特性,因而具有更加平衡的空穴/电子传输速率和化学稳定性,进而将其作为发光层的主体材料应用至有机电致发光器件时,显著提高器件在启动电压、电流效率、寿命等方面的性能,并使得发光波长蓝移,发出更纯净的深蓝光,是一种理想的发光层材料,尤其是发光主体材料。
器件实施例2
本发明所提供的杂蒽衍生物作为空穴传输材料进行的器件制备可按照本方法制备。
在高真空条件下,在相继经过清洗剂和去离子水超声波清洗的氧化铟锡(ITO)玻璃衬底上进行蒸镀。首先蒸镀一层10nm的三氧化钼(MoO3)作为空穴注入层,其次,蒸镀一层80nm的本发明的杂蒽衍生物作为空穴传输层,接着混合蒸镀15nm三(2-苯基吡啶)合铱(Ir(ppy)3)与4,4'-二(9-咔唑)联苯(CBP)作为发光层材料,Ir(ppy)3的掺杂浓度为6%(以质量分数计),随后再蒸镀一层30nm的3,3'-[5'-[3-(3-吡啶基)苯基][1,1':3',1”-三联苯]-3,3”-二基]二吡啶(TmPyPB)作为电子传输层,最后在电子传输层上真空蒸镀一层1nm的氟化锂(LiF)和100nm的镁银合金(Mg/Ag)分别作为电子注入层和阴极。具体结构为:ITO/MoO3(10nm)/本发明的杂蒽衍生物(80nm)/CBP:6%wt Ir(ppy)3(15nm)/TmPyPB(30nm)/LiF(1nm)/Mg:Ag(100nm)。
分别采用本发明所提供的杂蒽衍生物中的化合物332、341、349、352、364、367、374、378、389、395、399、404、407、410、417以及下列结构式的对比物1、对比物4和对比物5及1,3,5-三[(3-吡啶基)-3-苯基]苯(TmPyPB)作为空穴传输材料完成有机发光器件2-1至2-19的制备,并对制备的发光器件进行性能检测。
具体检测数据见表2:
表2有机电致发光器件性能表征
检测结果表明,在杂蒽基团的2,3,7位利用本申请所提供的空穴传输型基团修饰,从而构建得到的本申请中的杂蒽衍生物表现出了优异的空穴传输特性。具体表现为,将本申请的杂蒽衍生物作为空穴传输材料制备得到的有机电致发光器件,相比于具有同样器件结构的以现有技术中常用的NPB、对杂蒽基团单取代和双取代形成的化合物分别作为空穴传输材料制备的器件,在启动电压、电流效率、光色、热稳定性及寿命等方面的综合性能上具有显著的优势,增大幅度达到1.72倍以上。本申请中的杂蒽衍生物在杂蒽的2,3,7位修饰本申请提供的特定的空穴传输型基团,杂蒽核心基团兼具蒽的刚性结构和,氧、硫等杂原子的强吸电子特性,空穴传输型基团的三取代修饰,大大提高材料本征空穴迁移率的同时,保证了材料的热稳定性,有效解决了现有技术中空穴/电子迁移率不匹配和易结晶的问题,进而将其作为空穴传输材料应用至有机电致发光器件时,显著提高器件在启动电压、电流效率、热稳定性寿命等方面的性能,是一种理想的空穴传输材料,亦是一种较好的电子阻挡材料。
以上所述仅为本发明的较佳实施例,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种杂蒽衍生物,其特征在于,所述杂蒽衍生物为式(I)所示结构:
其中,各X分别选自:O、S、S=O或S(=O)2;
L1、L2、L3各自独立的选自:单键;未取代的或由烷烃基、烷氧基、腈基、硝基、氟基取代的亚苯基;未取代的或由烷烃基、烷氧基、腈基、硝基、氟基取代的亚联苯基;
L1、L2、L3相同或不同;
其中,R4-R9、R13-R15分别独立的选自:氢、烷烃基、未取代的或由烷烃基取代的苯基、未取代的或由烷烃基取代的联苯基;
R10-R12、R16-R19分别独立的选自:烷烃基;未取代的或由烷烃基、烷氧基、腈基、硝基、氟基取代的苯基;未取代的或由烷烃基、烷氧基、腈基、硝基、氟基取代的联苯基;未取代的或由烷烃基、烷氧基、腈基、硝基、氟基取代的三联苯基;未取代的或由烷烃基、烷氧基、腈基、硝基、氟基、苯基取代的萘基;
Ar1、Ar2、Ar3分别独立的表示为不存在或为单环芳烃,所述Ar1、Ar2、Ar3与连接的萘环之间直接稠合;
Y1选自:O、S、N(R20)、C(R21)(R22);
Y2、Y3分别独立的选自:O、S、N(R23);
R20、R23分别独立的选自:甲基;乙基;未取代的或由甲基、烷氧基、腈基、硝基、氟基取代的苯基;未取代的或由甲基、烷氧基、腈基、硝基、氟基取代的联苯基;未取代的或由甲基、烷氧基、腈基、硝基、氟基取代的萘基;
R21与R22相同,选自甲基、乙基或者苯基,当R21、R22选自苯基时,基团之间相互独立或通过单键连接;
T、Q各自独立的为CH或N,各基团中,Q为N的个数为1或2,T为N的个数为0或1;
R1、R2、R3相同或不同;
*为取代位点。
5.根据权利要求1所述的一种杂蒽衍生物,其特征在于,L1与L2相同,R1与R2相同。
6.根据权利要求1至5任一所述的一种杂蒽衍生物,其特征在于,所述杂蒽衍生物的分子量在850以下。
8.一种根据权利要求1-7任一所述的一种杂蒽衍生物的应用,其特征在于,用作有机电致发光器件的空穴传输层和/或发光层。
9.一种根据权利要求1-7任一所述的一种杂蒽衍生物的应用,其特征在于:
R1、R2、R3中1-2个选自空穴传输基团,其余选自电子传输基团时,用作机电致发光器件的发光层,和/或R1、R2、R3均选自空穴传输基团时,用作机电致发光器件的空穴传输层。
10.一种有机电致发光器件,至少包括阴极、阳极和两电极之间的有机层,或者至少包括出光层、阴极、阳极和两电极之间的有机层,两电极之间的有机层至少包括空穴传输层或发光层,其特征在于,空穴传输层和/或发光层含有权利要求1-7任一所述的杂蒽衍生物。
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