CN111039881B - 有机化合物和电子装置 - Google Patents
有机化合物和电子装置 Download PDFInfo
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- CN111039881B CN111039881B CN201910911675.4A CN201910911675A CN111039881B CN 111039881 B CN111039881 B CN 111039881B CN 201910911675 A CN201910911675 A CN 201910911675A CN 111039881 B CN111039881 B CN 111039881B
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- 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
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- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
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- 229910052700 potassium Inorganic materials 0.000 description 1
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- 238000010248 power generation Methods 0.000 description 1
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- KATIRQRAVXTBNY-UHFFFAOYSA-N quinolin-4-ylboronic acid Chemical compound C1=CC=C2C(B(O)O)=CC=NC2=C1 KATIRQRAVXTBNY-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
Images
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- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/22—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing two or more pyridine rings directly linked together, e.g. bipyridyl
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- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
- C07D251/24—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to three ring carbon atoms
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- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing aromatic 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
Description
技术领域
本发明涉及有机材料技术领域,具体而言,涉及一种有机化合物及包含该有机化合物的和电子装置。
背景技术
近年来,有机电致发光器件(OLED:Organic electroluminescent device)作为新一代显示技术逐渐进入人们的视野。常见的有机电致发光器件是由阳极、阴极、以及在阴极和阳极之间设置一层以上的有机层构成。当阴阳两极施加电压时,两电极产生电场,在电场的作用下,阴极侧的电子向有机层内的发光层移动,阳极侧的也向发光层移动,两者在发光层结合形成激子,激子处于激发态向外释放能量,从激发态释放能量变为基态释放能量的过程对外发光。因此,提高OLED器件中电子和空穴的再结合性是至关重要的。
通常,将有机电致发光器件在高温下驱动时,会出现驱动电压上升、发光效率降低和寿命缩短等问题,导致有机电致发光器件的性能下降。
目前,虽然大量性能优良的有机电致发光材料已被陆续开发出来,但该技术仍然存在很多问题,如何设计新的性能更好的材料进行调节,以至于所有器件能够达到降低电压、提高效率和寿命的效果,一直是本领域技术人员亟待解决的问题。
发明内容
本发明的目的在于提供一种有机化合物及包含该有机化合物的和电子装置,解决现有技术存在的一种或多种问题。
根据本发明的一个方面,提供一种有机化合物,其结构如下式(1)所示:
其中,X1、X2和X3相同或不同,分别独立地选自C或N;
Ar1、Ar2、Ar3、Ar4相同或不同,且分别独立地选自取代或未取代的碳原子数为1-35的烷基、取代或未取代的碳原子数为2-35的烯基、取代或未取代的碳原子数为2-35的炔基、取代或未取代的碳原子数为3-35的环烷基、取代或未取代的碳原子数为2-35的杂环烷基、取代或未取代的碳原子数为7-30的芳烷基、取代或未取代的碳原子数为2-30的杂芳烷基、取代或未取代的碳原子数为6-30的芳基、取代或未取代的碳原子数为1-30的杂芳基。
根据本发明的另一个方面,还提供一种电子装置,包括阴极、阳极以及位于所述阴极和阳极之间的功能层,所述功能层中包含上述化合物。
在本发明的一种示例性实施方式中,所述电子装置为有机电致发光器件或太阳能电池。
在本发明的一种示例性实施方式中,所述功能层包括电子传输层,所述化合物位于所述电子传输层。
本发明的化合物在以2,4-二苯基-1,3,5-三嗪为电子注入和传输基团的基础上,引入了金刚烷-芴基团这一核心结构;此基团具有富电子特性,使得整个分子的极性增强,有利于材料分子的方向性排列,从而增强电子的注入和传输,提升器件的光电转换效率。同时,金刚烷-芴基团具有大的分子量和空间位阻效应,可以有效提升材料的玻璃化转变温度,同时抑制材料结晶,使得材料在光电转换器件使用中具有更好的寿命。以此化合物作为电子传输层材料,可以改善有机电致发光器件的寿命特性、效率特性、电化学稳定性和热稳定性并且降低驱动电压。
应当理解的是,以上的一般描述和后文的细节描述仅是示例性和解释性的,并不能限制本发明。
附图说明
此处的附图被并入说明书中并构成本说明书的一部分,示出了符合本公开的实施例,并与说明书一起用于解释本公开的原理。显而易见地,下面描述中的附图仅仅是本公开的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。
图1为本发明实施方式有机电致发光器件的结构示意图;
图2为本发明实施方式太阳能电池的结构示意图。
图1中:10、阳极;20、功能层;201、空穴注入层;202、空穴传输层;203、电子阻挡层;204、发光层;205、空穴阻挡层;206、电子传输层;207、电子注入层;30、阴极;40、覆盖层;
图2中:50、阳极;60、功能层;601、空穴传输层;602、光敏活性层;603、电子传输层;70、阴极。
具体实施方式
现在将更全面地描述示例实施方式。然而,示例实施方式能够以多种形式实施,且不应被理解为限于在此阐述的实施方式;相反,提供这些实施方式使得本发明将全面和完整,并将示例实施方式的构思全面地传达给本领域的技术人员。
本发明实施方式提供一种有机化合物,其结构如化学式1所示:
其中,X1、X2和X3相同或不同,分别独立地选自C或N;
Ar1、Ar2、Ar3、Ar4相同或不同,且分别独立地选自取代或未取代的碳原子数为1-35的烷基、取代或未取代的碳原子数为2-35的烯基、取代或未取代的碳原子数为2-35的炔基、取代或未取代的碳原子数为3-35的环烷基、取代或未取代的碳原子数为2-35的杂环烷基、取代或未取代的碳原子数为7-30的芳烷基、取代或未取代的碳原子数为2-30的杂芳烷基、取代或未取代的碳原子数为6-30的芳基、取代或未取代的碳原子数为1-30的杂芳基。
在本公开中,当没有另外提供具体的定义时,“杂”是指在一个官能团中包括至少1个B、N、O、S或P等杂原子且其余原子为碳和氢。
芳基可以是单环芳基、稠环芳基、通过碳碳键共轭连接的两个单环芳基、通过碳碳键共轭连接的单环芳基和稠环芳基、通过碳碳键共轭连接的两个稠环芳基。即,通过碳碳键共轭连接的两个或者多个芳香基团也可以视为本公开的芳基。其中,芳基中不含有B、N、O、S或P等杂原子。
杂芳基可以是单环杂芳基、稠环杂芳基、通过碳碳键共轭连接的两个芳香环系且至少其中一个芳香环系含有杂原子,其中,芳香环系可以为单环芳香环系或者稠环芳香环系。
该化合物在以2,4-二苯基-1,3,5-三嗪为电子注入和传输基团的基础上,引入了金刚烷-芴基团这一核心结构。金刚烷-芴基团具有富电子特性,使得整个分子的极性增强,有利于材料分子的方向性排列,从而增强电子的注入和传输,提升器件效率。同时,金刚烷-芴基团具有大的分子量和空间位阻效应,可以有效提升材料的玻璃化转变温度,同时抑制材料结晶,使得材料在器件使用中具有更好的寿命。以此化合物作为电子传输层材料,可以改善有机电致发光器件的寿命特性、效率特性、电化学稳定性和热稳定性并且降低驱动电压。
优选地,上述结构中的X1、X2和X3均相同,且均为N。
优选地,Ar1、Ar2、Ar3、Ar4的取代基相同或不同,且分别独立地选自氘、氰基、硝基、卤素、羟基、取代或未取代的碳原子数1-33的烷基、取代或未取代的碳原子数3-33的环烷基、取代或未取代的碳原子数2-33的烯基、取代或未取代的碳原子数2-33的炔基、取代或未取代的碳原子数2-40的杂环烷基、取代或未取代的碳原子数7-33的芳烷基、取代或未取代的碳原子数2-33的杂芳烷基、取代或未取代的碳原子数6-33的芳基、取代或未取代的碳原子数1-33的杂芳基、取代或未取代的碳原子数1-40的烷氧基、取代或未取代的碳原子数1-33的烷氨基、取代或未取代的碳原子数6-33的芳氨基、取代或未取代的碳原子数为1-33的烷硫基、取代或未取代的碳原子数7-33的芳烷氨基、取代或未取代的碳原子数1-24的杂芳氨基、取代或未取代的碳原子数为1-33的烷基甲硅烷基、取代或未取代的碳原子数为6-33的芳基甲硅烷基、取代或未取代的碳原子数为6-30的芳氧基、取代或未取代的碳原子数为6-30芳硫基。
优选地,Ar1、Ar2分别独立的选自取代或未取代的成环碳原子数为5-18的芳基或杂芳基。
进一步地,所述Ar1、Ar2分别独立的选自以下基团组成的组:
优选地,所述Ar3选自以下基团组成的组:
优选地,Ar4选自甲基、取代或未取代的成环碳原子数为6-25的芳基、取代或未取代的成环碳原子数为4-24的杂芳基。
优选地,Ar4选自以下基团组成的组:
作为进一步的优选,该化合物选自如下化合物:
下面对本发明实施方式的化合物的制备方法进行详细说明:
化合物1的合成
将镁条(15.44g,643.5mmol)和乙醚(100mL)置于氮气保护下干燥的圆底烧瓶中,加入碘(119mg)。而后将溶有2-溴联苯2-溴甲苯(50.00g,214.49mmol)的乙醚(200mL)溶液缓慢滴入烧瓶中,滴加完毕后升温至35℃,搅拌3小时;将反应液降至0℃,向其中缓慢滴入溶有金刚烷酮(48.33g,321.7mmol)的乙醚(200mL)溶液,滴加完毕后升温至35℃,搅拌6小时;将反应液冷却至室温,向其中加入5%盐酸至pH<7,搅拌1小时,加入乙醚(200mL)进行萃取,合并有机相,使用无水硫酸镁进行干燥,过滤,减压除去溶剂;所得粗品使用乙酸乙酯/正庚烷(1:2)为流动相进行硅胶柱色谱提纯,得到白色固体中间体I-A-1(43g,收率66.34%)。
将中间体I-A-1(43g,141.2mmol)、三氟乙酸(40.26g,353.1mmol)和二氯甲烷(300mL)加入圆底烧瓶中,氮气保护下搅拌2小时;而后向反应液中加入氢氧化钠水溶液至pH=8,分液,有机相使用无水硫酸镁进行干燥,过滤,减压除去溶剂;所得粗品使用二氯甲烷/正庚烷(1:2)进行硅胶柱色谱提纯,得到白色固体状中间体I-A-2(36.5g,收率90.24%)。
将中间体I-A-2(36g,125.6mmol)、N-溴代琥珀酰亚胺(26.84g,150.82mmol)和二氯甲烷(800mL)加入圆底烧瓶中,氮气保护下搅拌5小时;分液,有机相使用无水硫酸镁进行干燥,过滤,减压除去溶剂,得到白色固体状中间体I-A-3(38.9g,收率85.2%)。
将中间体I-A-3(38g,104.0mmol)加入圆底烧瓶中,600ml的四氢呋喃(THF)经过除水后加入到烧瓶中,给体系用液氮降温至-80℃~-90℃,开始滴加正丁基锂(nBuLi,6.66g,104.0mmol),滴毕,保温1h。滴加硼酸三甲酯(14.05g,135.2mmol),温度保持-80℃~-90℃,滴毕,保温1h后,自然升至室温,反应结束,加入HCl的水溶液,搅拌0.5h。加入二氯甲烷和水进行分液萃取,有机相洗至中性PH=7,合并有机相,无水MgSO4干燥10min后,过滤,滤液旋干,用正庚烷打浆2次得到白色固体中间体I-A-4(22.32g,收率65.21%)。
将2-氯-4,6-二苯基-1,3,5-三嗪(6g,22.4mmol)、3-溴-5-甲基苯基硼酸(5.29g,24.6mmol)、四(三苯基膦)钯(1.29g,1.12mmol)、碳酸钾(6.19g,44.8mmol)、四丁基氯化铵(0.30g,1.12mmol)、甲苯(PhMe,50mL)、乙醇(25mL)和去离子水(12mL)加入三口烧瓶中,氮气保护下升温至76℃,加热回流搅拌6h。反应结束后,溶液冷却至室温,加入甲苯和水萃取反应溶液,合并有机相,无水硫酸镁干燥有机层,过滤,进行浓缩;粗品利用硅胶柱色谱进行提纯,得到中间体II-A(7.07g,78.56%)。
将中间体II-A(2.5g,6.21mmol)、中间体I-A-4(2.25g,6.83mmol)、四(三苯基膦)钯(0.36g,0.31mmol)、碳酸钾(1.72g,12.42mmol)、四丁基氯化铵(0.08g,0.31mmol)、甲苯(24mL)、乙醇(12mL)和去离子水(6mL)加入三口烧瓶中,氮气保护下升温至76℃,加热回流搅拌8h。反应结束后,溶液冷却至室温,反应固体析出,抽滤,用水进行淋洗,接着用乙醇带去水,得到黄色固体,用甲苯进行重结晶得到固体化合物1(3.16g,收率84.52%)。质谱:m/z=608.30(M+H)+。
化合物2的合成
将2-氯-4,6-二苯基-1,3,5-三嗪(20g,74.70mmol)、3-溴-5-氯苯硼酸(21.09g,89.64mmol)、四(三苯基膦)钯(4.32g,3.73mmol)、碳酸钾(20.64g,149.41mmol)、四丁基氯化铵(1.01g,3.73mmol)、甲苯(24mL)、乙醇(12mL)和去离子水(6mL)加入三口烧瓶中,氮气保护下升温至76℃,加热回流搅拌8h。反应结束后,溶液冷却至室温,反应固体析出,抽滤,用水进行淋洗,接着用乙醇带去水,得到灰色固体,粗品利用硅胶柱色谱进行提纯得到中间体II-B-1(25.88g,收率82.10%)。
将中间体II-B-1(6g,14.19mmol)、二苯并呋喃-2-硼酸(3.61g,17.03mmol)、四(三苯基膦)钯(0.82g,0.71mmol)、碳酸钾(3.92g,28.39mmol)、四丁基氯化铵(0.19g,0.71mmol)、甲苯(48mL)、乙醇(24mL)和去离子水(12mL)加入三口烧瓶中,氮气保护下升温至76℃,加热回流搅拌7h。反应结束后,溶液冷却至室温,反应固体析出,抽滤,用水进行淋洗,接着用乙醇带去水,得到固体,粗品利用硅胶柱色谱进行提纯得到中间体II-B(6.23g,收率86.21%)。
将中间体II-B(6g,11.76mmol),中间体I-A-4(4.27g,12.94mmol)、四(三苯基膦)钯(0.68g,0.58mmol)、碳酸钾(3.25g,23.53mmol)、四丁基氯化铵(0.16g,0.58mmol)、甲苯(48mL)、乙醇(24mL)和去离子水(12mL)加入三口烧瓶中,氮气保护下升温至76℃,加热回流搅拌7h。反应结束后,溶液冷却至室温,反应固体析出,抽滤,用水进行淋洗,接着用乙醇带去水,得到灰色固体,粗品利用硅胶柱色谱进行提纯得到化合物2(7.11g,收率79.56%)。质谱:m/z=760.32(M+H)+。
化合物3的合成
将中间体II-B-1(6g,14.19mmol)、苯硼酸(1.9g,15.61mmol)、四(三苯基膦)钯(0.32g,0.28mmol)、碳酸钾(3.92g,28.38mmol)、四丁基氯化铵(0.19g,0.70mmol)、甲苯(48mL)、乙醇(24mL)和去离子水(12mL)加入三口烧瓶中,氮气保护下升温至76℃,加热回流搅拌7h。反应结束后,溶液冷却至室温,反应液水洗后加入硫酸镁干燥,过滤后将滤液通过短硅胶柱,减压除去溶剂;使用二氯甲烷/正庚烷体系对粗品进行重结晶提纯,得到中间体II-C(4.82g,收率81.10%)。
将中间体II-C(4.5g,10.71mmol)、中间体I-A-4(3.89g,11.78mmol)、四(三苯基膦)钯(0.24g,0.21mmol)、碳酸钾(2.76g,21.43mmol)、四丁基氯化铵(0.15g,0.53mmol)、甲苯(24mL)、乙醇(12mL)和去离子水(6mL)加入三口烧瓶中,氮气保护下升温至76℃,加热回流搅拌7h。反应结束后,溶液冷却至室温,反应液使用水洗后加入硫酸镁干燥,过滤后将滤液通过短硅胶柱,减压除去溶剂;粗品利用硅胶柱色谱进行提纯得到化合物3(5.17g,收率72.00%)。质谱:m/z=670.31(M+H)+。核磁共振数据:1H NMR(CDCl3,400MHz):9.13(s,1H),8.97(s,1H),8.82(d,4H),8.60(s,1H),8.17(d,1H),8.11(s,1H),7.94(d,1H),7.87(d,1H),7.84-7.80(m,3H),7.64(t,2H),7.61-7.56(m,6H),7.47(t,1H),7.42(t,1H),7.34(t,1H),3.18(d,2H),3.01(d,2H),2.36(s,1H),2.27(s,1H),2.07(s,2H),1.94(d,2H),1.87(d,2H),1.76(s,2H)。
化合物4的合成
将中间体II-B-1(5g,11.83mmol)、二苯并噻吩-2-硼酸(2.75g,12.06mmol)、四(三苯基膦)钯(0.68g,0.59mmol)、碳酸钾(3.19g,23.65mmol)、四丁基氯化铵(0.16g,0.59mmol)、甲苯(40mL)、乙醇(20mL)和去离子水(10mL)加入三口烧瓶中,氮气保护下升温至76℃,加热回流搅拌7h。反应结束后,溶液冷却至室温,反应液使用水洗后加入硫酸镁干燥,过滤后将滤液通过短硅胶柱,减压除去溶剂;粗品利用硅胶柱色谱进行提纯,得到白色固体中间体II-D(4.61g,收率74.12%)。
将中间体II-D(4.5g,8.55mmol),中间体I-A-4(2.88g,8.72mmol)、四(三苯基膦)钯(0.49g,0.42mmol)、碳酸钾(2.36g,17.10mmol)、四丁基氯化铵(0.11g,0.42mmol)、甲苯(40mL)、乙醇(20mL)和去离子水(10mL)加入三口烧瓶中,氮气保护下升温至76℃,加热回流搅拌7h。反应结束后,溶液冷却至室温,反应固体析出,抽滤,用水进行淋洗,接着用乙醇带去水,得到白色固体,用甲苯进行重结晶得到化合物4(5.20g,收率78.47%)。质谱:m/z=776.30(M+H)+。
化合物5的合成
将中间体II-B-1(4g,9.46mmol)、N-苯基-3-咔唑硼酸(2.77g,9.65mmol)、四(三苯基膦)钯(0.55g,0.47mmol)、碳酸钾(2.61g,18.92mmol)、四丁基氯化铵(0.13g,0.47mmol)、甲苯(32mL)、乙醇(16mL)和去离子水(8mL)加入三口烧瓶中,氮气保护下升温至76℃,加热回流搅拌7h。反应结束后,溶液冷却至室温,反应液使用水洗后加入硫酸镁干燥,过滤后将滤液通过短硅胶柱,减压除去溶剂;粗品利用硅胶柱色谱进行提纯得到中间体II-E(4.20g,76.12%)。
将中间体II-E(4.0g,6.83mmol)、中间体I-A-4(2.00g,6.97mmol)、四(三苯基膦)钯(0.39g,0.34mmol)、碳酸钾(1.88g,13.67mmol)、四丁基氯化铵(0.09g,0.34mmol)、甲苯(32mL)、乙醇(16mL)和去离子水(8mL)加入三口烧瓶中,氮气保护下升温至76℃,加热回流搅拌7h。反应结束后,溶液冷却至室温,反应液使用水洗后加入硫酸镁干燥,过滤后将滤液通过短硅胶柱,减压除去溶剂;粗品利用硅胶柱色谱进行提纯得到中间体得到化合物5(4.52g,79.46%)。质谱:m/z=835.37(M+H)+。
化合物6的合成
将中间体II-B-1(5.5g,13.01mmol)、9,9'-螺二[9H-芴]-2-硼酸(4.80g,13.27mmol)、四(三苯基膦)钯(0.75g,0.65mmol)、碳酸钾(3.59g,26.02mmol)、四丁基氯化铵(0.18g,0.65mmol)、甲苯(44mL)、乙醇(22mL)和去离子水(11mL)加入三口烧瓶中,氮气保护下升温至76℃,加热回流搅拌5h。反应结束后,溶液冷却至室温,反应结束后,溶液冷却至室温,反应液使用水洗后加入硫酸镁干燥,过滤后将滤液通过短硅胶柱,减压除去溶剂;粗品利用硅胶柱色谱进行提纯得到中间体II-F(6.99,收率81.46%)。
将中间体II-F(5.0g,7.57mmol)、中间体I-A-4(2.62g,7.95mmol)、四(三苯基膦)钯(0.43g,0.37mmol)、碳酸钾(2.09g,15.14mmol)、四丁基氯化铵(0.10g,0.37mmol)、甲苯(40mL)、乙醇(20mL)和去离子水(10mL)加入三口烧瓶中,氮气保护下升温至76℃,加热回流搅拌4h。反应结束后,溶液冷却至室温,反应固体析出,抽滤,用水进行淋洗,接着用乙醇带去水,得到白色固体,用甲苯进行重结晶得到化合物6(5.20g,收率75.49%)。质谱:m/z=909.41(M+H)+。
化合物7的合成
将镁条(14.90g,620.93mmol)和乙醚(120mL)置于氮气保护下干燥的圆底烧瓶中,加入碘(103.42,407.49mg)。而后将溶有1-溴-2,4-二(苯基)苯(60.00g,194.04mmol)的乙醚(220mL)溶液缓慢滴入烧瓶中,滴加完毕后升温至35℃,搅拌3小时;将反应液降至0℃,向其中缓慢滴入溶有金刚烷酮(46.63g,310.46mmol)的乙醚(220mL)溶液,滴加完毕后升温至35℃,搅拌6小时;将反应液冷却至室温,向其中加入5%盐酸至pH<7,搅拌1小时,加入乙醚(200mL)进行萃取,合并有机相,使用无水硫酸镁进行干燥,过滤,减压除去溶剂;所得粗品使用乙酸乙酯/正庚烷(1:2)为流动相进行硅胶柱色谱提纯,得到白色固体中间体I-B-1(45.54g,收率67.49%)。
将中间体I-B-1(45.50g,125.51mmol)、N-溴代琥珀酰亚胺(26.80,150.61mmol)和二氯甲烷(450mL)加入圆底烧瓶中,氮气保护下搅拌5小时;分液,有机相使用无水硫酸镁进行干燥,过滤,减压除去溶剂,得到白色固体状中间体I-B-2(41.67g,收率87.25%)。
将中间体I-B-2(41.0g,125.6mmol)、N-溴代琥珀酰亚胺(31.12g,150.82mmol)和二氯甲烷(800mL)加入圆底烧瓶中,氮气保护下搅拌5h;分液,有机相使用无水硫酸镁进行干燥,过滤,减压除去溶剂,得到白色固体状中间体I-B-3(42.9g,85.2%)。
将中间体I-B-3(41.5g,94.01mmol)加入圆底烧瓶中,630ml的THF经过除水后加入到烧瓶中,给体系用液氮降温至-80℃~-90℃,开始滴加正丁基锂(6.02g,94.01mmol),滴毕,保温1h。滴加硼酸三甲酯(12.70g,122.22mmol),温度保持-80℃~-90℃,滴毕,保温1h后,自然升至室温,反应结束,加入HCl的水溶液,搅拌0.5h。加入二氯甲烷和水进行分液萃取,有机相洗至中性PH=7,合并有机相,无水MgSO4干燥10min后,过滤,滤液旋干,用正庚烷打浆2次得到白色固体中间体I-B-4(26.78g,收率70.12%)。
将中间体II-B-1(4.0g,12.81mmol)、苯硼酸(1.59g,13.06mmol)、四(三苯基膦)钯(0.74g,0.64mmol)、碳酸钾(3.54g,25.62mmol)、四丁基氯化铵(0.17g,0.64mmol)、甲苯(32mL)、乙醇(16mL)和去离子水(8mL)加入三口烧瓶中,氮气保护下升温至76℃,加热回流搅拌7h。反应结束后,溶液冷却至室温,反应固体析出,抽滤,用水进行淋洗,接着用乙醇带去水,得到白色固体,用甲苯进行重结晶得到中间体II-G(4.42g,收率82.10%)。
将中间体II-G(4g,9.54mmol)、中间体I-B-4(3.95g,9.73mmol)、四(三苯基膦)钯(0.55g,0.47mmol)、碳酸钾(2.63g,19.09mmol)、四丁基氯化铵(0.13g,0.47mmol)、甲苯(32mL)、乙醇(16mL)和去离子水(8mL)加入三口烧瓶中,氮气保护下升温至76℃,加热回流搅拌6h。反应结束后,溶液冷却至室温,反应液使用水洗后加入硫酸镁干燥,过滤后将滤液通过短硅胶柱,减压除去溶剂;粗品利用硅胶柱色谱进行提纯得到化合物7(5.31,收率74.63%)。质谱:m/z=746.35(M+H)+。
化合物8的合成
将中间体II-B-1(5.0g,11.82mmol),2-联苯硼酸(2.81g,14.19mmol)、四(三苯基膦)钯(0.27g,0.23mmol)、碳酸钾(3.27g,23.65mmol)、四丁基氯化铵(0.16g,0.59mmol)、甲苯(40mL)、乙醇(20mL)和去离子水(10mL)加入三口烧瓶中,氮气保护下升温至76℃,加热回流搅拌7h。反应结束后,溶液冷却至室温,反应固体析出,抽滤,用水进行淋洗,接着用乙醇带去水,得到白色固体,用甲苯进行重结晶得到中间体II-H(4.16,收率71.89%)。
将中间体II-H(4g,8.06mmol),中间体I-B-4(1.91g,9.67mmol)、四(三苯基膦)钯(0.16g,0.18mmol)、碳酸钾(2.23g,16.12mmol)、四丁基氯化铵(0.18g,0.16mmol)、甲苯(32mL)、乙醇(16mL)和去离子水(8mL)加入三口烧瓶中,氮气保护下升温至76℃,加热回流搅拌7h。反应结束后,溶液冷却至室温,反应固体析出,抽滤,用水进行淋洗,接着用乙醇带去水,得到白色固体,用甲苯进行重结晶得到化合物8(4.74g,收率73.87%)。质谱:m/z=746.35(M+H)+。
化合物9的合成
将中间体II-D(3.5g,6.52mmol),中间体I-B-4(2.78g,6.85mmol)、四(三苯基膦)钯(0.37g,0.32mmol)、碳酸钾(1.80g,13.05mmol)、四丁基氯化铵(0.09g,0.33mmol)、甲苯(28mL)、乙醇(14mL)和去离子水(7mL)加入三口烧瓶中,氮气保护下升温至76℃,加热回流搅拌7h。反应结束后,溶液冷却至室温,反应液使用水洗后加入硫酸镁干燥,过滤后将滤液通过短硅胶柱,减压除去溶剂;粗品利用硅胶柱色谱进行提纯得到化合物9(4.36,收率75.86%)。质谱:m/z=822.38(M+H)+。
化合物10的合成
将中间体II-B-1(4.00g,9.47mmol)、4-(4-吡啶基)苯硼酸(1.92g,9.66mmol)、四(三苯基膦)钯(0.54g,0.47mmol)、碳酸钾(2.62g,18.94mmol)、四丁基氯化铵(0.13g,0.47mmol)、甲苯(32mL)、乙醇(16mL)和去离子水(8mL)加入三口烧瓶中,氮气保护下升温至76℃,加热回流搅拌7h。反应结束后,溶液冷却至室温,反应固体析出,抽滤,用水进行淋洗,接着用乙醇带去水,得到白色固体,用甲苯进行重结晶得到中间体II-I(3.61g,收率76.84%)。
将中间体II-I(3.50g,7.04mmol),中间体I-B-4(2.91g,7.18mmol)、四(三苯基膦)钯(0.40g,0.35mmol)、碳酸钾(1.94g,14.08mmol)、四丁基氯化铵(0.09g,0.35mmol)、甲苯(28mL)、乙醇(16mL)和去离子水(8mL)加入三口烧瓶中,氮气保护下升温至76℃,加热回流搅拌7h。反应结束后,溶液冷却至室温,反应固体析出,抽滤,用水进行淋洗,接着用乙醇带去水,得到白色固体,用甲苯进行重结晶得到化合物10(4.32g,收率74.75%)。质谱:m/z=823.37(M+H)+。
化合物11的合成
将中间体II-B-1(4.00g,9.46mmol),3-甲基苯硼酸(1.35g,9.93mmol)、四(三苯基膦)钯(0.54g,0.47mmol)、碳酸钾(2.61g,18.92mmol)、四丁基氯化铵(0.13g,0.47mmol)、甲苯(32mL)、乙醇(16mL)和去离子水(8mL)加入三口烧瓶中,氮气保护下升温至76℃,加热回流搅拌7h。反应结束后,溶液冷却至室温,反应固体析出,抽滤,用水进行淋洗,接着用乙醇带去水,得到白色固体,用甲苯进行重结晶得到中间体II-J(3.21g,收率76.85%)。
将中间体II-J(3.00g,6.91mmol),中间体I-B-4(3.09g,7.60mmol)、四(三苯基膦)钯(0.39g,0.34mmol)、碳酸钾(1.91g,13.82mmol)、四丁基氯化铵(0.09g,0.34mmol)、甲苯(24mL)、乙醇(12mL)和去离子水(6mL)加入三口烧瓶中,氮气保护下升温至76℃,加热回流搅拌7h。反应结束后,溶液冷却至室温,反应固体析出,抽滤,用水进行淋洗,接着用乙醇带去水,得到白色固体,用甲苯进行重结晶得到化合物11(4.21g,收率80.23%)。质谱:m/z=760.36(M+H)+。
化合物12的合成
将中间体II-B-1(6.00g,14.19mmol),4-吡啶苯硼酸(2.09g,17.03mmol)、四(三苯基膦)钯(0.32g,0.28mmol)、碳酸钾(3.92g,28.38mmol)、四丁基氯化铵(0.19g,0.47mmol)、甲苯(48mL)、乙醇(24mL)和去离子水(12mL)加入三口烧瓶中,氮气保护下升温至76℃,加热回流搅拌7h。反应结束后,溶液冷却至室温,反应固体析出,抽滤,用水进行淋洗,接着用乙醇带去水,得到白色固体,用甲苯进行重结晶得到中间体II-J(4.39g,收率73.65%)。
将中间体II-K(4.00g,9.05mmol)、中间体I-B-4(4.24g,10.45mmol)、四(三苯基膦)钯(0.21g,0.19mmol)、碳酸钾(2.62g,19.00mmol)、四丁基氯化铵(0.12g,0.44mmol)、甲苯(32mL)、乙醇(16mL)和去离子水(8mL)加入三口烧瓶中,氮气保护下升温至76℃,加热回流搅拌7h。反应结束后,溶液冷却至室温,反应液使用水洗后加入硫酸镁干燥,过滤后将滤液通过短硅胶柱,减压除去溶剂;粗品用甲苯进行重结晶得到化合物12(5.26g,收率82.46%)。质谱:m/z=685.33(M+H)+。
化合物13的合成
将中间体II-B-1(7.00g,16.55mmol),4-联苯硼酸(3.60g,18.21mmol)、四(三苯基膦)钯(0.38g,0.33mmol)、碳酸钾(4.57g,33.11mmol)、四丁基氯化铵(0.22g,0.82mmol)、甲苯(56mL)、乙醇(28mL)和去离子水(14mL)加入三口烧瓶中,氮气保护下升温至76℃,加热回流搅拌7h。反应结束后,溶液冷却至室温,反应固体析出,抽滤,用水进行淋洗,接着用乙醇带去水,得到白色固体,用甲苯进行重结晶得到II-L(6.52g,收率79.48%)。
将中间体II-L(6.00g,12.09mmol),中间体I-B-4(5.40g,13.30mmol)、四(三苯基膦)钯(0.27g,0.24mmol)、碳酸钾(3.34g,24.19mmol)、四丁基氯化铵(0.16g,0.60mmol)、甲苯(48mL)、乙醇(24mL)和去离子水(12mL)加入三口烧瓶中,氮气保护下升温至76℃,加热回流搅拌7h。反应结束后,溶液冷却至室温,反应固体析出,抽滤,用水进行淋洗,接着用乙醇带去水,得到白色固体,用甲苯进行重结晶得到化合物13(7.49g,收率75.34%)。质谱:m/z=822.38(M+H)+。
化合物14的合成
将中间体II-B-1(6.0g,14.19mmol)、2-萘硼酸(2.68g,15.61mmol)、四(三苯基膦)钯(0.32g,0.28mmol)、碳酸钾(3.92g,28.38mmol)、四丁基氯化铵(0.19g,0.71mmol)、甲苯(48mL)、乙醇(24mL)和去离子水(12mL)加入三口烧瓶中,氮气保护下升温至76℃,加热回流搅拌5h。反应结束后,溶液冷却至室温,反应结束后,溶液冷却至室温,反应液使用水洗后加入硫酸镁干燥,过滤后将滤液通过短硅胶柱,减压除去溶剂;粗品利用硅胶柱色谱进行提纯得到中间体II-M(5.43g,收率81.46%)。
将中间体II-M(5.0g,10.63mmol)、中间体I-B-4(4.75g,11.70mmol)、四(三苯基膦)钯(0.24g,0.21mmol)、碳酸钾(2.94g,21.27mmol)、四丁基氯化铵(0.14g,0.53mmol)、甲苯(40mL)、乙醇(20mL)和去离子水(10mL)加入三口烧瓶中,氮气保护下升温至76℃,加热回流搅拌6h。反应结束后,溶液冷却至室温,反应固体析出,抽滤,用水进行淋洗,接着用乙醇带去水,得到白色固体,用甲苯进行重结晶得到化合物14(6.10g,收率72.22%)。质谱:m/z=798.37(M+H)+。
化合物15的合成
将中间体II-B-1(4.00g,9.46mmol),喹啉-4-硼酸(1.96g,11.35mmol)、四(三苯基膦)钯(0.22g,1.89mmol)、碳酸钾(2.62g,18.92mmol)、四丁基氯化铵(0.13g,0.47mmol)、甲苯(32mL)、乙醇(16mL)和去离子水(8mL)加入三口烧瓶中,氮气保护下升温至76℃,加热回流搅拌5h。反应结束后,溶液冷却至室温,反应固体析出,抽滤,用水进行淋洗,接着用乙醇带去水,得到白色固体,用甲苯进行重结晶得到中间体II-N(3.24g,72.84%)
将中间体II-N(3.20g,6.79mmol),中间体I-B-4(3.31g,8.15mmol)、四(三苯基膦)钯(0.15g,0.13mmol)、碳酸钾(1.87g,13.58mmol)、四丁基氯化铵(0.09g,0.34mmol)、甲苯(28mL)、乙醇(16mL)和去离子水(8mL)加入三口烧瓶中,氮气保护下升温至76℃,加热回流搅拌7h。反应结束后,溶液冷却至室温,反应固体析出,抽滤,用水进行淋洗,接着用乙醇带去水,得到白色固体,用甲苯进行重结晶得到化合物15(4.00g,74.75%)。质谱:m/z=797.36(M+H)+。
化合物16的合成
将中间体II-B-1(4.20g,9.93mmol),嘧啶-4-硼酸(1.47g,11.92mmol)、四(三苯基膦)钯(0.23g,1.19mmol)、碳酸钾(2.74g,19.87mmol)、四丁基氯化铵(0.14g,0.49mmol)、甲苯(32mL)、乙醇(16mL)和去离子水(8mL)加入三口烧瓶中,氮气保护下升温至76℃,加热回流搅拌7h。反应结束后,溶液冷却至室温,反应固体析出,抽滤,用水进行淋洗,接着用乙醇带去水,得到白色固体,用甲苯进行重结晶得到中间体II-O(3.13g,74.85%)。
将中间体II-O(3.20g,7.34mmol),中间体I-B-4(3.58g,8.82mmol)、四(三苯基膦)钯(0.17g,0.15mmol)、碳酸钾(2.03g,14.69mmol)、四丁基氯化铵(0.10g,0.36mmol)、甲苯(28mL)、乙醇(16mL)和去离子水(8mL)加入三口烧瓶中,氮气保护下升温至76℃,加热回流搅拌7h。反应结束后,溶液冷却至室温,反应固体析出,抽滤,用水进行淋洗,接着用乙醇带去水,得到白色固体,用甲苯进行重结晶得到化合物16(4.47g,81.46%)。质谱:m/z=745.34(M+H)+。
化合物17的合成
将中间体II-B-1(6.00g,14.19mmol),4-(萘-2-)苯硼酸(3.87g,11.92mmol)、四(三苯基膦)钯(0.32g,0.28mmol)、碳酸钾(3.92g,28.38mmol)、四丁基氯化铵(0.19g,0.71mmol)、甲苯(48mL)、乙醇(24mL)和去离子水(12mL)加入三口烧瓶中,氮气保护下升温至76℃,加热回流搅拌7h。反应结束后,溶液冷却至室温,反应固体析出,抽滤,用水进行淋洗,接着用乙醇带去水,得到白色固体,用甲苯进行重结晶得到中间体II-P(5.80g,74.85%)
将中间体II-P(5.50g,10.07mmol),中间体I-B-4(4.50g,11.07mmol)、四(三苯基膦)钯(0.23g,0.20mmol)、碳酸钾(2.78g,20.14mmol)、四丁基氯化铵(0.14g,0.50mmol)、甲苯(48mL)、乙醇(24mL)和去离子水(12mL)加入三口烧瓶中,氮气保护下升温至76℃,加热回流搅拌7h。反应结束后,溶液冷却至室温,反应固体析出,抽滤,用水进行淋洗,接着用乙醇带去水,得到白色固体,用甲苯进行重结晶得到化合物17(6.17g,70.32%)。质谱:m/z=872.39(M+H)+。
化合物18的合成
将中间体II-B-1(6.00g,14.19mmol),3-吡啶苯硼酸(2.09g,17.03mmol)、四(三苯基膦)钯(0.32g,0.28mmol)、碳酸钾(3.92g,28.38mmol)、四丁基氯化铵(0.19g,0.47mmol)、甲苯(48mL)、乙醇(24mL)和去离子水(12mL)加入三口烧瓶中,氮气保护下升温至76℃,加热回流搅拌7h。反应结束后,溶液冷却至室温,反应固体析出,抽滤,用水进行淋洗,接着用乙醇带去水,得到白色固体,用甲苯进行重结晶得到中间体II-Q(4.39g,收率73.65%)。
将中间体II-Q(4.00g,9.05mmol)、中间体I-A-4(4.24g,10.45mmol)、四(三苯基膦)钯(0.21g,0.19mmol)、碳酸钾(2.62g,19.00mmol)、四丁基氯化铵(0.12g,0.44mmol)、甲苯(32mL)、乙醇(16mL)和去离子水(8mL)加入三口烧瓶中,氮气保护下升温至76℃,加热回流搅拌7h。反应结束后,溶液冷却至室温,反应液使用水洗后加入硫酸镁干燥,过滤后将滤液通过短硅胶柱,减压除去溶剂;粗品用甲苯进行重结晶得到化合物18(5.26g,收率81.46%)。质谱:m/z=671.31(M+H)+。核磁共振数据:1H NMR(CDCl3,400MHz):9.18(s,1H),9.11(s,1H),8.96(s,1H),8.82(d,4H),8.71(d,1H),8.59(s,1H),8.17(d,1H),8.12-8.09(m,3H),7.95(d,1H),7.87(d,1H),7.80(d,1H),7.64(t,2H),7.60(t,4H),7.51-7.49(m,1H),7.43(t,1H),7.34(t,1H),3.17(d,2H),3.00(d,2H),2.36(s,1H),2.27(s,1H),2.07(s,2H),1.94(d,2H),1.87(d,2H),1.75(s,2H)。
化合物19的合成
将中间体II-B-1(6.00g,14.19mmol),9,9-二甲基芴-2-硼酸(2.09g,17.03mmol)、四(三苯基膦)钯(0.32g,0.28mmol)、碳酸钾(3.92g,28.38mmol)、四丁基氯化铵(0.19g,0.47mmol)、甲苯(48mL)、乙醇(24mL)和去离子水(12mL)加入三口烧瓶中,氮气保护下升温至76℃,加热回流搅拌7h。反应结束后,溶液冷却至室温,反应固体析出,抽滤,用水进行淋洗,接着用乙醇带去水,得到白色固体,用甲苯进行重结晶得到中间体II-R(4.19g,收率72.65%)。
将中间体II-R(4.00g,9.05mmol)、中间体I-A-4(4.24g,10.45mmol)、四(三苯基膦)钯(0.21g,0.19mmol)、碳酸钾(2.62g,19.00mmol)、四丁基氯化铵(0.12g,0.44mmol)、甲苯(32mL)、乙醇(16mL)和去离子水(8mL)加入三口烧瓶中,氮气保护下升温至76℃,加热回流搅拌7h。反应结束后,溶液冷却至室温,反应液使用水洗后加入硫酸镁干燥,过滤后将滤液通过短硅胶柱,减压除去溶剂;粗品用甲苯进行重结晶得到化合物20(5.27g,收率72.46%)。质谱:m/z=786.38(M+H)+。
本发明实施方式还提供一种电子装置,包括阴极、阳极以及位于阴极和阳极之间的功能层,功能层中包含上述实施例的化合物。
在本实施方式中,该电子装置为有机电致发光器件。其中,阳极材料优选地是有助于空穴注入至功能层中的具有大逸出功(功函数,work function)的材料。具体可以包括:金属如镍、铂、钒、铬、铜、锌和金或它们的合金;金属氧化物如氧化锌、氧化铟、氧化铟锡(ITO)和氧化铟锌(IZO);组合的金属和氧化物,如ZnO:Al或SnO2:Sb;或导电聚合物,如聚(3-甲基噻吩)、聚[3,4-(亚乙基-1,2-二氧基)噻吩](PEDT)、聚吡咯和聚苯胺,但不限于此。优选包含氧化铟锡(铟锡氧化物,indium tin oxide)(ITO)作为阳极的透明电极。
阴极材料是有助于电子注入至功能层中的具有小逸出功的材料。具体可以包括:金属如镁、钙、钠、钾、钛、铟、钇、锂、钆、铝、银、锡和铅或它们的合金;或多层材料,如LiF/Al、Liq/Al、LiO2/Al、LiF/Ca、LiF/Al和BaF2/Ca,但不限于此。优选包含铝的金属电极作为阴极。
如图1所示,有机电致发光器件的功能层20为多层结构,这些多层结构可以包括:空穴注入层201、空穴传输层202、发光层204、电子传输层206、电子注入层207等。当然,还可以包括电子阻挡层203、空穴阻挡层205、有机覆盖层40等结构。本实施例的化合物可以位于电子传输层206。
上述有机电致发光器件可以应用于多种电子装置,例如,该电子装置可以为显示装置、照明装置、光通讯装置或者其他类型的电子装置,例如可以包括但不限于电脑屏幕、手机屏幕、电视机、电子纸、应急照明灯、光模块等。
以下给出本实施方式有机电致发光器件的制备实施例,以对其结构进行具体说明。
蓝色有机电致发光器件的制作
实施例1
通过以下过程制备阳极10:将厚度为的ITO基板切割成40mm×40mm×0.7mm的尺寸,采用光刻工序,将其制备成具有阴极搭接区域、阳极以及绝缘层图案的顶发射实验基板,利用紫外臭氧以及O2:N2等离子进行表面处理,以增加阳极(实验基板)的功函数和清洗实验基板。
其中,HAT-CN、NPB、TCTA、α,β-ADN、BD-1、CP-1的结构式如下所示:
以上实施例仅给出了蓝色发光器件的制备方法,本领域技术人员可以理解的是,本发明的有机化合物还可以用在其他颜色发光器件的制备中,此处不再赘述。同理,以上实施例仅给出了蓝色发光器件的一种具体制备方法,本领域技术人员可以理解的是,该发光器件中,其他层还可以采用其他同样功能的材料,电子传输层也可以以其他掺杂材料按照其他掺杂比例掺杂,而且,电子传输层也可以制备成其他厚度。这些改变并不会影响本发明化合物给器件所带来的性能。
实施例2-19
采用与实施例1相同的方法制作有机电致发光器件,区别在于,在形成电子传输层(ETL)206时,各自使用表1中所示的化合物替代化合物1。
比较例1-3
比较例1-3的有机电致发光器件制备方法与实施例1相同,区别在于,在形成电子传输层206时分别使用Alq3、TmPyPB、Bphen作为电子传输层材料替代化合物1。Alq3、TmPyPB、Bphen的结构式如下所示:
器件性能测试中,IVL数据对比的是在10mA/cm2下的测试结果,寿命是15mA/cm2电流密度下的测试结果。
表1实施例1-19和比较例1-3的器件性能
根据上述[表1]的结果,可知,作为电子传输层(ETL)的化合物1~19与使用已公知的Alq3、TmPyPB及Bphen的比较例1~3相比,本发明中使用的化合物1~19作为电子传输层(ETL)制备的上述有机电致发光器件的工作电压最少降低了0.41V,同时发光效率(Cd/A)最少提高了16.1%,寿命至少提高了13.5%。
究其原因是由于本发明实施例中使用的化合物在400(V/cm)1/2电场强度下,电子迁移率可以达到4×10-3cm2/V.s以上,所以制备得到的有机电致发光器件具有较高的电流效率;又因为该化合物具有与相邻层更匹配的LUMO能级,故而制备得到的有机电致发光器件的驱动电压与比较例相比会有一定程度的降低;最后该化合物引入的金刚烷基提升了材料分子量并降低分子对称性,提高了材料的玻璃化转变温度以及蒸镀温度,控制材料结晶性,使得材料用于量产时有更好的物理和热学稳定性,具有很好的耐久性与耐热性,从而使得器件寿命得到大幅度提升。
总而言之,在电子传输层(ETL)中使用本发明的化合物1~19,由此制备的有机电致发光器件可实现低驱动电压、高发光效率及长寿命。
在其他实施方式中,该电子装置也可以是太阳能电池等光电转化器件。太阳能电池以具有光敏性质的有机物作为半导体的材料,以光伏效应而产生电压形成电流,实现太阳能发电的效果。如图2所示,太阳能电池也由阴极、阳极和功能层组成,太阳能电池的功能层60通常包括光敏活性层602、空穴传输层601、电子传输层603等。其中,光敏活性层602用于吸收光子产生激子和载流子,空穴传输层601和电子传输层603用于提高空穴和电子的电极的收集效率。本发明的化合物可以用于太阳能电池的电子传输层603,以增强电子的传输效率,进而提升太阳能电池的光电转换效率,改善太阳能电池的寿命特性、效率特性、电化学稳定性和热稳定性并且提高开路电压。
本领域技术人员在考虑说明书及实践这里公开的发明后,将容易想到本发明的其它实施方案。本申请旨在涵盖本发明的任何变型、用途或者适应性变化,这些变型、用途或者适应性变化遵循本发明的一般性原理并包括本发明未公开的本技术领域中的公知常识或惯用技术手段。说明书和实施例仅被视为示例性的,本发明的真正范围和精神由所附的权利要求指出。
Claims (5)
3.一种电子装置,包括阴极、阳极以及位于所述阴极和阳极之间的功能层,其特征在于,所述功能层中包含权利要求1或2所述的化合物。
4.根据权利要求3所述的电子装置,其特征在于,所述电子装置为有机电致发光器件或太阳能电池。
5.根据权利要求4所述的电子装置,其特征在于,所述功能层包括电子传输层,所述化合物位于所述电子传输层。
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CN110615759B (zh) * | 2019-09-25 | 2020-08-11 | 陕西莱特光电材料股份有限公司 | 化合物、光电转化器件及电子装置 |
CN111018797B (zh) * | 2019-12-26 | 2021-01-05 | 陕西莱特光电材料股份有限公司 | 有机化合物、包含该有机化合物的电子元件及电子装置 |
CN111377853B (zh) * | 2019-12-27 | 2021-04-13 | 陕西莱特光电材料股份有限公司 | 含氮化合物、电子元件和电子装置 |
CN111825518B (zh) | 2019-12-30 | 2021-06-11 | 陕西莱特光电材料股份有限公司 | 有机化合物、有机电致发光器件和电子装置 |
CN111995533B (zh) * | 2020-04-27 | 2022-01-28 | 陕西莱特光电材料股份有限公司 | 含氮化合物、电子元件和电子装置 |
CN111848501B (zh) * | 2020-05-08 | 2021-06-01 | 陕西莱特光电材料股份有限公司 | 一种含氮化合物以及使用其的电子元件和电子装置 |
CN111740020B (zh) * | 2020-06-07 | 2023-05-26 | 上海传勤新材料有限公司 | 一种高效长寿命的蓝光器件 |
CN111961038B (zh) * | 2020-07-20 | 2021-10-08 | 陕西莱特光电材料股份有限公司 | 化合物、有机致电发光器件及电子装置 |
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