CN108264505B - 一种含有1,2,4-三嗪基团的双极性主体材料及应用 - Google Patents
一种含有1,2,4-三嗪基团的双极性主体材料及应用 Download PDFInfo
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Abstract
本发明涉及一种含有1,2,4‑三嗪基团的双极性主体材料及应用,基于1,2,4‑三嗪基的双极性主体材料,具有式(I)所述结构的化合物,其中,R1‑R6为示为取代或未取代的吖啶基、吩噻嗪基、吩噁嗪基、咔唑、二苯胺、氢、卤素、取代或未取代的烷基。R1‑R6至少一个为取代或未取代的吖啶基、吩噻嗪基、吩噁嗪基、咔唑、二苯胺。实验表明,本发明的化合物比常用主体材料CBP具有更高的玻璃化转变温度,热稳定性好;使用本发明化合物的电致发光器件启亮电压更低,在相同电流密度下,电流效率更高,更利于载流子注入和传输平衡,使用本发明的有机材料制备的器件具有更好的电致发光性能,更符合高性能有机半导体器件对主体材料的要求。
Description
技术领域
本发明涉及新型的双极性主体材料,属于有机发光材料技术领域,具体涉及一种以1,2,4-三嗪为中心核的新型的双极性主体材料及其应用。
背景技术
有机发光二极管(OLED)具有相应速度快、耗能低、亮度高、视角广、可弯曲、主动发光等特性,受到了科学界和产业界的高度重视。其在显示、照明等方面的应用具有较大的潜力。电致荧光和电致磷光分别被称为第一代和第二代OLED。基于荧光材料的OLED具有稳定性高的特点,但受限于量子统计学定律,在电激活作用下,产生的单线态激子和三线态激子的比例为1:3,所以荧光材料电致发光内量子效率最大仅有25%。而磷光材料具有重原子的自旋轨道耦合作用,可以综合利用单线态激子和三线态激子,理论的内量子效率可达100%,但是基于磷光的OLED具有明显的效率滚降效应,在高亮度应用中有一定的阻碍。另外,磷光材料需用使用Pt,Ir等贵价金属,因此磷光材料价格较高。而目前,OLED器件中客体材料主要应用磷光材料。
磷光材料可以综合利用单线态激子和三线态激子,实现100%的内量子效率。然而,由于过渡金属配合物的激发态激子寿命相对过长,导致三线态-三线态(T1-T1)在器件实际工作中淬灭。为了克服这个问题,研究者们常将磷光材料掺杂于有机主体材料中。因此,对于高效有机发光二极管,开发高性能的主体材料以及客体材料十分重要。
目前,广泛应用于磷光器件的主体材料为CBP(4,4’-二(9-咔唑基)联苯),但是它要求的驱动电压较高、玻璃化转变温度(Tg)低(Tg=62℃),易于结晶。另外,CBP是一种P型材料,空穴迁移率远高于电子迁移率,不利于载流子注入和传输平衡,且发光效率低。
发明内容
针对现有主体(CBP)材料要求的驱动电压较高、玻璃化转变温度易于结晶、载流子注入和传输不平衡等问题,本发明提供一种双极性主体材料,该材料以1,2,4-三嗪基作为强拉电子中心核,具有强给电子能力的二苯胺类、咔唑、吖啶等衍生物作为连接基团,形成D-A型、D-A-D型双极性材料。
基于1,2,4-三嗪基的双极性主体材料,具有式(I)所述结构的化合物,
其中,R1-R6表示为取代或未取代的吖啶基、吩噻嗪基、吩噁嗪基、咔唑、二苯胺,氢,卤素,C1-C4烷基,R1-R6至少一个为取代或未取代的吖啶基、吩噻嗪基、吩噁嗪基、咔唑、二苯胺,所述取代为C1-C4的烷基取代、苯基取代、或烷苯基取代。
优选:其中,R5、R6独立地表示为氢;R1与R2中的一个为氢,另一个为取代或者未取代的吖啶基、吩噻嗪基、吩噁嗪基、咔唑、二苯胺;R3与R4中的一个为氢,另一个为烷基取代或者未取代的吖啶基、吩噻嗪基、吩噁嗪基、咔唑、二苯胺。
更优选:其中R1与R3相同,R2与R4相同。
进一步优选:R1、R3为氢,R2、R4为C1-C4烷基或苯基取代或者未取代的吖啶基、咔唑。
式(I)所述的化合物为下列结构化合物
有机电致发光器件,包括阴极、阳极和有机层,所述有机层为空穴传输层、空穴阻挡层、电子传输层、发光层中的一层或多层。需要特别指出,上述有机层可以根据需要,这些有机层不必每层都存在。
所述式(I)所述的化合物为空穴传输层的材料。
本发明的电子器件有机层的总厚度为1-1000nm,优选1-500nm,更优选5-300nm。
所述有机层可以通过蒸渡或旋涂形成薄膜。
如上面提到,本发明的式(I)所述的化合物如下,但不限于所列举的结构:
上述双极材料的制备方法,包括以下制备步骤:
首先将二卤素取代芳基乙二酮(a)与取代或未取代的芳酰肼(b)在叔丁醇钠条件下反应,得到亚胺中间体溶液,抽滤的溶液,减压除去溶剂后加入醋酸,并加入醋酸铵加热回流。得到3,5,6-(取代或未取代的苯基)-1,2,4-三嗪(c)。最后3,5,6-三(卤素取代苯)-1,2,4-三嗪(c)与取代或未取代的吖啶基、吩噻嗪基、吩噁嗪基、咔唑、二苯胺(d)通过钯催化的Buchwald反应,得到所述的双极主体材料。
化合物a是由卤代苯甲醛通过安息香缩合反应,再氧化所得;化合物b是通过取代的苯甲酸甲酯的酰肼化制得;化合物d为市售所得。
实验表明,本发明的化合物比常用主体材料CBP具有更高的玻璃化转变温度,本发明显著提高了主体材料的热稳定性。使用本发明的双极性主体材料制备的有机电致发光器件,稳定性高,具有更好的应用前景,更符合有机发光二极管对主体材料的要求。
附图说明
图1为化合物4的DSC曲线;
图2为本发明的器件结构图,其中10代表为玻璃基板,20代表为阳极,30代表为空穴注入层,40代表为空穴传输层,50代表发光层,60代表为空穴阻挡层,70代表为电子传输层,80代表为电子注入层,90代表为阴极。
图3为实施例器件与比较例器件电流密度-电流效率图(其中4为实施例,5为比较例)
具体实施方式
下面结合实施例对本发明作进一步详细的描述,但本发明的实施方式不限于此。
实施例1
(1)5,6-二(4-溴苯基)-3-苯基-1,2,4-三嗪(c1)的合成
合成路线如下所示:
具体合成步骤为:
称取叔丁醇钠(1.44g,15mmol)加至干燥四氢呋喃(50mL)中,加入苯酰肼(1.36g,10mmol)(b1),随后加入1,2-二(4-溴苯基)乙基-1,2-二酮(3.68g,10mmol)(a1)(通过4-溴苯甲醛的安息香缩合再氧化制备),搅拌1小时,抽滤并用二氯甲烷洗涤,得滤液。旋转蒸发仪除去溶剂后,加入20mL冰醋酸和醋酸铵(7.7g,100mmol),升温至回流反应搅拌4小时。反应结束后,自然冷却至室温,析出黄色固体,砂芯漏斗抽滤,水洗。硅胶柱层析分离得到3g黄色固体。产率:64%。
(2)9,9’-((3-苯基-1,2,4-三嗪-5,6-二基)二(4,1-亚苯基))二(9H-咔唑)(1)的合成
合成路线如下所示:
具体合成步骤为:
称取5,6-二(4-溴苯基)-3-苯基-1,2,4-三嗪(0.93g,2mmol)(c1),咔唑(0.67g,4mmol),Pd2(dba)3(0.19g,0.2mmol),NaOtBu(0.77g,8mmol)于25mL三口烧瓶中,换氮气三次。三叔丁基膦甲苯溶液(0.16g,0.4mmol)溶于10mL干燥的甲苯中,注入到反应瓶中。升温回流16小时。反应结束后,加入5%的亚硫酸氢钠溶液,二氯甲烷萃取,合并有机层,无水硫酸镁干燥。砂芯漏斗过滤,旋干溶剂,以正己烷:二氯甲烷=2:1为洗脱剂,硅胶层析柱提纯,分离得到1.27g黄色粉末固体。产率:93.5%。产物鉴定数据如下:
1H NMR(400MHz,CDCl3)δ=8.80-8.69(m,2H),8.16(d,J=7.7Hz,4H),8.06(d,J=8.4Hz,2H),7.99(d,J=8.4Hz,2H),7.73(d,J=8.4Hz,4H),7.67-7.57(m,3H),7.56-7.48(m,4H),7.44(t,J=7.6Hz,4H),7.32(dt,J=3.2,7.2Hz,4H)ppm.13C NMR(100MHz,CDCl3)=161.6,154.8,154.6,140.4,140.2,139.3,134.6,134.2,134.2,131.9,131.6,131.1,129.0,128.5,127.0,126.7,126.3,126.2,123.9,123.7,120.6,120.5,120.5,120.5,109.7ppm.Ms(ESI:Mz 640)(M+1)实施例2
(1)5,6-二(3-溴苯基)-3-苯基-1,2,4-三嗪(c2)的合成
合成路线如下所示:
具体合成步骤为:
称取叔丁醇钠(1.44g,15mmol)加至干燥四氢呋喃(50mL)中,加入苯酰肼(1.36g,10mmol)(b1),随后加入1,2-二(3-溴苯基)乙基-1,2-二酮(3.68g,10mmol)(a2)(通过3-溴苯甲醛的安息香缩合再氧化制备),搅拌1小时,抽滤并用二氯甲烷洗涤,得滤液。旋转蒸发仪除去溶剂后,加入20mL冰醋酸和醋酸铵(7.7g,100mmol),升温至回流反应搅拌4小时。反应结束后,减压旋干过量的醋酸。硅胶柱层析分离得到3.2g浅黄色油状物。产率:69%。
(2)10,10’-((3-苯基-1,2,4-三嗪-5,6-二基)二(3,1-亚苯基))二(9,9-二甲基吖啶)(4)的合成
合成路线如下所示:
具体合成步骤为:
称取5,6-二(3-溴苯基)-3-苯基-1,2,4-三嗪(0.93g,2mmol)(c2),9,9-二甲基吖啶(0.84g,4mmol)(d2),Pd2(dba)3(0.19g,0.2mmol),NaOtBu(0.77g,8mmol)于25mL三口烧瓶中,换氮气三次。三叔丁基膦甲苯溶液(0.16g,0.4mmol)溶于10mL干燥的甲苯中,注入到反应瓶中。升温回流16小时。反应结束后,加入5%的亚硫酸氢钠溶液,二氯甲烷萃取,合并有机层,无水硫酸镁干燥。砂芯漏斗过滤,旋干溶剂,以正己烷:二氯甲烷=2:1为洗脱剂,硅胶层析柱提纯,分离得到1.3g黄色粉末固体。再用10mL二氯甲烷溶解,加入20mL乙酸乙酯,放置于5℃冰箱析晶,得到1.1g浅黄色晶体。产率:74%。
产物鉴定数据如下:
1H NMR(400MHz,CDCl3)δ=8.81-8.67(m,2H),8.03(d,J=8.4Hz,2H),7.97(d,J=8.3Hz,2H),7.67-7.56(m,3H),7.52-7.38(m,8H),6.92(dt,J=3.4,6.4Hz,8H),6.34(dd,J=3.5,5.9Hz,4H),1.68(s,12H)ppm.13C NMR(100MHz,CDCl3)δ=161.8,155.1,155.0,144.0,142.8,140.6,140.5,135.3,135.3,134.6,132.5,132.1,132.0,131.8,131.2,130.7,130.4,129.0,128.6,126.5,125.3,125.2,121.2,121.0,114.3,114.0,36.1,36.1,31.6,31.0,30.9,22.7,14.2
实施例3
玻璃化转变温度测试:
氮气保护下,以20℃/min的加热和冷却速率用示差扫描量热法(DSC)测试化合物4的玻璃化转变温度。测得化合物4的玻璃化转变温度Tg为129℃(图1)。而文献所报道的CBP的玻璃化转变温度仅为62℃。
可见,本发明中的化合物比常用主体材料CBP具有更高的玻璃化转变温度,本发明显著提高了主体材料的热稳定性。
实施例4
有机电致发光器件的制备
器件结构为ITO/MoO3(10nm)/NPB(40nm)/化合物4:Ir(ppy):(7wt%,30nm)/BCP(10nm)/Alq3(30nm)/LiF(1nm)/AL(100nm)
器件制备方式描述如下:见图2
首先,将透明导电ITO玻璃基板(包含10和20)按照以下步骤处理:预先用洗涤剂溶液、去离子水,乙醇,丙酮,去离子水洗净,再经氧等离子处理30秒。
然后,在ITO上蒸渡10nm厚的MoO3作为空穴注入层30。
然后,在空穴注入层上蒸渡40nm厚的NPB作为空穴传输层40。
然后,在空穴传输层上蒸渡30nm厚的化合物4:Ir(ppy):(7wt%)作为发光层50。
然后,在发光层上蒸渡10nm厚的BCP作为空穴阻挡层60。
然后,在空穴阻挡层上蒸渡30nm厚的Alq3作为电子传输层70。
然后,在电子传输层上蒸渡1nm厚的Alq3作为电子注入层80。
最后,在电子注入层上蒸渡100nm厚的铝作为器件阴极90。
所制备的器件器件启亮电压为4.1V,在1000nit亮度下,电流密度为3.33mA/cm2,电流效率为30.33cd/A,发光效率为14.16lm/W,发射绿光CIEx为0.303,CIEy为0.626;电流在20mA/cm2的工作电流密度下,亮度4836cd/m2,电流效率为24.18cd/A,发射绿光CIEx为0.299,CIEy为0.626。
比较例
电致发光器件的制备
器件结构为ITO/MoO3(10nm)/NPB(40nm)/CBP:Ir(ppy):(7wt%,30nm)/BCP(10nm)/Alq3(30nm)/LiF(1nm)/AL(100nm)
方法同实施例4,但使用常用市售化合物CBP作为主体材料,制作对比用电致发光有机半导体二极管器件。
所制备的器件启亮电压为6.2V,在1000nit亮度下,电流密度为3.89mA/cm2,电流效率为25.52cd/A,发光效率为6.85lm/W,发射绿光CIEx为0.312,CIEy为0.612;在20mA/cm2的工作电流密度下,亮度4579cd/m2,电流效率为22.9cd/A,发射绿光CIEx为0.311,CIEy为0.612。
实验表明,使用本发明的双极性主体材料制备的电致发光器件,比于广泛使用的主体材料CBP制备的器件,启亮电压更低,在相同电流密度下,电流效率更高,更利于载流子注入和传输平衡,使用本发明的有机材料制备的器件具有更好的电致发光性能,更符合高性能有机半导体器件对主体材料的要求。
Claims (9)
1.一种基于1,2,4-三嗪基的双极性主体材料,具有式(I)所述结构的化合物,
其中,R5、R6为氢;R1与R2中的一个为氢,另一个为取代或者未取代的吖啶基、咔唑基或二苯胺基;R3与R4中的一个为氢,另一个为烷基取代或者未取代的吖啶基、咔唑基或二苯胺基,所述取代为C1-C4的烷基取代、苯基取代、或烷苯基取代。
2.根据权利要求1所述的双极性主体材料,其中R1与R3相同,R2与R4相同。
3.根据权利要求2所述的双极性主体材料,R1、R3为氢,R2、R4为C1-C4烷基或苯基取代或者未取代的吖啶基或咔唑基。
4.根据权利要求1所述的双极性主体材料,为下列结构的化合物之一:
5.根据权利要求4所述的双极性主体材料,为下列结构的化合物之一:
6.一种根据权利要求1-5中任一项所述的双极性主体材料的制备方法,包括以下制备步骤:
(1)将二卤素取代芳基乙二酮与未取代的芳酰肼在叔丁醇钠条件下于溶剂中反应,得到亚胺中间体溶液,过滤,溶液减压除去溶剂后加入醋酸,并加入醋酸铵加热回流,得到5,6-二(卤素取代苯)-3-苯基-1,2,4-三嗪;
(2)5,6-二(卤素取代苯)-3-苯基-1,2,4-三嗪与烷基或苯基取代或未取代的吖啶基、咔唑基、二苯胺基通过钯催化的布赫瓦尔德反应,得到所述的双极性主体材料。
7.根据权利要求6所述的方法,所述二卤素取代芳基乙二酮为二溴芳基乙二酮,通过3-溴苯甲醛的安息香缩合再氧化而制得。
8.根据权利要求6所述的方法,所述步骤(1)中的溶剂为干燥的四氢呋喃。
9.权利要求1-5任一所述的双极性主体材料在有机电致发光器件中的应用。
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