CN111205295A - 一种以咪唑并咔唑为受体的化合物及其应用 - Google Patents
一种以咪唑并咔唑为受体的化合物及其应用 Download PDFInfo
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- CN111205295A CN111205295A CN202010144028.8A CN202010144028A CN111205295A CN 111205295 A CN111205295 A CN 111205295A CN 202010144028 A CN202010144028 A CN 202010144028A CN 111205295 A CN111205295 A CN 111205295A
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- imidazocarbazole
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 50
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- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 claims abstract description 4
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- 125000004625 phenanthrolinyl group Chemical group N1=C(C=CC2=CC=C3C=CC=NC3=C12)* 0.000 claims abstract description 4
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- 125000000714 pyrimidinyl group Chemical group 0.000 claims abstract description 4
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/06—Peri-condensed systems
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
- C07F7/0816—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring comprising Si as a ring atom
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
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- H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
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Abstract
本发明公开了一种以咪唑并咔唑为受体的化合物,属于有机电致发光材料技术领域。该类化合物的结构通式如式(I)所示,其中,Ar1为给电子基团或受电子基团,当Ar1为给电子基团时,选自取代或未被取代的咔唑基、吖啶基、呋喃基、胺基、9,9‑二甲基‑9H‑芴基、吩嗪基或吩噻嗪基;当Ar1为受电子基团时,选自取代或未被取代的三嗪基、嘧啶基、吡啶基、菲洛林基、砜基、苯并咪唑基、三苯基环硼烷基、菲基、二苯甲酮基或螺二芴基。本发明通过特定位置引入特定的基团修饰构成的全新化合物具有较好的能量传输能力和电荷传输能力,具有合适的HOMO/LUMO值以及三线态能量,用于有机电致发光器件中可以实现高亮度、低电压、高效率以及使用寿命长。结构通式如式(I)所示:
Description
技术领域
本发明属于有机电致发光功能材料及器件技术领域,具体涉及一种以咪唑并咔唑为受体的化合物及其应用。
背景技术
有机电致发光二极管(OLED:Organic Light Emission Diodes)作为一种自发光的电子元件,发光机理是在直流电场的作用下借助有机半导体功能材料将电能直接转化为光能的新型光电信息技术。其发光色彩可为单独的红、绿、蓝、黄光或者是组合白光。OLED发光显示技术的最大特点在于超薄、响应速度快、超轻量、面发光及柔性显示,可用于制造单色或全色显示器,作为新型光源技术,还可以制作照明、显示产品或新型背光源技术用于制造液晶显示器。
按照发光原理,有机电致发光元件(有机EL元件)可分为荧光型与磷光型这两类。对于有机电致发光元件施加电压,注入来自阳极的空穴与来自阴极的电子,他们在发光层中再次结合形成激子。依据电子自旋统计法,单线态激子与三重态激子以25%:75%的比例生成。荧光型因为利用了单线态激子来发光,故其内部量子效率只能达到25%。磷光材料由重金属元素构成,通过隙间穿越可以同时利用单线态和三线态能量,内量子效率可以达到100%。热活性延迟荧光(Thermally Activated Delayed Fluorescence,TADF)材料是继有机荧光材料和有机磷光材料之后发展的第三代有机发光材料。该类材料一般具有较小的单线态-三线态能级差(ΔEst),三线态激子可以通过反隙间穿越转变成单线态激子发光,可以充分利用电激发下形成的单线态激子和三线态激子,器件的内量子效率可以达到100%,同时材料结构可控,性质稳定,价格便宜无需铱、铂等贵重金属,在OLEDs领域的应用前景广阔。近几年的研究结果表明:绿光和红光磷光材料可以实现产业化要求,但是仍然存在价格昂贵的问题,而蓝光磷光材料寿命无法满足应用要求因此无法实现产业化,目前OLED产品中的蓝光材料仍为传统的荧光材料。
TADF材料不仅可以作为发光层中的发光材料(emitter),也可以做为发光层中的主体材料或辅助主体材料来敏化emitter,这类器件有助于提高传统器件的效率,改善器件的色纯度,提高器件的工作寿命,是一类具有广阔应用前景的有机电致发光功能材料。TADF材料结构上一般由给电子基团-吸电子基团通过π健连接而成,但是目前能够被利用的吸电子基团种类很少,尤其是具有高品质TADF蓝光材料比较少,而且目前所报道的蓝光材料色纯度存在缺陷,器件寿命不够理想还无法达到实用化要求,因此设计发明新型吸电子基团开发新型蓝光TADF材料非常重要。
咪唑并咔唑由于其分子内特有的分子共轭结构具有较高的热稳定性与电子亲和势能。该结构通过连接典型给电子基团可以构筑给-受体型分子结构,得到具有双极性特点的TADF材料,可以用作发光层主体材料或发光染料;连接典型受电子基团时进一步优化了材料的轨道能级,增强分子的电子传输能力,可以作为电子传输材料或主体材料应用。
发明内容
本发明的目的是提供一种以咪唑并咔唑为受体的化合物,充分利用电子受体能力以及三线态能量,经过不同给电子基团或受电子基团的修饰,该类化合物可以作为发光层中的主体材料或发光材料或空穴阻挡材料或电子传输材料,该类材料应用到有机电致发光器件中,能够显著改善有机电致发光器件的器件性能。
本发明的第一个目的是提供一种以咪唑并咔唑为受体的化合物,结构通式如式(I)所示:
其中,Ar1为给电子基团或受电子基团,
当Ar1为给电子基团时,选自取代或未被取代的咔唑基、吖啶基、呋喃基、胺基、9,9-二甲基-9H-芴基、吩嗪基或吩噻嗪基;
当Ar1为受电子基团时,选自取代或未被取代的三嗪基、嘧啶基、吡啶基、菲洛林基、砜基、苯并咪唑基、三苯基环硼烷基、菲基、二苯甲酮基或螺二芴基。
优选的,所述Ar1为给电子基团时,选自以下结构式中的任意一种:
优选的,所述Ar1为受电子基团时,选自以下结构式中的任意一种:
优选的,具体为如下化合物中的任意一种:
本发明第二个目的是提供上述的以咪唑并咔唑为受体的化合物在有机电致发光器件中的应用。
本发明第三个目的是提供一种有机电致发光器件,包括发光层,所述发光层的主体材料和/或发光染料为上述的任一所述的以咪唑并咔唑为受体的化合物。
本发明第四个目的是提供一种有机电致发光器件,包括发光层和空穴阻挡层,所述空穴阻挡层所用材料为上述任一所述的以咪唑并咔唑为受体的化合物。
本发明第五个目的是提供一种有机电致发光器件,包括发光层和电子传输层,所述电子传输层所用材料为上述任一所述的以咪唑并咔唑为受体的化合物。
本发明的第六个目的是提供上述有机电致发光器件在有机电致发光显示装置中的应用。
与现有技术相比,本发明的有益效果在于:
本发明通过特定位置引入特定的给体基团或受体基团修饰咪唑并咔唑构成全新化合物;
1、通过在咪唑并咔唑特定位置上引入给电子基团,改善了咪唑并咔唑核心结构的轨道能级及三线态能量;所开发的材料为典型的给-受体结构,具有双极性特点及TADF性质,可以作为发光层主体材料或发光染料使用;
2、在在咪唑并咔唑特定位置上引入受电子基团,优化了分子轨道能级,提升了材料的电子传输性质,所开发材料可以应用于空穴阻挡材料或空穴阻挡材料或发光层主体材料;
该类系列化合物在有机电致发光(OLED)器件中作为主体材料或者空穴阻挡材料或者TADF材料或电子传输材料表现出优良的性能。
附图说明
图1为本发明实施例中提供的一种有机电致发光元件的结构示意图。
附图标记说明:
1、衬底,2、阳极层,3、空穴注入层,4、第一空穴传输层,5、第二空穴传输层,6、发光层,7、空穴阻挡层,8、电子传输层,9、电子注入层,10、阴极层。
具体实施方式
为了使本领域技术人员更好地理解本发明的技术方案能予以实施,下面结合具体实施例和附图对本发明作进一步说明,但所举实施例不作为对本发明的限定。
下述各实施例中所述实验方法和检测方法,如无特殊说明,均为常规方法;所述试剂和材料,如无特殊说明,均可在市场上购买得到。
本发明提供的以咪唑并咔唑为受体的化合物是在咪唑并咔唑分子上链接给电子基团或受电子基团修饰。
本发明提供一种以咪唑并咔唑为受体的化合物,结构通式如式(I)所示:
其中Ar1为给电子基团或受电子基团,
当Ar1为给电子基团时,选自取代或未被取代的咔唑基、吖啶基、呋喃基、胺基、9,9-二甲基-9H-芴基、吩嗪基或吩噻嗪基;
当Ar1为受电子基团时,选自取代或未被取代的三嗪基、嘧啶基、吡啶基、菲洛林基、砜基、苯并咪唑基、三苯基环硼烷基、菲基、二苯甲酮基或螺二芴基。
本发明通过在咪唑并咔唑特定位置上引入给电子基团,改善了咪唑并咔唑核心结构的轨道能级及三线态能量;所开发的材料为典型的给-受体结构,具有双极性特点及TADF性质,可以作为发光层主体材料或发光染料使用;
在咪唑并咔唑特定位置上引入受电子基团,优化了分子轨道能级,提升了材料的电子传输性质,所开发材料可以应用于空穴阻挡材料或空穴阻挡材料或发光层主体材料;
该类系列化合物在有机电致发光(OLED)器件中作为主体材料或者空穴阻挡材料或者TADF材料或电子传输材料表现出优良的性能。
下面,我们提供制备上述化合物所对应的几个中间体的具体合成方法。
(1)中间体1-2的合成:
在1L三口瓶中加入50g中间体1-1,500ml醋酸,搅拌条件下分批加入42.4g N-溴代琥珀酰亚胺,加料完毕后常温条件下搅拌反应4h,TLC监测原料完全反应后停止搅拌,将反应液倒入水中搅拌析出固体。过滤,将所得粗品溶于二氯甲烷,水洗至中性后无水硫酸钠干燥,过硅胶柱纯化得64.1g中间体1-2,收率93.5%。
中间体1-2的核磁波谱数据:1H NMR(400MHz,CDCl3)δ10.16(br,1H),8.01(d,J=7.6,1H),7.94(d,J=7.6,1H),7.72(s,1H),7.29(d,J=7.2,1H),7.26(m,2H)。
(2)中间体1-3的合成:
在1L三口瓶中加入63g中间体1-2,56.6g锌粉,630ml四氢呋喃,搅拌条件下滴加100ml冰醋酸,加料完毕后反应体系加热至66℃回流反应6h,TLC检测原料完全反应后将反应体系降至室温。加入饱和碳酸钠溶液将反应液调至中性,分液,有机相用饱和食盐水洗后无水硫酸钠干燥,过硅胶柱纯化得48.4g中间体1-3,收率85.6%。
中间体1-3的核磁波谱数据:1H NMR(400MHz,CDCl3)δ10.12(br,1H),7.72(s,1H),7.29(d,J=7.2,1H),7.25(d,J=7.2,1H),6.91(d,J=6.8,1H),6.75(t,J=6.8,1H),6.28(d,J=6.8,1H),4.00(br,2H)。
(3)中间体1的合成:
在1L三口瓶中加入48g中间体1-3,21.5g中间体1-4,500ml甲苯,0.3g对甲苯磺酸,通氮气排除体系内氧气后加热至110℃回流反应4h,TLC检测原料完全反应后将反应体系降至室温。减压蒸除反应溶剂,将所得固体加入到600ml四氢呋喃中,然后加入45.9g二氯二氰基苯醌,加热至60℃搅拌反应3h,TLC检测原料完全反应后将反应体系降至室温。过滤,有机相用饱和碳酸钠溶液洗涤两次后无水硫酸钠干燥,过硅胶柱纯化得42.3g中间体1,收率67.2%。
中间体1的核磁波谱数据:1H NMR(400MHz,CDCl3)δ7.70(m,2H),7.48(d,J=6.4,2H),7.25-7.32(m,6H),7.22(d,J=6.4,1H。
下面我们具体以部分以咪唑并咔唑为受体的化合物为例,提供这些化合物的合成方法。
实施例1:化合物3的制备
在500ml三口瓶中加入10g中间体1,9.1g化合物3-1,7.9g碳酸钾,0.93g四丁基溴化铵,200ml甲苯,60ml乙醇,40ml水,通入氮气5min排出体系内的氧气,加入1.66g四(三苯基膦)钯。将体系加热至80℃反应6h后取样TCL监测反应,当原料完全反应时停止加热,降至室温。反应液过滤后水洗至pH=7,有机相用无水硫酸钠干燥后过硅胶柱纯化除去不溶杂质,洗脱液浓缩所得粗品经甲苯重结晶后得化合物3共12.5g,收率85.3%。
化合物3的核磁波谱数据:1H NMR(400MHz,CDCl3)δ7.77(s,1H),7.70(d,J=8.4,1H),7.55(d,J=6.8,2H),7.40-7.48(m,7H),7.26-7.32(m,7H),7.22(d,J=6.4,1H),7.08(t,J=7.2,2H),7.00(t,J=7.2,2H);
实施例2:化合物13的制备
在500ml三口瓶中加入10g中间体1,14.3g化合物13-1,7.9g碳酸钾,0.93g四丁基溴化铵,200ml甲苯,60ml乙醇,40ml水,通入氮气5min排出体系内的氧气,加入1.66g四(三苯基膦)钯。将体系加热至80℃反应6h后取样TCL监测反应,当原料完全反应时停止加热,降至室温。反应液过滤后水洗至pH=7,有机相用无水硫酸钠干燥后过硅胶柱纯化除去不溶杂质,洗脱液浓缩所得粗品经甲苯重结晶后得化合物13共14.1g,收率72.6%。
化合物13的核磁波谱数据:1H NMR(400MHz,CDCl3)δ7.84(d,J=6.8,2H),7.77(s,1H),7.70(d,J=8.4,1H),7.55(d,J=7.2,2H),7.48(m,3H),7.38(t,J=6.8,2H),7.22-7.32(m,10H),6.82(m,4H),6.50-6.52(m,4H),6.34(d,J=7.2,2H);
实施例3:化合物14的制备
在500ml三口瓶中加入10g中间体1,10.4g化合物14-1,7.9g碳酸钾,0.93g四丁基溴化铵,200ml甲苯,60ml乙醇,40ml水,通入氮气5min排出体系内的氧气,加入1.66g四(三苯基膦)钯。将体系加热至80℃反应6h后取样TCL监测反应,当原料完全反应时停止加热,降至室温。反应液过滤后水洗至pH=7,有机相用无水硫酸钠干燥后过硅胶柱纯化除去不溶杂质,洗脱液浓缩所得粗品经甲苯重结晶后得化合物14共12.4g,收率78.2%。
化合物14的核磁波谱数据:1H NMR(400MHz,CDCl3)δ7.77(s,1H),7.70(d,J=8.4,1H),7.48(m,3H),7.32(m,3H),7.26(m,2H),7.23(m,3H),6.88(d,J=7.2,2H),6.83(t,J=7.2,2H),6.54(m,4H),6.38(d,J=7.2,2H),1.67(s,6H);
实施例4:化合物21的制备
在500ml三口瓶中加入10g中间体1,12.8g化合物21-1,7.9g碳酸钾,0.93g四丁基溴化铵,200ml甲苯,60ml乙醇,40ml水,通入氮气5min排出体系内的氧气,加入1.66g四(三苯基膦)钯。将体系加热至80℃反应6h后取样TCL监测反应,当原料完全反应时停止加热,降至室温。反应液过滤后水洗至pH=7,有机相用无水硫酸钠干燥后过硅胶柱纯化除去不溶杂质,洗脱液浓缩所得粗品经甲苯重结晶后得化合物21共13.7g,收率76.1%。
化合物21的核磁波谱数据:1H NMR(400MHz,CDCl3)δ8.06(d,J=7.2,1H),7.77(s,1H),7.70(d,J=8.4,1H),7.61(d,J=7.2,1H),7.55(d,J=7.2,1H),7.43-7.48(m,7H),7.40(d,J=7.2,1H),7.24-7.32(m,8H),7.22(d,J=6.4,1H),7.14(d,J=7.2,1H),7.08(t,J=7.2,1H),7.00(t,J=7.2,1H),1.67(s,6H);
实施例5:化合物46的制备
在500ml三口瓶中加入10g中间体1,11.2g化合物46-1,7.9g碳酸钾,0.93g四丁基溴化铵,200ml甲苯,60ml乙醇,40ml水,通入氮气5min排出体系内的氧气,加入1.66g四(三苯基膦)钯。将体系加热至80℃反应6h后取样TCL监测反应,当原料完全反应时停止加热,降至室温。反应液过滤后水洗至pH=7,有机相用无水硫酸钠干燥后过硅胶柱纯化除去不溶杂质,洗脱液浓缩所得粗品经甲苯重结晶后得化合物46共14.3g,收率86.2%。
化合物46的核磁波谱数据:1H NMR(400MHz,CDCl3)δ7.77(s,1H),7.70(d,J=8.4,1H),7.54(d,J=6.4,4H),7.48(d,J=6.4,6H),7.46(d,J=8.0,1H),7.32(t,J=6.4,6H),7.30(d,J=8.0,1H),7.26(m,2H),7.22(d,J=6.4,3H);
实施例6:化合物48的制备
在500ml三口瓶中加入10g中间体1,11.9g化合物48-1,7.9g碳酸钾,0.93g四丁基溴化铵,200ml甲苯,60ml乙醇,40ml水,通入氮气5min排出体系内的氧气,加入1.66g四(三苯基膦)钯。将体系加热至80℃反应6h后取样TCL监测反应,当原料完全反应时停止加热,降至室温。反应液过滤后水洗至pH=7,有机相用无水硫酸钠干燥后过硅胶柱纯化除去不溶杂质,洗脱液浓缩所得粗品经甲苯重结晶后得化合物48共13.7g,收率79.3%。
化合物48的核磁波谱数据:1H NMR(400MHz,CDCl3)δ8.05(d,J=6.4,2H),7.99(d,J=6.4,2H),7.77(s,1H),7.70(m,4H),7.57(d,J=6.4,2H),7.48(d,J=6.4,2H),7.46(d,J=8.0,1H),7.43(m,3H),7.32-7.35(m,5H),7.28(t,J=6.4,1H),7.26(m,2H),7.22(d,J=6.4,1H);
实施例7:化合物49的制备
在500ml三口瓶中加入10g中间体1,11.2g化合物46-1,7.9g碳酸钾,0.93g四丁基溴化铵,200ml甲苯,60ml乙醇,40ml水,通入氮气5min排出体系内的氧气,加入1.66g四(三苯基膦)钯。将体系加热至80℃反应6h后取样TCL监测反应,当原料完全反应时停止加热,降至室温。反应液过滤后水洗至pH=7,有机相用无水硫酸钠干燥后过硅胶柱纯化除去不溶杂质,洗脱液浓缩所得粗品经甲苯重结晶后得化合物49共13.2g,收率79.8%。
化合物49的核磁波谱数据:1H NMR(400MHz,CDCl3)δ7.77(s,1H),7.70(d,J=8.4,2H),7.44-7.48(m,9H),7.38(d,J=6.8,1H),7.32(t,J=6.4,6H),7.30(d,J=8.0,1H),7.26(m,2H),7.22(d,J=6.4,3H);
实施例8:化合物50的制备
在500ml三口瓶中加入10g中间体1,10.0g化合物50-1,7.9g碳酸钾,0.93g四丁基溴化铵,200ml甲苯,60ml乙醇,40ml水,通入氮气5min排出体系内的氧气,加入1.66g四(三苯基膦)钯。将体系加热至80℃反应6h后取样TCL监测反应,当原料完全反应时停止加热,降至室温。反应液过滤后水洗至pH=7,有机相用无水硫酸钠干燥后过硅胶柱纯化除去不溶杂质,洗脱液浓缩所得粗品经甲苯重结晶后得化合物50共11.4g,收率73.9%。
化合物50的核磁波谱数据:1H NMR(400MHz,CDCl3)δ7.77(s,1H),7.70(m,4H),7.44-7.48(m,5H),7.26-7.38(m,13H),7.22(d,J=6.4,1H);
对上述实施例提供的部分化合物及现有材料分别进行T1能级以及HOMO、LUMO能级测试,结果如表1所示:
表1本发明化合物T1能级以及HOMO、LUMO
注:最高分子占有轨道(HOMO)和最低分子未占有轨道(LUMO)三线态能量(T1)以及ΔEst为Gaussian 09软件进行模拟计算所得数据,计算方法采用B3LYP杂化泛函,基组6-31g(d,P)。
由表1可得,本发明的有机化合物具有较高的三线态能量和较合适的HOMO/LUMO,在OLED器件中有利于载流子的传输和能量的转移,这些化合物可以作为磷光主体材料、荧光主体材料或TADF主体材料使用,也可以作为TADF发光材料使用。在没有特定限制的情况下,上述有机电致发光器件可以是磷光器件也可以是荧光器件或者是包含热活性延迟荧光(TADF)材料器件。因此,本发明以咪唑并咔唑为核心的化合物在应用于OLED器件发光层或空穴阻挡或电子传输层后,可以有效地提高器件的发光效率及使用寿命等性能。
下面以本发明提供的部分化合物为例,将其分别作为作为发光层材料(主体材料和/或掺杂染料)、空穴阻挡材料、电子传输材料应用到有机电致发光器件中,以验证其所取得的优异效果。
具体通过器件实施例1~9和对比例1~2的器件性能详细说明本发明的OLED材料应用在器件中的优异效果。本发明器件实施例1~9和对比例1~2的结构制作工艺完全相同,并且采用了相同的玻璃基板和电极材料,电极材料膜厚也保持一致,所不同的是发光层材料做了调整,具体如下。
器件应用实施例
器件实施例1
本实施例提供了一种有机电致发光器件,其结构具体如图1所示,包括依次层叠设置的衬底1、阳极层2、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、空穴阻挡层7、电子传输层8、电子注入层9和阴极层10。
其中,阳极层2材料选择具有高功函数的铟锡氧化物(ITO),空穴注入层3材料选择HAT-CN,厚度为5nm;第一空穴传输层4材料选择NPB,厚度为60nm;第二空穴传输层5材料选择TCTA,厚度为15nm;发光层6使用化合物3作为主体材料,GD01作为发光材料,掺杂质量比为6%,厚度为30nm;空穴阻挡层7的材料选择TPBI,厚度为10nm;电子传输层8的材料选择ET-1,厚度为35nm;电子注入层9的材料选择Liq,厚度为2nm;阴极层的材料选择Al,厚度为100nm。
器件中各功能层所使用基本材料结构式如下:
上述有机电致发光器件的具体制备步骤如下:
1)清洗透明玻璃基板上的ITO阳极,分别用去离子水、丙酮、乙醇各超声清洗20分钟,然后进行氧气氛围下等离子(Plasma)处理5分钟;
2)在ITO阳极层上,通过真空蒸镀方式蒸镀空穴注入层材料HAT-CN,厚度为5nm,这层作为空穴注入层;
3)在空穴注入层上通过真空蒸镀方式蒸镀空穴传输材料NPB,厚度为60nm,该层作为第一空穴传输层;
4)在第一空穴传输层NPB上通过真空蒸镀方式蒸镀空穴传输材料TCTA,厚度为15nm,这层作为第二空穴传输层;
5)在第二空穴传输层上,通过真空蒸镀方式共蒸镀发光层,使用化合物化合物3作为主体材料,GD01作为发光材料,掺杂质量比为6%,厚度为30nm;
6)在发光层之上,通过真空蒸镀的方式蒸镀空穴阻挡材料TPBI,厚度为10nm,这一层作为空穴阻挡层;
7)在空穴阻挡层上,通过真空蒸镀的方式蒸镀电子传输材料ET-1,厚度为35nm,这一层作为电子传输层;
8)在电子传输层上,通过真空蒸镀的方式蒸镀电子注入材料Liq,厚度为2nm,这一层作为电子注入层;
9)在电子注入层上,通过真空蒸镀的方式蒸镀阴极Al,厚度为100nm,该层作为阴极导电电极使用。
器件实施例2
与器件实施例1相同,不同之处:将化合物13作为主体材料替代化合物3。
器件实施例3
与器件实施例1相同,不同之处:将化合物14作为主体材料替代化合物3。
器件实施例4
与器件实施例1相同,不同之处:将化合物21作为主体材料替代化合物3。
器件实施例5
与器件实施例1相同,不同之处:将化合物49作为主体材料替代化合物3。
器件实施例6
与器件实施例1相同,不同之处:将CBP作为主体材料,化合物3作为发光材料。
器件实施例7
与器件实施例6相同,不同之处:将化合物14作为发光材料。
器件实施例8
与器件实施例6相同,不同之处:将GD01作为发光材料,化合物46作为空穴阻挡材料。
器件实施例9
与器件实施例6相同,不同之处:将GD01作为发光材料,化合物48作为电子传输材料。
对比例1
与器件实施例1相同,不同之处:CBP作为主体材料替代化合物3。
对比例2
与对比例1相同,不同之处:GD02作为发光材料替代GD01。
本发明器件实施例1~9、对比例1~2所制备的不同器件构成成分,如表2所示:
表2各器件实施例的有机电致发光器件构成成分对比表
将各组有机电致发光器件用公知的驱动电路将阴极和阳极连接起来,通过标准的方法采用Keithley2400电源结合PR670光度计测试OLED器件的电压-效率-电流密度关系;器件的寿命通过恒流法测试,测试条件为恒定电流密度为10mA/cm2,测试亮度衰减到初始亮度的95%的时间,即为器件LT95寿命,测试结果如表3所示:
表3各组有机电致发光器件性能结果
由表3可知,本发明提供的化合物作为发光层的主体材料应用到OLED绿光发光器中,性能优良。如器件实施例4中的化合物21作为磷光主体材料与对比例1CBP相比,发光效率和使用寿命都得到了显著的提高,发光效率提高了14.1%,使用寿命提高了29.5%以上;如器件实施例6~7中的化合物作为TADF发光材料性能优良,如化合物14与对比例2中的GD02相比,发光效率提高了17.1%,使用寿命提高了50%,且色坐标优良。核心结构经过修饰可以作为空穴阻挡材料使用,如实施例8中化合物46替代TPBI后,器件效率提升8.1%,寿命提高35.2%;作为电子传输材料如实施例9中的化合物48与对比例1中的ET-1比,器件效率提高了10.2%,器件寿命提升了44.8%。可见选用本发明的化合物作为OLED器件的主体材料或发光材料或空穴阻挡材料或电子传输材料,对比现有材料应用到OLED发光器件,器件的发光效率、寿命、色纯度等光电性能均有良好的表现,而且材料的合成工艺简单,在OLED器件的应用上具有很大的应用价值,具有良好的产业化前景。
本发明在已有苯基苯并咪唑基础上通过锁定自由转动的苯基构成咪唑并咔唑全新受体骨架,通过在固定的取代位置连接胺类、咔唑衍生物、吖啶衍生物等给体基团修饰进而得到给-受体型化合物;或者在固定取代位置用典型受体基团三嗪、嘧啶、吡啶、苯并咪唑等基团修饰,进一步优化分子轨道能级以及电子传输性能。经过特定基团修饰的该类化合物具有合适的前线轨道能级以及三线态能量,所创新的系列化合物在有机电致发光(OLED)器件中作为主体材料或者发光材料或者电子传输材料表现出优良的性能。
显然,本领域的技术人员可以对本发明进行各种改动和变型而不脱离本发明的精神和范围。这样,倘若本发明的这些修改和变型属于本发明权利要求及其等同技术的范围之内也意图包含这些改动和变型在内。
Claims (9)
5.一种权利要求1~4任一项所述的以咪唑并咔唑为受体的化合物在有机电致发光器件中的应用。
6.一种有机电致发光器件,包括发光层,其特征在于,所述发光层的主体材料和/或发光染料为权利要求1~4任一所述的以咪唑并咔唑为受体的化合物。
7.一种有机电致发光器件,包括发光层和空穴阻挡层,其特征在于,所述空穴阻挡层所用材料为权利要求1~4任一所述的以咪唑并咔唑为受体的化合物。
8.一种有机电致发光器件,包括发光层和电子传输层,其特征在于,所述电子传输层所用材料为权利要求1~4任一所述的以咪唑并咔唑为受体的化合物。
9.权利要求6所述的有机电致发光器件在有机电致发光显示装置中的应用。
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CN114560872A (zh) * | 2022-03-15 | 2022-05-31 | 上海八亿时空先进材料有限公司 | 一种杂环咪唑化合物及其应用 |
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