CN103664909A - 联咔唑类衍生物及制备方法、应用和有机发光器件 - Google Patents
联咔唑类衍生物及制备方法、应用和有机发光器件 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims description 7
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- 239000000463 material Substances 0.000 claims abstract description 19
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 4
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- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
技术领域
本发明涉及有机光电材料领域,尤其涉及一类联咔唑类化合物、制备方法及其应用。
背景技术
有机电致发光(EL)器件(在下文中,简称为“有机EL器件”)。一般由两个对置的电极和插入在该两个电极之间的至少一层有机发光化合物组成。电荷被注入到在阳极和阴极之间形成的有机层中,以形成电子和空穴对,使具有荧光或磷光特性的有机化合物产生了光发射。
对于有机EL材料的研究是从1950年Bernanose对含有有机色素的高分子薄膜施加高电流电压观测到的发光开始,1965年,Pope等人首次发现了蒽单晶的电致发光性质。1987年,柯达公司的Tang等人发现,由有机材料形成的具有分离功能叠层的有机发光器件即使在10V或更小的低电压下也能提供1000cd/cm2或更高的高亮度。
由于在有机材料中空穴的迁移率显著高于电子迁移率,所以当使用合适的空穴传输层和电子传输层时可以更有效地向发光层传输空穴和电子。另外,当发光层中的空穴密度与电子密度平衡时,可以提高发光效率。
当电子、空穴在有机分子中再结合,会因电子自旋对称方式不同,产生两种激发态的形式。一种是由非自旋对称的基态电子形成的单重激发态形式,它会以荧光的形式释放能量回到基态;另一种是由自旋对称的基态电子形成的三重激发态形式,以磷光的形式释放出能量回到基态。根据理论推测,由电荷的再结合而引起的单重激发态与三重激发态的比例为1:3,如将单重激发态的能量转移到三重激发态中,进而发出磷光,由此内部量子效率可接近100%。
一般磷光主体发光材料有CBP等咔唑环化合物,磷光客体发光材料有Ir,Pt等为中心金属原子附着的化合物被广泛使用。然而,这种有机EL器件只有150小时的短寿命,因为CBP的玻璃化温度很低,仅110℃,并有结晶的可能,所以它不适用于商业用途。
发明内容
本发明是为了解决上述技术的问题,提供了一种用于磷光绿色主体材料,空穴注入材料或者空穴传输材料,所述主体材料有改善的电稳定性,更好的电荷传输能力,高的玻璃化温度并且不结晶。
本发明还提供一种低电压,高效率,高亮度,长寿命、稳定的咔唑类诱导体制作的有机电致发光(EL)器件。
本发明提供了一种联咔唑类化合物的下式(1)化合物:
通式(1)中,A选自通式(2)含吡啶类衍生物基团的化合物。
其中,X、Y、Z代表碳原子或者氮原子。
上述优选本发明的联咔唑类化合物,具体的结构式分别对应为如下化学结构式:
本发明还提供了所述的联咔唑类衍生物的制备方法,包括如下步骤:
步骤S1:向脱气后的反应容器中加入联咔唑、所述A基团的溴化物、氢氧化钾、溶剂和催化剂;
步骤S2:升高反应温度并回流,充分反应;
步骤S3:过滤、精制、重结晶、干燥得到所述的联咔唑类衍生物。
本发明实施例还提供了一种所述的联咔唑类衍生物在所述有机电致发光器件中的应用;优选地,所述联咔唑类衍生物用作磷光主体材料。
本发明还提供了一种有机发光器件,包括第一电极、第二电极和置于所述两电极之间的一个或多个有机化合物层,其中,至少一个有机化合物层包含至少一种所述联咔唑类衍生物。
本发明提供的联咔唑类衍生物,电稳定性得到提高,具有更好的电荷传输能力,高的玻璃化温度并且不结晶,用于有机电致发光器件中表现出高效率、高亮度、长寿命,具有制造成本较低的优点,并且延长了有机电致发光器件的寿命,降低了有机电致发光器件的制造成本。
具体实施方式
本发明提供了一种联咔唑类衍生物,所述联咔唑类衍生物的分子结构通式为:
通式(1)中,A选自通式(2)含吡啶类衍生物基团的化合物。
其中,X、Y、Z代表碳原子或者氮原子。
优选的,联咔唑衍生物至少为下面化学式所示001~004化合物之一:
本发明还提供了所述的联咔唑类衍生物的制备方法,包括如下步骤:
步骤S1:向脱气后的反应容器中加入联咔唑、所述A基团的溴化物、氢氧化钾、溶剂和催化剂;
步骤S2:升高反应温度并回流,充分反应;
步骤S3:;过滤、精制、重结晶、干燥得到所述的联咔唑类衍生物。
该制备方法的具体步骤和条件如下:
具体的,化合物001的合成
在氮气保护下,将联咔唑6.64g(0.02mol)、2-(4-溴苯基)-4,6-二苯基-1,3,5-三嗪17.08g(0.044mol),叔丁醇钾4.94g(0.044mol),乙酸钯(Ⅱ)0.045g(0.0002mol),三叔丁基磷0.04g(0.0002mol),用100ml甲苯溶解,于110℃反应20小时。过滤反应溶液,用硅胶色谱精制得到的粗产物,再用甲苯对得到的固体进行重结晶,干燥,得到14.96g米白色固体化合物001,产率79%。
HPLC纯度大于99%。质谱:计算值为947.09;测试值为947.08。元素分析:计算值为C:83.70%;H:4.47%;N:11.83%;测试值为C:83.69%;H:4.46%;N:11.85%。
化合物002的合成
在氮气保护下,将联咔唑6.64g(0.02mol)、2-(4-溴苯基)-4,6-二苯基嘧啶17.04g(0.044mol)、叔丁醇钾4.94g(0.044mol)、乙酸钯(Ⅱ)0.045g(0.0002mol)、三叔丁基磷0.04g(0.0002mol),用100ml甲苯溶解,于110℃反应20小时。过滤反应溶液,用硅胶色谱精制得到的粗产物,再用甲苯对得到的固体进行重结晶,干燥,得到15.12g白色固体化合物002,产率80%。
HPLC纯度大于99%。质谱:计算值为945.12;测试值为945.12。元素分析:计算值为C:86.42%;H:4.69%;N:8.89%;测试值为C:86.42%;H:4.68%;N:8.90%。
化合物003的合成
在氮气保护下,将联咔唑6.64g(0.02mol)、4-(4-溴苯基)-2,6-二苯基嘧啶17.04g(0.044mol)、叔丁醇钾4.94g(0.044mol)、乙酸钯(Ⅱ)0.045g(0.0002mol)、三叔丁基磷0.04g(0.0002mol),用100ml甲苯溶解,于110℃反应20小时。过滤反应溶液,用硅胶色谱精制得到的粗产物,再用甲苯对得到的固体进行重结晶,干燥,得到15.50g米白色固体化合物003,产率82%。
HPLC纯度大于99%。质谱:计算值为945.12;测试值为945.14。元素分析:计算值为C:86.42%;H:4.69%;N:8.89%;测试值为C:86.41%;H:4.68%;N:8.89%。
化合物004的合成
在氮气保护下,将联咔唑6.64g(0.02mol)、2-(4-溴苯基)-4,6-二苯基吡啶17.00g(0.044mol)、叔丁醇钾4.94g(0.044mol)、乙酸钯(Ⅱ)0.045g(0.0002mol)、三叔丁基磷0.04g(0.0002mol),用100ml甲苯溶解,于110℃反应20小时。过滤反应溶液,用硅胶色谱精制得到的粗产物,再用甲苯对得到的固体进行重结晶,干燥,得到15.28g米白色固体化合物004,产率81%。
HPLC纯度大于99%。质谱:计算值为943.14;测试值为943.13。元素分析:计算值为C:89.14%;H:4.92%;N:5.94%;测试值为C:89.16%;H:4.91%;N:5.93%。
本发明实施例还提供了一种所述的联咔唑类衍生物在所述有机电致发光器件中的应用;优选地,本发明实施例中的所述联咔唑类衍生物用作磷光主体材料。
本发明还提供了一种有机发光器件,包括第一电极、第二电极和置于所述两电极之间的一个或多个有机化合物层,其中,至少一个有机化合物层包含至少一种所述联咔唑类衍生物。
通过下面的实例更详细的说明本发明。但是,下面的实例只是为了更加具体的说明本发明而已,本发明的范围不只限定于实例。下面的实例在本发明范围内根据使用者可以修正,变更。
比较实施例1
下面化学式a作为发光层磷光主体材料,下面化学式b作为掺杂材料,2-TNATA(4,4,4-三(N-萘基)-N-苯基氨基)-三苯胺)为空穴输送材料,α-NPD(N,N’-二(萘基)-N,N’-二苯基联苯胺)为空穴传输材料,制作了下面结构的有机发光器件对比样品。
TNATA(80nm)/α-NPD(30nm)/化合物a+化合物b(30nm)/Al q3(30nm)/LiF(0.5nm)/Al(60nm)。本实施例以及以下实施例中采用韩国DOV公司制造的EL蒸镀机制作器件。
Corning(康宁)社15Ω/cm2(1000□)ITO玻璃基板50mm*50mm*0.7mm大小切断后在丙酮,异丙醇,纯水中各在微波中洗净15分钟,在紫外中再洗净30分钟。在基板上面真空蒸镀80nm厚度的2-TNATA,形成空穴注入层。空穴注入层上面真空蒸镀30nm厚度的α-NPD,形成了空穴输送层。空穴输送层上面真空蒸镀30nm厚度的化学式a表示的化合物和化学式b表示的化合物(掺杂率10%),形成了发光层。电子输送层上面一次真空蒸镀LiF0.5nm(电子注入)和Al60nm制作了有机发光器件。
应用实施例1-4:
上面比较实施例中,作为发光层磷光主体化合物a用化合物001-004代替,除此外其他采用的是比较实施例1中同样的方法ITO/2-TNATA(80nm)/α-NPD(30nm)/[磷光绿色主体化合物001~004中一种]/b(10%)](30nm)/Alq3(30nm)/LiF(0.5nm)/Al(60nm)的结构的有机发光器件,得到样品1-4。
测量实施例1:对比样品以及样品1-4的发光性能
测量对比样品以及样品1-4是采用Keithley source meter“2400”,KONIKA MINOLTA“CS-2000”评价驱动电压,发光亮度,发光效率,发光颜色。对比样品以及样品1-4进行同样试验。结果列于表1中:
根据表1所表示,样品1到4跟对比样品比较,上面的样品在范围511-517nm内显示绿色发光峰值。所述咔唑类化合物发光效率得到了明显的提高。
Claims (6)
3.一种如权利要求1所述的联咔唑类衍生物的制备方法,其特征在于,包括如下步骤:
步骤S1:向脱气后的反应容器中加入联咔唑、所述A基团的溴化物、氢氧化钾、溶剂和催化剂;
步骤S2:升高反应温度并回流,充分反应;
步骤S3:过滤、精制、重结晶、干燥得到所述的联咔唑类衍生物。
4.根据权利要求1~2任一项所述的联咔唑类衍生物在有机电致发光器件中的应用,其特征在于,所述的联咔唑类衍生物在所述有机电致发光器件中用作磷光主体材料。
5.根据权利要求4所述的联咔唑类衍生物在有机电致发光器件中的应用,其特征在于,所述的联咔唑类衍生物在所述有机电致发光器件中用作磷光绿色主体材料。
6.一种有机发光器件,包括第一电极、第二电极和置于所述两电极之间的一个或多个有机化合物层,其特征在于,至少一个有机化合物层包含至少一种如权利要求1~2任一项所述联咔唑类衍生物。
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