CN114057775A - 一种超级碱材料及其制备方法与有机发光二极管 - Google Patents
一种超级碱材料及其制备方法与有机发光二极管 Download PDFInfo
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6561—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing systems of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring or ring system, with or without other non-condensed hetero rings
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6561—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing systems of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring or ring system, with or without other non-condensed hetero rings
- C07F9/65616—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing systems of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring or ring system, with or without other non-condensed hetero rings containing the ring system having three or more than three double bonds between ring members or between ring members and non-ring members, e.g. purine or analogs
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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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
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Abstract
本发明公开了一种超级碱材料及其制备方法与有机发光二极管,所述超级碱材料具有以下结构通式:其中,芳香环Ar1、Ar2、Ar3和Ar4分别独立地选自取代或者未取代的芳基或杂芳基;N为氮原子;E是相同或者不同的,且每个E均是sp2‑杂化的碳或氮原子;Cy1、Cy2、Cy3和Cy4分别独立地选自取代或者未取代的杂环。通过酸解离常数(pKa)呈碱性的官能团的引入,可以有效的改善器件中电子注入性能,并且采用了平面刚性结构,有利于材料密堆表现出高电子迁移率,同时提高材料的玻璃化转变温度(Tg),提高器件的稳定性。在保持HOMO、LUMO能级的前提下,减小注入能垒,降低启亮电压,其作为有机发光二极管的电子传输材料时,具有载流子迁移率高、器件性能优异和稳定性好等优点。
Description
技术领域
本发明涉及有机显示领域,尤其涉及一种超级碱材料及其制备方法与有机发光二极管。
背景技术
有机材料的电致发光现象最早可以追溯到1963年,Pope等人发现单层蒽(anthracene)晶体作为电子传输层发出微弱的蓝光,但因为驱动电压高达100V以上未得到发展。直到1987年,美国Kodak公司的C.W.Tang等人使用8-羟基喹啉铝(AlQ3)作为电子传输层制备的有机发光二极管(Organic Light Emission Diodes,OLED),启亮电压低至几伏特,亮度高达1000cd/m2,有机发光二极管才取得了极大的进步。
电子传输材料是OLED的关键材料,其需要有良好的电子接受能力,可在一定的正向偏压下有效传递电子(参见有机电致发光材料与器件导论,黄春辉、李富有、黄维,143页),以保证在发光器件中电子的顺利注入、传输以及载流子的平衡。这就使得电子传输材料需要具备以下性质:(1)可逆的电化学还原性和足够高的还原电位;(2)合适的最高占据分子轨道(Highest Occupied Molecular Orbital,简称HOMO)和最低未占分子轨道(Lowest Occupied Molecular Orbital,简称LUMO);(3)较高的电子迁移率;(4)高的玻璃化转变温度(Tg);(5)非结晶性薄膜(参见OLED有机电致发光材料与器件,陈金鑫、黄孝文著,52页)。
然而,目前的电子传输材料在性能上还有待于进一步的改进和发展。
发明内容
鉴于上述现有技术的不足,本发明的目的在于提供一种超级碱材料及其制备方法与有机发光二极管,旨在通过超级碱官能团的引入,改善材料分子堆积以及电子注入能力,提升电子迁移速率,从而提高器件稳定性和工作寿命。
本发明的技术方案如下:
一种超级碱材料,其中,具有以下结构通式:
其中,芳香环Ar1、Ar2、Ar3和Ar4分别独立地选自取代或者未取代的芳基或杂芳基;N为氮原子;上述各个E可以是相同或者不同的,并且每个E均是sp2-杂化的碳或氮原子;Cy1、Cy2、Cy3和Cy4是相同或不同的,Cy1、Cy2、Cy3和Cy4分别独立地选自取代或者未取代的杂环。
可选地,所述取代或者未取代的芳基或杂芳基包括但不限于苯、噻吩、呋喃、吡啶。
可选地,所述Ar1、Ar2、Ar3和Ar4分别独立地选自取代或者未取代的苯基、萘基、(9,9-二烷基)芴基、(9,9-二取代或者未取代的芳基)芴基、9,9-螺芴基、嘌呤基、二苯基磷氧基、吡啶基团、咪唑基团、咪唑衍生物基团、嘧啶基、哒嗪基、咪唑联嘧啶基、吡嗪基、三嗪基或三嗪联苯基,但不限于此。
可选地,所述Ar1、Ar2、Ar3和Ar4分别独立地选自以下结构中的一种:
可选地,所述超级碱材料具有以下结构中的一种:
一种超级碱材料的制备方法,其中,包括以下步骤:
S01、将胺类衍生物加入第一溶剂中,反应后得到第一中间产物;
S02、将所述第一中间产物溶于第二溶剂中,加入二苯醚进行反应,将反应获得的产物与三溴氧磷进行反应,得到第二中间产物;
S03、将所述第二中间产物溶于第三溶剂中,加入联硼酸频哪醇酯进行反应,得到超级碱硼酸酯产物;
S04、将所述超级碱硼酸酯产物与溴代原料溶解于第四溶剂中,进行反应,得到所述超级碱材料。
可选地,所述胺类衍生物具有以下结构中的一种:
在一些优选的实施方式中,步骤S01具体包括:在氮气气氛保护下将原料胺类衍生物在施兰克瓶中溶解于0.1M的酸(如盐酸、磺酸、甲磺酸、对甲苯磺酸)处理过的的第一溶剂中或者直接高温煅烧,在饱和氯化铵溶液中冷却、过滤。90℃下加热15min后,将反应溶液减压蒸馏,通过色谱柱分离得到第一中间产物。
在一些优选的实施方式中,步骤S02具体包括:将所述第一中间产物在90℃溶解于第二溶剂中,加入二苯醚进行反应,将反应获得的产物与三溴氧磷进行反应,加热回流24小时,将溶液倒入水中,过滤得到白色沉淀,将白色沉淀溶解于二氯甲烷中,加水洗涤若干次,分液。用无水硫酸钠干燥后旋干得到第二中间产物。
在一些优选的实施方式中,步骤S03具体包括:将所述第二中间产物溶于第三溶剂中,在氮气气氛中加入双三苯基磷二氯化钯(5mol%)、2当量醋酸钾、联硼酸频哪醇酯,加热回流24小时,将反应溶液用无水硫酸钠干燥,通过色谱柱分离得到超级碱硼酸酯产物。
在一些优选的实施方式中,步骤S04具体包括:将所述超级碱硼酸酯产物与所选溴代原料溶解于第四溶剂中,在氮气气氛中加入四(三苯基磷)钯(10mol%)、2M碳酸钾水溶液、适量四氢呋喃溶液,加热回流24小时,将反应溶液用二氯甲烷萃取分液,用无水硫酸钠干燥后通过色谱柱分离得到所述超级碱材料。
可选地,所述第一溶剂包括N,N-二甲基甲酰胺、N-甲基吡咯烷酮、邻二甲苯、二甲亚砜、乙醇、甲醇、等中的一种或多种,所述第二溶剂包括N,N-二甲基甲酰胺、N-甲基吡咯烷酮、邻二甲苯、二甲亚砜、乙醇、甲醇、四氢呋喃、碳酸丙烯酯、碳酸乙烯酯、碳酸二乙酯、甲苯、水等中的一种或多种,所述第三溶剂包括苯、甲苯、氯苯、二甲苯、1,4-二氧六环、四氢呋喃、N,N-二甲基甲酰胺、N-甲基吡咯烷酮等中的一种或多种,所述第四溶剂包括苯、甲苯、氯苯、二甲苯、1,4-二氧六环、四氢呋喃、N,N-二甲基甲酰胺、N-甲基吡咯烷酮等中的一种或多种,但不限于此。
其中,所述第一溶剂可选择利于反应物溶解的高沸点溶剂,所述第二溶剂可选择离子型电解质或利于溶解反应底物的溶剂。
可选地,双三苯基磷二氯化钯浓度为5mol%,在节省催化剂的基础上,可使反应产率最大程度地得到提高。
可选地,四(三苯基磷)钯浓度为10mol%,碳酸钾水溶液浓度为2M,在节省催化剂的基础上,可充分发挥催化剂作用达到反应产率最大化。
一种超级碱材料的制备方法,其制备路线包括但不限于:
或者
或者
一种有机发光二极管,其中,包括电子传输层,所述电子传输层材料包括如上任一所述的超级碱材料。进一步地,所述电子传输层材料为如上任一所述的超级碱材料。
所述的有机发光二极管,其中,包括依次层叠设置的金属阴极、电子传输层、发光层、空穴传输层、空穴注入层以及阳极。
有益效果:本发明提供的一种超级碱材料,通过酸解离常数(pKa)呈碱性的官能团的引入,可以有效的改善器件中电子注入性能,并且采用了平面刚性结构,有利于材料密堆表现出高电子迁移率,同时提高材料的玻璃化转变温度(Tg),提高器件的稳定性,在保持HOMO、LUMO能级的前提下,减小注入能垒,降低启亮电压;不对称修饰利于偶极矩增加,提高分子三线态能级,阻挡激子并减少有效激子在传输层的淬灭。采用本发明提供的超级碱材料作为有机发光二极管的电子传输材料时,可省去电子注入层的蒸镀,具有载流子迁移率高、器件发光效率得到提升以及稳定性好等优点。
附图说明
图1为本发明实施例中所制备的超级碱材料化合物58的1H NMR图。
图2为本发明实施例中所制备的超级碱材料化合物58的13C NMR图。
图3为本发明实施例中基于超级碱材料作为电子传输层所制备的有机发光二极管的结构示意图。
具体实施方式
本发明提供一种超级碱材料及其制备方法与应用,为使本发明的目的、技术方案及效果更加清楚、明确,以下对本发明进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。
需要说明的是,本申请的说明书和权利要求书及上述附图中的术语“包括”,意图在于覆盖不排他的包含,例如,包含了一系列步骤或单元的过程、方法、***、产品或设备不必限于清楚地列出的那些步骤或单元,而是可包括没有清楚地列出的或对于这些过程、方法、产品或设备固有的其它步骤或单元。还需要说明的是,在不冲突的情况下,本申请中的实施例及实施例中的特征可以相互组合。
实施例中未注明具体实验步骤或条件者,按照本领域内的文献所描述的常规实验步骤或条件即可进行。所用试剂或仪器未注明生产厂商者,均为可通过市购获得的常规产品。实施例中未提及合成方法的化合物均为通过商业途径获得的原料产品。
下面通过具体实施例对本发明一种超级碱材料及其制备方法与应用做进一步的解释说明:
实施例1
本实施例提供一种超级碱材料,记为化合物16,其合成路线如下所示:
化合物16的合成方法具体包括以下步骤:
中间体1的合成:将原料1(0.1mol)和原料2(9.5g,0.1mol)放入100ml圆底烧瓶中,在155℃下缓慢搅拌。在原料溶解后(约20分钟),气态氨开始形成,8h后,将反应混合物冷却至60℃,加入甲醇30ml。均质后,加入0.1M甲醇钠溶液。混合物在减压下蒸发,以除去大部分甲醇。然后加入30ml二氯甲烷。过滤掉氯化钠,蒸发二氯甲烷溶液,具体先在旋转蒸发器中蒸发,然后在高真空(<5Torr)90℃下蒸发2h,得到微黄色软质中间体1(12.9g,产率93%)。
中间体2的合成:将中间体1(1.87g,3.0mmol)和甲苯(160mL)装入用烘箱干燥过的圆底烧瓶中,在90℃下加热以溶解中间体1,得到混合物。混合物被冷却到室温后添加醋酸钯(450mg,2.0mmol),搅拌30min,然后添加原料3(11.9g,50mmol)和叔丁醇钾(15.3g,140mmol),在90℃下搅拌反应过夜。冷却至室温后,在反应后体系中加入***,用硅藻土过滤。滤液蒸发后,用二丁基醚重结晶纯化残渣,得到淡黄色固体中间体2(13.0g,36.8mmol,产率74%)。
中间体3的合成:取500mL双颈圆底烧瓶,上接球形冷凝管,分别加入中间体2(3.53g,0.01mol)、70mL碳酸丙烯酯(PC),加热至完全溶解。冷却至室温,加入N-溴代琥珀酰亚胺(简写为NBS,2.13g,0.015mol),在90℃下反应18h。冷却至室温,将溶液倒入水中,过滤得到白色沉淀,粗产物使用乙醇重结晶得到中间体3(3.88g,0.09mol,产率90%)。
中间体4的合成:取100mL双颈圆底烧瓶,上接球形冷凝管,分别加入中间体3(4.3g,0.01mol),联硼酸频哪醇脂(2.54g,0.01mol),双三苯基磷二氯化钯(100mg),过量醋酸钾(2.5g)和50mL甲苯;将反应体系在氮气气氛下进行多次除氧操作后密封,并将反应体系在85℃下搅拌24h;之后旋干甲苯,用少量二氯甲烷溶解,经水洗两遍,将水相用二氯甲烷反萃一遍,并重复此操作两遍。然后用无水硫酸镁干燥,过滤旋干;并将其用混合溶剂(石油醚/乙酸乙酯,v/v=5:1)作为洗脱液进行柱色谱纯化,得到中间体4的白色固体,再用甲醇/二氯甲烷重结晶得无色透明晶体(4.3g,产率90%)。
化合物16的合成:取50mL圆底烧瓶,上接球形冷凝管,干燥后充入氮气,分别加入中间体4(2.40g,5mmol),原料4(1.49g,4.16mmol),四三苯基膦钯(115.6mg,0.1mmol),2M碳酸钾水溶液10mL,50mL甲苯,加热回流24h。冷却至室温,将溶液倒入水中,过滤得到白色沉淀,粗产物使用柱层析色谱法分离得到化合物16(3.75g,产率67%)。
实施例2
本实施例提供一种超级碱材料,记为化合物42,其合成路线如下所示:
化合物42的合成方法具体包括以下步骤:
中间体5的合成:在氮气气氛中,-20℃下,取Schlenk瓶将原料5溶解于(15.8g,0.1mol)干燥的乙醇中,加入8当量的原料6(113g,0.8mol)。再将1.2当量的间氯过氧苯甲酸(20.7084g,1.2mol)在1.5h内分三次加入。通过TLC监测反应进程,直到原料点完全消失。加入饱和碳酸钠水溶液和碳酸钾。用负载硫酸镁和碳酸钾的布氏漏斗过滤,之后用二氯甲烷洗涤旋干得到粗产物,再用硅胶柱层析纯化(EtOAc/CH2Cl2)得到中间体5(1.94g,产率42%)
中间体6的合成:将中间体5(0.8g,2.12mmol)和乙酸钠(0.172g,2.12mmol)加入到80mL二苯醚(Ph2O)中,然后置于装有特氟龙内胆的不锈钢反应釜中(容量为100mL)。进行剧烈的搅拌以分散混合物,然后静止,在250℃烘箱中热处理16h。离心重复用甲醇洗涤得到中间体6(2.6g,产率69%)。
中间体7的合成:将磷溴氧化物(POBr3,2.97g,10.4mmol)和中间体6(0.520g,2.08mmo)混合,在氩气气氛中于200℃下搅拌30分钟。反应结束后分别用二氯甲烷(200mL)、甲醇(20mL)、6mol/L氢氧化钾溶液(20mL)、水(200mL)洗涤。加入少量脱色碳,用无水硫酸镁过滤并干燥有机层,得到中间体7(0.433g,产率66%)。
中间体8的合成:同中间体4的合成,区别在于使用中间体7(1.535g,5mmol),最后得到中间体8(3.06g,产率86%)。
化合物42的合成:同化合物16的合成,区别在于使用中间体8(1.54g,5mmol)和原料7(2.68g,7.5mmol),最后得到化合物42(1.76g,产率70%)。
实施例3
本实施例提供一种超级碱材料,记为化合物58,其合成路线如下所示:
化合物58的合成:同化合物16的合成,区别在于使用中间体8(1.54g,5mmol)和原料8(3.09g,7.5mmol),最后得到化合物58(0.99g,产率35%)。化合物58的1H NMR图和13CNMR图分别见图1和图2。
实施例4
本实施例提供了基于超级碱材料作为电子传输层的有机发光二极管,如图3所示,包括从上至下依次层叠设置的金属阴极10、电子传输层20、发光层30、空穴传输层40、空穴注入层50、阳极60以及玻璃基板70。
在本实施例中,金属阴极10的材料选用铝;
电子传输层20的材料选用化合物58;
发光层30的材料由主体材料和客体材料共掺杂形成,其中主体材料选用具有以下结构的化合物2,6-DCzPPy,客体材料选用具有以下结构的Firpic,主体材料与客体材料掺杂的质量比为80:20:
空穴传输层40的材料选用具有如下结构的化合物NPB:
空穴注入层50的材料选用具有如下结构的化合物HATCN:
阳极60的材料选用氧化铟锡。
对本实施例制备的器件进行性能测试,结果如表1所示:
表1、器件性能
由表1可知,本实施例提供的超级碱材料58可以匹配多数发光层,并且器件表现出较低的工作过电压和较高的效率,表明该种电子传输材料具有一定的空穴、激子阻挡能力,与此同时,器件的启亮电压较低,说明通过超级碱材料的应用器件中电子得到有效注入。
综上所述,本发明提供了一种超级碱材料,通过酸解离常数(pKa)呈碱性的官能团的引入,可以有效的改善器件中电子注入性能,并且采用了平面刚性结构,有利于材料密堆表现出高电子迁移率,同时提高材料的玻璃化转变温度(Tg),提高器件的稳定性,在保持HOMO、LUMO能级的前提下,减小注入能垒,降低启亮电压;不对称修饰利于偶极矩增加,提高分子三线态能级,阻挡激子并减少有效激子在传输层的淬灭。采用本发明提供的超级碱材料作为有机发光二极管的电子传输材料时,可省去电子注入层的蒸镀,具有载流子迁移率高、器件发光效率得到提升以及稳定性好等优点。
应当理解的是,本发明的应用不限于上述的举例,对本领域普通技术人员来说,可以根据上述说明加以改进或变换,所有这些改进和变换都应属于本发明所附权利要求的保护范围。
Claims (10)
2.根据权利要求1所述的超级碱材料,其特征在于,所述Ar1、Ar2、Ar3和Ar4分别独立地选自取代或者未取代的苯基、萘基、(9,9-二烷基)芴基、(9,9-二取代或者未取代的芳基)芴基、9,9-螺芴基、嘌呤基、二苯基磷氧基、吡啶基团、咪唑基团、咪唑衍生物基团、嘧啶基、哒嗪基、咪唑联嘧啶基、吡嗪基、三嗪基或三嗪联苯基。
5.一种超级碱材料的制备方法,其特征在于,包括以下步骤:
将胺类衍生物加入到第一溶剂中,反应后得到第一中间产物;
将所述第一中间产物溶于第二溶剂中,加入二苯醚进行反应,将反应获得的产物与三溴氧磷进行反应,得到第二中间产物;
将所述第二中间产物溶于第三溶剂中,加入联硼酸频哪醇酯进行反应,得到超级碱硼酸酯产物;
将所述超级碱硼酸酯产物与溴代原料溶解于第四溶剂中,进行反应,得到所述超级碱材料。
7.根据权利要求5所述的超级碱材料的制备方法,其特征在于,所述第一溶剂包括N,N-二甲基甲酰胺、N-甲基吡咯烷酮、邻二甲苯、二甲亚砜、乙醇、甲醇、四氢呋喃中的一种或多种,所述第二溶剂包括N,N-二甲基甲酰胺、N-甲基吡咯烷酮、邻二甲苯、二甲亚砜、乙醇、甲醇、四氢呋喃、碳酸丙烯酯、碳酸乙烯酯、碳酸二乙酯、甲苯、水中的一种或多种。
8.根据权利要求5所述的超级碱材料的制备方法,其特征在于,所述第三溶剂包括苯、甲苯、氯苯、二甲苯、1,4-二氧六环、四氢呋喃、N,N-二甲基甲酰胺、N-甲基吡咯烷酮中的一种或多种,所述第四溶剂包括苯、甲苯、氯苯、二甲苯、1,4-二氧六环、四氢呋喃、N,N-二甲基甲酰胺、N-甲基吡咯烷酮中的一种或多种。
9.一种有机发光二极管,其特征在于,包括电子传输层,所述电子传输层材料包括权利要求1-4任一所述的超级碱材料。
10.根据权利要求9所述的有机发光二极管,其特征在于,所述有机发光二极管包括依次层叠设置的金属阴极、电子注入层,电子传输层、发光层、空穴传输层、空穴注入层以及阳极。
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