CN110204565B - 一种含硼化合物、显示面板及显示装置 - Google Patents
一种含硼化合物、显示面板及显示装置 Download PDFInfo
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- CN110204565B CN110204565B CN201910579047.0A CN201910579047A CN110204565B CN 110204565 B CN110204565 B CN 110204565B CN 201910579047 A CN201910579047 A CN 201910579047A CN 110204565 B CN110204565 B CN 110204565B
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 101
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 28
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 45
- -1 nitro, amino, methyl Chemical group 0.000 claims description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052794 bromium Inorganic materials 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- OJWYYSVOSNWCCE-UHFFFAOYSA-N 2-methoxyethyl hypofluorite Chemical compound COCCOF OJWYYSVOSNWCCE-UHFFFAOYSA-N 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 abstract description 6
- 125000001072 heteroaryl group Chemical group 0.000 abstract description 6
- 238000004220 aggregation Methods 0.000 abstract description 4
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- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 17
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- 239000010405 anode material Substances 0.000 description 2
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- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 2
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- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
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- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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Abstract
Description
技术领域
本申请涉及有机电致发光材料技术领域,尤其涉及一种含硼化合物、显示面板及显示装置。
背景技术
根据发光机制,可用于OLED发光层材料主要有以下4种:
1、荧光材料
材料的单线激发态S1,通过辐射跃迁回到基态S0。
2、磷光材料
三线激发态T1直接辐射衰减到基态S0(Nature,1998,395,151)。
3、三线态-三线态湮灭(TTA)材料
两个三线态激子相互作用产生一个单线态激子,通过辐射跃迁回到基态S0(Adv.Funct.Mater.,2013,23,739)。
4、热活化延迟荧光(Thermally Active Delayed Fluorescence,TADF)材料
当S1态与T1态之间的能隙值较小且T1态激子寿命较长时,在一定温度条件下,T1态激子可以逆向系间窜越(RISC)实现T1→S1的过程,再由S1态辐射衰减至基态S0(Nature,2012,492,234-238)。
以上几种材料的理论最大内量子产率、结构设计多样化及材料成本如表1所示:
表1
荧光材料:根据自旋统计,激子中单线态和三线态激子的比例是1:3,所以荧光材料最大内量子产率不超过25%。依据朗伯发光模式,光取出效率为20%左右,故基于荧光材料的OLED器件的EQE不超过5%。
磷光材料:磷光材料由于重原子效应,可以通过自旋偶合作用,加强分子内部系间窜越,可以直接利用75%的三线态激子,从而实现在室温下S1和T1共同参与的发射,理论最大内量子产率可达100%。依据朗伯发光模式,光取出效率为20%左右,故基于磷光材料的OLED器件的EQE可以达到20%。但是磷光材料基本为Ir、Pt、Os、Re、Ru等重金属配合物,生产成本较高,不利于大规模生产。在高电流密度下,磷光材料存在严重的效率滚降现象,同事磷光器件的稳定性并不好。
三线态-三线态湮灭(TTA)材料:两个相邻的三线态激子,复合生成一个更高能级的单线激发态分子和一个基态分子,但是两个三线态激子产生一个单线态激子,所以理论最大内量子产率只能达到62.5%。为了防止产生较大的效率滚降现象,在这个过程中三线态激子的浓度需要调控。
热激活延迟荧光(TADF)材料:当单线激发态和三线激发态的能级差较小时,分子内部发生反向系间窜越RISC,T1态激子通过吸收环境热上转换到S1态,可同时利用75%的三线态激子和25%的单线态激子,理论最大内量子产率可达100%。主要为有机化合物,不需要稀有金属元素,生产成本低。可通过多种方法进行化学修饰。但目前已发现的TADF材料较少,新型的可用于OLED器件的TADF材料亟待开发。
发明内容
有鉴于此,本发明的目的是提供一种含硼化合物结构通式如式I所示:
其中,R为电子给体,选自取代或未取代的芳基、取代或未取代的杂芳基。
本发明提供的含硼化合物是一种新型硼杂环有机小分子发光材料,通过接入具有大位阻的基团,避免了化合物的聚集,避免共轭平面的直接堆积形成π聚集或激基缔合物,从而提高了发光效率。
本发明提供的含硼化合物具有TADF特性,可以利用传统荧光分子跃迁禁阻得三线态激子来发光,从而提高器件效率,本发明提供的含硼化合物具有大的刚性扭曲,降低了HOMO和LUMO之间的重叠,使得三重态和单重态之间的能级差可以降低到0.25eV以下,满足三线态能量向单线态逆向窜越从而提高发光效率。
本发明提供的含硼化合物作为新型硼杂环类TADF发光材料,其本身具有Bipolar特性,作为发光层必将大大提高两种载流子的传输能力和改善载流子平衡,提高荧光量子效率和降低器件电压。
附图说明
图1是本发明实施例提供的一种利用gaussian软件计算手段模拟化合物M1的HOMO能级示意图。
图2是本发明实施例提供的一种利用gaussian软件计算手段模拟化合物M1的LUMO能级示意图。
图3是本发明实施例提供的有机光电装置的结构示意图。
具体实施方式
为了更好的理解本申请的技术方案,下面对本申请实施例进行详细描述。
应当明确,所描述的实施例仅仅是本申请一部分实施例,而不是全部的实施例。基于本申请中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其它实施例,都属于本申请保护的范围。
在本申请实施例中使用的术语是仅仅出于描述特定实施例的目的,而非旨在限制本申请。在本申请实施例和所附权利要求书中所使用的单数形式的“一种”、“所述”和“该”也旨在包括多数形式,除非上下文清楚地表示其他含义。
应当理解,本文中使用的术语“和/或”仅仅是一种描述关联对象的关联关系,表示可以存在三种关系,例如,A和/或B,可以表示:单独存在A,同时存在A和B,单独存在B这三种情况。另外,本文中字符“/”,一般表示前后关联对象是一种“或”的关系。
本说明书的描述中,需要理解的是,本申请权利要求及实施例所描述的“基本上”、“近似”、“大约”、“约”、“大致”、“大体上”等词语,是指在合理的工艺操作范围内或者公差范围内,可以大体上认同的,而不是一个精确值。
本发明的一方面是提供一种含硼化合物,结构通式如式I所示:
其中,R为电子给体,选自取代或未取代的芳基、取代或未取代的杂芳基。
根据本发明所述含硼化合物的一个实施方式,所述R为取代或未取代的芳基、取代或未取代的含有氮、硫、氧中的至少一种的杂芳基。
根据本发明所述含硼化合物的一个实施方式,所述R为取代或未取代的苯基、取代或未取代的联苯基、取代或未取代的三联苯基、取代或未取代的萘基、取代或未取代的蒽基、取代或未取代的菲基、取代或未取代的苊烯基、取代或未取代的芘基、取代或未取代的芴基、取代或未取代的螺双芴基、取代或未取代的苯并菲基、取代或未取代的苯并蒽基、取代或未取代的荧蒽基、取代或未取代的苉基、取代或未取代的呋喃基、取代或未取代的苯并呋喃基、取代或未取代的二苯并呋喃基、取代或未取代的噻吩基、取代或未取代的苯并噻吩基、取代或未取代的二苯并噻吩基、取代或未取代的吩噁嗪基、取代或未取代的吩嗪基、取代或未取代的吩噻嗪基、取代或未取代的噻蒽基、咔唑类衍生物基团、吖啶类衍生物基团、三芳胺类基团中的一种。
根据本发明所述含硼化合物的一个实施方式,所述R为以下基团的一种:
其中,#表示连接位置;
R1选自氢原子、卤素、羟基、硝基、C1-C20烷基、C1-C20烷氧基、取代或未取代氨基、C4-C8环烷基、C4-C40芳基、C4-C40杂芳基。
根据本发明所述含硼化合物的一个实施方式,所述含硼化合物为以下结构中的一种:
R1选自氢原子、卤素、羟基、硝基、C1-C20烷基、C1-C20烷氧基、取代或未取代氨基、C4-C8环烷基、C4-C40芳基、C4-C40杂芳基。
根据本发明所述含硼化合物的一个实施方式,所述R1为以下基团的一种:氢、氟、氯、溴、羟基、硝基、氨基、甲基、乙基、甲氧基、乙氧基、
其中,#表示连接位置。
根据本发明所述含硼化合物的一个实施方式,所述化合物选自以下结构的一种:
本发明还提供一种显示面板,包括有机发光器件,其中所述有机发光器件包括相对设置的阳极、阴极,以及位于阳极和阴极之间的发光层,其中所述发光层包括主体材料和客体材料,所述发光层的主体材料或客体材料为所述的含硼化合物中的至少一种。
本发明还提供一种显示面板,包括有机发光器件,其中所述有机发光器件包括相对设置的阳极、阴极,以及位于所述阳极背离所述阴极一侧的基底层,以及位于所述阳极与所述阴极之间的有机膜层,所述有机膜层包括电子传输层、空穴传输层和发光层,所述电子传输层、空穴传输层、发光层中的至少一者的材料为所述的含硼化合物。
根据本发明所述显示面板的一个实施方式,本发明还提供一种显示装置,包括所述的显示面板。
在本发明所述的显示面板中,有机发光器件的阳极材料可以选自金属例如,铜、金、银、铁、铬、镍、锰、钯、铂等及它们的合金;金属氧化物例如,氧化铟、氧化锌、氧化铟锡(ITO)、氧化铟锌(IZO)等;导电性聚合物例如,聚苯胺、聚吡咯、聚(3-甲基噻吩)等。除了以上有助于空穴注入材料及其组合之外,阳极材料还可包括其他已知的适合做阳极的材料。
在本发明所述的显示面板中,有机发光器件的阴极材料可以选自金属例如,铝、镁、银、铟、锡、钛等及它们的合金;多层金属材料例如,LiF/Al、LiO2/Al、BaF2/Al等。除以上有助于电子注入的材料及其组合之外,阴极材料还可包括其他已知的适合做阴极的材料。
在本发明的一个实施例中,所述的显示面板中的有机发光器件可以这样制作:在透明或不透明的光滑的基板上形成阳极,在阳极上形成有机薄层,在有机薄层上形成阴极。有机薄层的形成可以采用如蒸镀、溅射、旋涂、浸渍、离子镀等已知的成膜方法。最后在阴极上制备一层有机光学覆盖层CPL(盖帽层)。光学覆盖层CPL的材料为本发明所述的化合物。光学覆盖层CPL可以通过蒸镀或溶液法加工制备。溶液加工法包括喷墨打印法、旋转涂布、刮刀涂布、丝网印刷、卷对卷印刷等方法。
下面提供几个示例性的化合物的合成示例。
实施例1
在250ml三口瓶中,依次加入3.56g(20mmol)菲即化合物1、化合物2即苯1.56g(20mmol)、乙醛酸1.78g(24mmol),混合并冷却至0℃,然后缓慢加入负载三氟甲磺酸的聚乙烯吡咯烷酮PVP-TfOH(3g),将反应混合物升至室温并搅拌,通过TLC(己烷/乙酸乙酯=3:1)监测反应进程。反应完成后,将混合物倒入冰水中,用饱和碳酸氢钠中和,并用乙醚(3×15mL)萃取。合并有机萃取液,用水洗涤并用无水Na2SO4干燥,通过真空蒸发除去溶剂,粗产物通过硅胶柱色谱纯化,用己烷/乙酸乙酯作为洗脱剂。获得产品中加入75ml亚硫酰氯冷混合,将反应混合物在回流条件下加热3小时并冷却,蒸发过量的亚硫酰氯,得到化合物3。
1H NMR(400MHz,Chloroform)δ8.98(s,1H),8.84(s,1H),8.01–7.84(m,3H),7.76–7.55(m,4H),7.37(s,3H),7.21(s,2H),5.46(s,1H).
13C NMR(100MHz,Chloroform)δ176.82(s),140.03(s),139.17(s),136.62(s),134.31(s),131.03(s),130.42(s),129.51(s),129.12(s),128.90(s),128.57(s),128.29(d,J=11.1Hz),127.69(s),126.81(dd,J=23.2,10.4Hz),124.35(s),64.44(s).
在250ml三口瓶中依次加入25g无水三氯化铝和150mL无水DCM,置于冰盐水中冷却半小时,再加入40ml化合物3的DCM溶液(0.5mol/l),50min内加完,冰盐水条件下搅拌24h。将10%的稀盐酸25mL加到三口瓶中,分液,有机层用5%的碳酸钠水溶液洗至中性,过滤旋蒸得到中间体;另取一个250ml三口瓶,依次加入上述中间体(20mg)、硼氢化钠(2.23mg)和甲醇水溶液(甲醇:水=1:1,50ml),在冰盐水中搅拌,反应完全后加入稀盐酸淬灭,用DCM萃取有机相,干燥过滤,旋蒸得到化合物4。
1H NMR(400MHz,Chloroform)δ8.86(d,J=16.0Hz,2H),7.88(d,J=14.9Hz,2H),7.80–7.45(m,4H),7.38–7.02(m,5H),6.24(s,1H),3.90(s,1H),1.80(s,1H).
13C NMR(100MHz,Chloroform)δ144.74(s),139.60(d,J=17.9Hz),133.39(s),132.81(s),132.23(s),129.92(d,J=1.6Hz),129.24(s),128.68(s),127.32–127.03(m),124.12(d,J=5.6Hz),123.07(s),120.49(s),120.03(s),81.44(s),58.59(s).
在250ml三口瓶中,依次加入化合物4(2.06g)、催化剂ZrCl4(0.16g)和溶剂CH3CN(100ml),将反应混合物升温至回流并搅拌3h,通过TLC监测反应进程,反应完成后,有机相用乙酸乙酯EA萃取,合并有机萃取液,用水洗涤并用无水Na2SO4干燥,通过真空蒸发除去溶剂,粗产物通过硅胶柱色谱纯化,得到化合物5。
1H NMR(400MHz,Chloroform)δ8.98(s,1H),8.84(s,1H),8.19(s,1H),8.10(s,1H),7.88(d,J=12.0Hz,2H),7.83–7.74(m,3H),7.65(d,J=20.0Hz,2H),7.43(d,J=20.0Hz,3H).
13C NMR(100MHz,Chloroform)δ138.49(s),137.44(s),135.76(s),135.43(s),133.39(s),132.59(s),129.85(d,J=12.6Hz),128.68(s),127.64(s),127.29–127.03(m),126.77(d,J=11.5Hz),125.74(s),124.09(s),122.66(s),118.91(s),117.65(s).
在250ml三口烧瓶中,依次加入5.56g化合物5(20mmol)、偶氮二异丁腈AIBN 0.2g(5%)和100ml CCl4,开动搅拌,氮气置换,加热至80℃回流,分批次加入NBS(7.05g),反应5h,HPLC监测反应终点,降至室温,干燥过柱得到化合物6。
1H NMR(400MHz,Chloroform)δ8.83(d,J=12.0Hz,2H),8.53(s,1H),8.09(s,1H),7.87(d,J=24.0Hz,2H),7.75–7.53(m,3H),7.44(s,1H),7.29(s,1H),7.03(s,1H).
13C NMR(100MHz,Chloroform)δ138.99(s),133.79(s),133.42(d,J=6.8Hz),132.00(s),130.83(d,J=1.8Hz),130.15–129.80(m),128.65(d,J=5.1Hz),127.15(d,J=2.0Hz),126.63(s),126.31(s),125.41(s),124.09(s),121.41(d,J=9.6Hz),117.78(s),115.11(s).
在250ml三口瓶中,加入8.68g化合物6(20mmol)、THF(80mL)溶解,氮气置换三次,降温至-78℃,待温度达到后控制温度在-65℃以下缓慢滴加n-BuLi 20mL(50mmol),滴加完全后搅拌30min,再缓慢滴加三甲基氯硅烷TMS-Cl 4.35g(40mmol),升温至0℃反应4h,结束后加入冰水淬灭,加入DCM(80mL*2)萃取,收集有机相旋蒸,得到淡黄色油状物,使用Tol(甲苯)/EtOH析晶得到淡黄色固体。
在200mL闷罐中依次加入上述淡黄色固体6.45g(15mmol)、无水甲苯(70mL)和三溴化硼0.76mL(8mmol),120℃搅拌12h,反应结束后用H2O(100mL)淬灭,用DCM(100mL*3)萃取反应液,收集有机相,干燥过滤,旋蒸去除溶剂,使用DCM/EtOH析晶得到化合物7。
1H NMR(400MHz,Chloroform)δ8.92(s,1H),8.84(d,J=3.6Hz,2H),7.94(s,1H),7.90(s,1H),7.77(s,1H),7.65(d,J=20.0Hz,3H),7.46(d,J=32.0Hz,2H),7.11(s,1H).
13C NMR(100MHz,Chloroform)δ183.85(s),143.36(s),137.21(s),134.24(s),133.50–132.95(m),132.63(s),130.64(s),130.32(s),130.02–129.60(m),128.68(s),127.41–127.03(m),125.35(s),124.39(s),124.09(s),118.61(s),108.34(s).
在250ml三口瓶中加入化合物7(1.95g)和乙醚(30mL),氮气置换三次,降温至-78℃,待温度达到后控制温度在-65℃以下缓慢滴加n-BuLi(0.34g),滴加完全后搅拌30min,再用30mL甲苯溶解化合物8-1(1.71g),缓慢滴加至反应液中,滴加完成后自然升至室温反应6h,反应结束后加入冰水(500mL)淬灭反应,再加入DCM(40mL*2)萃取,最后用饱和食盐水萃取一次,收集有机相旋蒸,得到淡黄色固体。加入15mL甲苯热溶析晶,得到化合物M1。
1H NMR(400MHz,Chloroform)δ8.91(d,J=6.8Hz,2H),8.84(s,1H),7.92(d,J=16.0Hz,4H),7.75(d,J=12.0Hz,2H),7.65(d,J=20.0Hz,2H),7.57(s,2H),7.50(s,1H),7.45(dt,J=9.4,4.8Hz,1H),7.42(s,1H),7.38(dd,J=3.4,1.6Hz,1H),7.34(s,1H),7.31(d,J=3.7Hz,1H),7.24(d,J=1.1Hz,4H),7.11(s,1H),4.81(s,1H).
13C NMR(100MHz,Chloroform)δ152.72(s),151.11(s),144.49(s),143.93(s),139.39(s),139.08(s),137.97(s),136.48(s),133.31(d,J=17.0Hz),132.63(s),131.57(s),130.56(d,J=18.7Hz),130.34–129.80(m),128.68(s),127.68(s),127.07(dd,J=16.2,5.3Hz),126.29(s),124.59(s),124.39(s),124.09(s),122.88(s),122.30(s),121.54(s),117.62(s),108.34(s),62.01(s).
图1是本发明实施例提供的一种利用gaussian软件计算手段模拟化合物M1的HOMO能级示意图。图2是本发明实施例提供的一种利用gaussian软件计算手段模拟化合物M1的LUMO能级示意图。由图1和2中可以明显看出,分子的HOMO和LUMO分别排布在不同的Unit上,实现了比较完全的分离separation,这有助于减小隙间能差△EST,从而提高逆隙间窜越能力。
实施例2
在250ml三口瓶中加入化合物7(1.95g)和乙醚(30mL),氮气置换三次,降温至-78℃,待温度达到后控制温度在-65℃以下缓慢滴加n-BuLi(0.34g),滴加完全后搅拌30min,再用30mL甲苯溶解化合物8-2(1.79g),缓慢滴加至反应液中,滴加完成后自然升至室温反应6h,反应结束后加入冰水(500mL)淬灭反应,再加入DCM(40mL*2)萃取,最后用饱和食盐水萃取一次,收集有机相旋蒸,得到淡黄色固体。加入15mL甲苯热溶析晶,得到化合物M2。
1H NMR(400MHz,Chloroform)δ8.92(d,J=2.0Hz,15H),8.84(s,7H),7.87(t,J=34.0Hz,21H),7.75(s,2H),7.74–7.61(m,29H),7.50(s,5H),7.42(s,4H),7.14(t,J=14.1Hz,39H),7.00(d,J=12.0Hz,28H),6.93(s,15H).
13C NMR(100MHz,Common NMR Solvents)δ152.75(d,J=6.5Hz),146.79(s),144.49(s),139.08(s),137.97(s),134.24(s),133.31(d,J=17.0Hz),132.63(s),132.27(s),131.57(s),130.46(s),130.34–129.80(m),128.68(s),127.68(s),127.11(dd,J=8.0,4.9Hz),126.29(s),124.39(s),124.09(s),123.59(d,J=16.4Hz),122.30(s),119.00(s),117.62(s),116.41(s),108.34(s).
实施例3
在250ml三口瓶中加入化合物7(1.95g)和乙醚(30mL),氮气置换三次,降温至-78℃,待温度达到后控制温度在-65℃以下缓慢滴加n-BuLi(0.34g),滴加完全后搅拌30min,再用30mL甲苯溶解化合物8-3(1.72g),缓慢滴加至反应液中,滴加完成后自然升至室温反应6h,反应结束后加入冰水(500mL)淬灭反应,再加入DCM(40mL*2)萃取,最后用饱和食盐水萃取一次,收集有机相旋蒸,得到淡黄色固体。加入15mL甲苯热溶析晶,得到化合物M3。
1H NMR(400MHz,Chloroform)δ9.15–8.82(m,35H),7.87(t,J=34.0Hz,43H),7.73(d,J=3.5Hz,7H),7.74–7.61(m,45H),7.50(s,8H),7.42(s,6H),7.24(s,54H),7.09(dd,J=41.9,30.1Hz,102H),7.00(s,29H),7.00(s,18H).
13C NMR(100MHz,Common NMR Solvents)δ152.72(s),151.71(s),146.93(s),144.49(s),139.08(s),137.97(s),134.01(s),133.31(d,J=17.0Hz),132.63(s),131.57(s),130.46(s),130.34–129.80(m),129.27(s),128.68(s),127.68(s),127.11(dd,J=7.8,5.1Hz),126.29(s),124.67(s),124.39(s),124.09(s),122.99(s),122.30(s),117.62(s),108.34(s).
实施例4
在250ml三口瓶中加入化合物7(1.95g)和乙醚(30mL),氮气置换三次,降温至-78℃,待温度达到后控制温度在-65℃以下缓慢滴加n-BuLi(0.34g),滴加完全后搅拌30min,再用30mL甲苯溶解化合物8-4(1.88g),缓慢滴加至反应液中,滴加完成后自然升至室温反应6h,反应结束后加入冰水(500mL)淬灭反应,再加入DCM(40mL*2)萃取,最后用饱和食盐水萃取一次,收集有机相旋蒸,得到淡黄色固体。加入15mL甲苯热溶析晶,得到化合物M4。
1H NMR(400MHz,Chloroform)δ8.92(d,J=2.0Hz,24H),8.84(s,11H),7.87(t,J=34.0Hz,44H),7.73(d,J=3.5Hz,7H),7.74–7.61(m,46H),7.50(s,8H),7.42(s,6H),7.26–7.11(m,104H),7.11(s,5H),6.97(s,17H).
13C NMR(100MHz,Common NMR Solvents)δ152.75(d,J=6.5Hz),144.49(s),141.45(s),139.08(s),137.97(s),134.24(s),133.31(d,J=17.0Hz),132.63(s),131.57(s),130.46(s),130.34–129.80(m),128.68(s),127.68(s),127.36-126.93(m),126.62(s),126.29(s),124.50–124.20(m),124.09(s),122.70(s),122.30(s),117.62(s),115.74(s),108.34(s).
实施例5
在250ml三口瓶中加入化合物7(1.95g)和乙醚(30mL),氮气置换三次,降温至-78℃,待温度达到后控制温度在-65℃以下缓慢滴加n-BuLi(0.34g),滴加完全后搅拌30min,再用30mL甲苯溶解化合物8-5(1.88g),缓慢滴加至反应液中,滴加完成后自然升至室温反应6h,反应结束后加入冰水(500mL)淬灭反应,再加入DCM(40mL*2)萃取,最后用饱和食盐水萃取一次,收集有机相旋蒸,得到淡黄色固体。加入15mL甲苯热溶析晶,得到化合物M5。
1H NMR(400MHz,Chloroform)δ8.96–8.82(m,91H),8.82(s,7H),7.87(t,J=34.0Hz,125H),7.75(s,9H),7.66(dd,J=16.0,8.0Hz,131H),7.50(s,22H),7.42(s,17H),7.11(s,33H),6.47(d,J=17.9Hz,63H),3.76(s,67H).
13C NMR(100MHz,Common NMR Solvents)δ152.72(s),144.49(s),141.79(s),139.08(s),137.97(s),136.16(s),133.85(s),133.31(d,J=17.0Hz),132.63(s),132.36(s),131.82(s),131.57(s),130.46(s),129.98(d,J=13.4Hz),129.36(s),128.68(s),128.24(s),127.68(s),127.14(dd,J=11.3,9.3Hz),126.29(s),125.58(s),124.44(d,J=10.7Hz),124.09(s),123.07(d,J=3.4Hz),122.30(s),117.62(s),108.34(s),35.61(s).
实施例6
在250ml三口瓶中加入化合物7(1.95g)和乙醚(30mL),氮气置换三次,降温至-78℃,待温度达到后控制温度在-65℃以下缓慢滴加n-BuLi(0.34g),滴加完全后搅拌30min,再用30mL甲苯溶解化合物8-6(1.93g),缓慢滴加至反应液中,滴加完成后自然升至室温反应6h,反应结束后加入冰水(500mL)淬灭反应,再加入DCM(40mL*2)萃取,最后用饱和食盐水萃取一次,收集有机相旋蒸,得到淡黄色固体。加入15mL甲苯热溶析晶,得到化合物M6。
1H NMR(400MHz,Chloroform)δ8.96–8.75(m,3H),7.92(d,J=16.0Hz,2H),7.77(s,1H),7.67(t,J=16.0Hz,4H),7.50(s,1H),7.42(s,1H),7.18(dd,J=8.0,4.0Hz,8H),7.11(s,1H),6.94(s,2H),1.69(s,6H).
13C NMR(100MHz,Common NMR Solvents)δ152.75(d,J=6.5Hz),144.49(s),142.44(s),139.08(s),137.97(s),134.24(s),133.33(t,J=8.5Hz),132.63(s),131.57(s),130.46(s),130.34–129.80(m),128.95(s),128.68(s),127.68(s),127.11(dd,J=8.0,4.9Hz),126.75(s),126.29(s),124.39(s),124.09(s),122.86(s),122.30(s),120.00(s),117.62(s),108.34(s),35.71(s),29.68(s).
实施例7
在250ml三口瓶中加入化合物7(1.95g)和乙醚(30mL),氮气置换三次,降温至-78℃,待温度达到后控制温度在-65℃以下缓慢滴加n-BuLi(0.34g),滴加完全后搅拌30min,再用30mL甲苯溶解化合物8-7(1.36g),缓慢滴加至反应液中,滴加完成后自然升至室温反应6h,反应结束后加入冰水(500mL)淬灭反应,再加入DCM(40mL*2)萃取,最后用饱和食盐水萃取一次,收集有机相旋蒸,得到淡黄色固体。加入15mL甲苯热溶析晶,得到化合物M7。
1H NMR(400MHz,Chloroform)δ8.89(t,J=16.2Hz,6H),8.51(s,2H),8.43(s,2H),8.09(s,2H),8.01(s,3H),7.87(t,J=34.0Hz,6H),7.76–7.34(m,13H),7.52(d,J=16.0Hz,6H),7.61–7.34(m,8H),7.42(s,1H),7.11(s,2H).
13C NMR(100MHz,Common NMR Solvents)δ152.72(s),144.49(s),139.08(s),137.97(s),136.32(s),134.21(s),133.31(d,J=17.0Hz),132.63(s),132.08(s),131.57(s),131.16(s),130.46(s),130.28–129.80(m),128.68(s),128.45(s),127.68(s),127.09(dd,J=12.3,1.3Hz),126.61(s),126.29(s),124.34(d,J=9.8Hz),124.09(s),123.64(s),123.39(s),122.30(s),117.62(s),108.34(s).
实施例8
在250ml三口瓶中加入化合物7(1.95g)和乙醚(30mL),氮气置换三次,降温至-78℃,待温度达到后控制温度在-65℃以下缓慢滴加n-BuLi(0.34g),滴加完全后搅拌30min,再用30mL甲苯溶解化合物8-8(1.08g),缓慢滴加至反应液中,滴加完成后自然升至室温反应6h,反应结束后加入冰水(500mL)淬灭反应,再加入DCM(40mL*2)萃取,最后用饱和食盐水萃取一次,收集有机相旋蒸,得到淡黄色固体。加入15mL甲苯热溶析晶,得到化合物M8。
1H NMR(400MHz,Chloroform)δ8.96–8.75(m,6H),7.92(d,J=16.0Hz,4H),7.87–7.68(m,9H),7.65(d,J=20.0Hz,3H),7.57(s,2H),7.51(d,J=4.0Hz,4H),7.42(s,2H),7.11(s,2H).
13C NMR(100MHz,Common NMR Solvents)δ152.72(s),144.49(s),139.08(s),137.97(s),136.79(s),134.34(s),133.31(d,J=17.0Hz),132.60(d,J=6.7Hz),131.57(s),130.57–129.80(m),128.75(d,J=14.6Hz),128.03(s),127.68(s),127.27–126.93(m),126.58–126.18(m),125.72(s),124.39(s),124.09(s),122.30(s),117.62(s),108.34(s).
实施例9
在250ml三口瓶中加入化合物7(1.95g)和乙醚(30mL),氮气置换三次,降温至-78℃,待温度达到后控制温度在-65℃以下缓慢滴加n-BuLi(0.34g),滴加完全后搅拌30min,再用30mL甲苯溶解化合物8-9(1.23g),缓慢滴加至反应液中,滴加完成后自然升至室温反应6h,反应结束后加入冰水(500mL)淬灭反应,再加入DCM(40mL*2)萃取,最后用饱和食盐水萃取一次,收集有机相旋蒸,得到淡黄色固体。加入15mL甲苯热溶析晶,得到化合物M9。
1H NMR(400MHz,Chloroform)δ9.15–8.82(m,3H),7.92(d,J=16.0Hz,4H),7.76(d,J=8.0Hz,5H),7.65(d,J=20.0Hz,2H),7.49(d,J=4.0Hz,3H),7.41(d,J=4.0Hz,1H),7.11(s,1H).
13C NMR(100MHz,Common NMR Solvents)δ152.72(s),144.49(s),143.40(s),140.35(s),139.08(s),137.97(s),136.45(s),133.31(d,J=17.0Hz),132.63(s),131.57(s),130.46(s),130.34–129.80(m),128.90(d,J=1.6Hz),128.68(s),127.88(s),127.68(s),127.40(s),127.27–126.93(m),126.29(s),124.39(s),124.09(s),122.30(s),117.62(s),108.34(s).
实施例10
在250ml三口瓶中加入化合物7(1.95g)和乙醚(30mL),氮气置换三次,降温至-78℃,待温度达到后控制温度在-65℃以下缓慢滴加n-BuLi(0.34g),滴加完全后搅拌30min,再用30mL甲苯溶解化合物8-10(1.30g),缓慢滴加至反应液中,滴加完成后自然升至室温反应6h,反应结束后加入冰水(500mL)淬灭反应,再加入DCM(40mL*2)萃取,最后用饱和食盐水萃取一次,收集有机相旋蒸,得到淡黄色固体。加入15mL甲苯热溶析晶,得到化合物M10。
1H NMR(400MHz,Chloroform)δ8.96–8.82(m,77H),8.82(s,6H),8.55(s,29H),8.19(s,24H),7.92(d,J=16.0Hz,70H),7.77(s,15H),7.65(d,J=20.0Hz,50H),7.51(d,J=8.0Hz,49H),7.41(d,J=8.0Hz,46H),7.26–7.08(m,138H).
13C NMR(100MHz,Common NMR Solvents)δ187.20(s),142.78(s),138.15(s),135.70(s),134.72(s),133.34(t,J=8.9Hz),132.63(s),129.91(s),129.57(s),128.94(s),128.68(s),128.32–127.87(m),127.27–126.98(m),126.21(s),124.39(s),124.09(s),122.47(s),120.82(s),116.47(s),108.35(d,J=2.3Hz),108.03(s).
实施例11
在250ml三口瓶中加入化合物7(1.95g)和乙醚(30mL),氮气置换三次,降温至-78℃,待温度达到后控制温度在-65℃以下缓慢滴加n-BuLi(0.34g),滴加完全后搅拌30min,再用30mL甲苯溶解化合物8-13(1.78g),缓慢滴加至反应液中,滴加完成后自然升至室温反应6h,反应结束后加入冰水(500mL)淬灭反应,再加入DCM(40mL*2)萃取,最后用饱和食盐水萃取一次,收集有机相旋蒸,得到淡黄色固体。加入15mL甲苯热溶析晶,得到化合物M13。
1H NMR(400MHz,Chloroform)δ8.93(d,J=6.2Hz,113H),8.84(s,51H),8.64(s,56H),8.55(s,51H),8.15(s,4H),8.15–7.76(m,261H),7.76–7.47(m,306H),7.52(t,J=8.0Hz,172H),7.52(t,J=8.0Hz,156H),7.40(d,J=12.0Hz,79H),7.31(s,30H),7.18–7.08(m,157H).
13C NMR(100MHz,Common NMR Solvents)δ187.20(s),158.06(s),156.61(s),143.36(s),142.67(s),138.15(s),135.70(s),134.72(s),133.34(t,J=8.9Hz),132.63(s),129.91(s),129.57(s),129.29(s),128.68(s),128.32–127.87(m),127.17(dd,J=11.8,9.8Hz),126.21(s),125.74(s),124.39(s),123.99(d,J=19.1Hz),123.57(s),122.82(s),122.07(s),121.10(s),116.47(s),112.87(s),112.06(s),108.34(s),107.86(s),107.53(d,J=6.4Hz),93.99(s).
实施例12
在250ml三口瓶中加入化合物7(1.95g)和乙醚(30mL),氮气置换三次,降温至-78℃,待温度达到后控制温度在-65℃以下缓慢滴加n-BuLi(0.34g),滴加完全后搅拌30min,再用30mL甲苯溶解化合物8-25(2.19g),缓慢滴加至反应液中,滴加完成后自然升至室温反应6h,反应结束后加入冰水(500mL)淬灭反应,再加入DCM(40mL*2)萃取,最后用饱和食盐水萃取一次,收集有机相旋蒸,得到淡黄色固体。加入15mL甲苯热溶析晶,得到化合物M25。
1H NMR(400MHz,Chloroform)δ8.93(d,J=5.4Hz,2H),8.84(s,1H),8.55(s,1H),7.93(dd,J=26.0,10.0Hz,5H),8.30–7.70(m,8H),8.30–7.56(m,11H),8.30–7.45(m,14H),8.30–7.33(m,16H),8.30–6.89(m,21H).
13C NMR(100MHz,Common NMR Solvents)δ155.79(s),152.72(s),149.53(s),146.20(s),144.49(s),139.08(s),137.97(s),135.80(s),134.40(s),133.31(d,J=17.0Hz),132.63(s),131.57(s),130.46(s),130.34–129.80(m),128.68(s),127.68(s),127.39(s),127.11(dd,J=8.0,4.9Hz),126.39–126.00(m),124.55–124.24(m),124.09(s),122.85(d,J=12.9Hz),122.52(s),122.41–121.98(m),120.63(d,J=3.5Hz),118.97(s),117.62(s),114.61(s),111.98(s),108.34(s).
表2化合物的能级值
由上表2可以看出,本发明提供的含硼化合物具有TADF特性,可以利用传统荧光分子跃迁禁阻得三线态激子来发光,从而提高器件效率,本发明提供的含硼化合物具有大的刚性扭曲,降低了HOMO和LUMO之间的重叠,使得三重态和单重态之间的能级差可以降低到0.25eV以下,满足三线态能量向单线态逆向窜越从而提高发光效率。
表3
与对比例相比较,本申请的器件发光效率大幅度提高,外量子效率普遍超出三倍以上,启动电压普遍偏低。
应用实施例1
本实施例提供一种有机光电装置,其结构如图3所示,所述有机光电装置包括:基板1、阳极2(ITO)、空穴注入层3、第一空穴传输层4、第二空穴传输层5、发光层6、第一电子传输层7、第二电子传输层8、电子注入层9和阴极10(铝电极),图3中向上的箭头代表出光方向,其中ITO阳极2的厚度是10nm,空穴注入层3的厚度是5nm,第一空穴传输层4的厚度是50nm、第二空穴传输层5的厚度是10nm、发光层6的厚度是20nm、第一电子传输层7的厚度是5nm、第二电子传输层8的厚度是20nm、电子注入层9的厚度是1nm,铝电极10的厚度是15nm。
所述有机光电装置的制备过程如下:
1)将玻璃基板1切成50mm×50mm×0.7mm的大小,分别在异丙醇和去离子水中超声处理30分钟,然后暴露在臭氧下约10分钟来进行清洁;将所得的具有ITO阳极2的玻璃基板安装到真空沉积设备上;
2)在真空度为2×10-6Pa下,在ITO阳极层2上,通过真空蒸镀方式蒸镀空穴注入层材料HAT-CN,厚度为5nm,该层作为空穴注入层3;
3)在空穴注入层3上真空蒸镀第一空穴传输层4材料为N,N'-二苯基-N,N'-(1-萘基)-1,1'-联苯-4,4'-二胺(α-NPD),厚度为50nm,作为第一空穴传输层4;
4)在第一空穴传输层4上真空蒸镀第二空穴传输层5材料为1,3-二咔唑-9-基苯(mCP),厚度为10nm,作为第二空穴传输层5;
5)第二空穴传输层5上共沉积发光层6,其中,用化合物M1作为发光层的主体材料,Ir(ppy)3作为掺杂材料,掺杂比例为8%(质量比),厚度为30nm;
6)在发光层6上真空蒸镀第一电子传输层7,第一电子传输层7的材料为二苯基[4-(三苯基硅烷基)苯基]氧膦(TSPO1),厚度为5nm;
7)在第一电子传输层7上真空蒸镀第二电子传输层8,第二电子传输层8的材料为TPBi,厚度为20nm;
8)在第二电子传输层8真空蒸镀电子注入层9,电子注入层9的材料为LiF,厚度为1nm;
9)在电子注入层9上真空蒸镀铝电极,厚度为15nm,作为阴极10。
化合物M1的结构式如下:
应用实施例2
与应用实施例1的区别在于,将化合物M1替换为化合物M2。
应用实施例3
与应用实施例1的区别在于,将化合物M1替换为化合物M3。
应用实施例4
与应用实施例1的区别在于,将化合物M1替换为化合物M4。
应用实施例5
与应用实施例1的区别在于,将化合物M1替换为化合物M5。
应用实施例6
与应用实施例1的区别在于,将化合物M1替换为化合物M6。
应用实施例7
与应用实施例1的区别在于,将化合物M1替换为化合物M7。
应用实施例8
与应用实施例1的区别在于,将化合物M1替换为化合物M8。
应用实施例9
与应用实施例1的区别在于,将化合物M1替换为化合物M9。
应用实施例10
与应用实施例1的区别在于,将化合物M1替换为化合物M10。
应用实施例11
与应用实施例1的区别在于,将化合物M1替换为化合物M13。
应用实施例12
与应用实施例1的区别在于,将化合物M1替换为化合物M25。
表4器件发光性能测试结果
由表4可知,本申请的器件CE普遍偏高,LT95普遍较长。
本发明的又一方面还提供一种显示装置,其包括如上文所述的有机发光显示面板。
在本发明中,有机发光器件可以是OLED,其可以用在有机发光显示装置中,其中有机发光显示装置可以是手机显示屏、电脑显示屏、液晶电视显示屏、智能手表显示屏、智能汽车显示面板、VR或AR头盔显示屏、各种智能设备的显示屏等。
以上所述仅为本申请的较佳实施例而已,并不用以限制本申请,凡在本申请的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本申请保护的范围之内。
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