CN113896723B - 一种基于苯并噻二唑衍生物的热激活延迟材料及其制备方法和应用 - Google Patents
一种基于苯并噻二唑衍生物的热激活延迟材料及其制备方法和应用 Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 55
- UELITFHSCLAHKR-UHFFFAOYSA-N acibenzolar-S-methyl Chemical compound CSC(=O)C1=CC=CC2=C1SN=N2 UELITFHSCLAHKR-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000007725 thermal activation Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 238000000034 method Methods 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 6
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 abstract description 4
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 abstract description 3
- 229950000688 phenothiazine Drugs 0.000 abstract description 3
- FNQJDLTXOVEEFB-UHFFFAOYSA-N 1,2,3-benzothiadiazole Chemical compound C1=CC=C2SN=NC2=C1 FNQJDLTXOVEEFB-UHFFFAOYSA-N 0.000 abstract description 2
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- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 4
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 2
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
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- 238000011161 development Methods 0.000 description 2
- 230000005525 hole transport Effects 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 235000011056 potassium acetate Nutrition 0.000 description 2
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- UWCZIRUJFYRXKE-UHFFFAOYSA-N 1,5-dimethylacridine Chemical compound C1=CC=C2C=C3C(C)=CC=CC3=NC2=C1C UWCZIRUJFYRXKE-UHFFFAOYSA-N 0.000 description 1
- QBKFSWPZWWKKMJ-UHFFFAOYSA-N 4,7-dibromo-1,2,3-benzothiadiazole Chemical compound BrC1=CC=C(Br)C2=C1N=NS2 QBKFSWPZWWKKMJ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
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- 238000000113 differential scanning calorimetry Methods 0.000 description 1
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- 238000002156 mixing Methods 0.000 description 1
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- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
- ARYHTUPFQTUBBG-UHFFFAOYSA-N thiophen-2-ylboronic acid Chemical compound OB(O)C1=CC=CS1 ARYHTUPFQTUBBG-UHFFFAOYSA-N 0.000 description 1
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- C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
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Abstract
本发明公开了一种基于苯并噻二唑衍生物的热激活延迟材料,具体结构如下:苯并噻二唑具有吸电子能力很强的受体材料,而吖啶类、吩噁嗪、吩噻嗪是一类很好的给体材料,通过二者的结合构建了一系列新型的红光TADF材料,这类材料制备成本低、热稳定性好,由于产品结构对称性好,所以成膜性要好,效率高,解决了OLED红光材料制备成本高、热稳定性低、成膜性差及效率不高的技术问题。
Description
技术领域
本发明涉及有机电致发光材料领域,具体涉及一种基于苯并噻二唑衍生物的热激活延迟材料及其制备方法和应用。
背景技术
TADF材料,也叫热激活延迟荧光材料,是指当三重激发态与单重态激发态能量接近时,三重态激子可以通过反系间窜越过程转变为单重态激子并通过延迟荧光过程发光。TADF材料的发光效率远远高于第一代荧光材料,且可与第二代磷光材料相抗衡。同时,TADF材料不含价格高昂的铱或铂等贵金属,因此成本比第二代磷光材料低。除了上述优点外,其合成步骤较少、容易快速生产。所以TADF材料有望成为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。
近几年来,TADF材料发展非常迅速,但材料的热稳定性低,成膜性差;在三基色材料的开发方面,主要集中在蓝光和绿光TADF材料的开发,由于红光TADF材料制备比较相对比较困难。因此,红光TADF种类相对较少,而且器件效率也不高。
发明内容
为克服上述缺点,本发明的目的在于提供一种基于苯并噻二唑衍生物的热激活延迟材料及其制备方法,解决了OLED红光材料制备成本高、热稳定性低、成膜性差及效率不高的技术问题。
为了达到以上目的,本发明采用的技术方案是:一种基于苯并噻二唑衍生物的热激活延迟材料,具体结构如下:
其中R包含以下基团:
优选地,所述的苯并噻二唑衍生物的热激活延迟材料包括以下一种或者几种化合物:
优选地,所述的苯并噻二唑衍生物的热激活延迟材料包括以下一种或者几种化合物:
优先地,所述的苯并噻二唑衍生物的热激活延迟材料包括以下一种或者两种化合物:
一种基于苯并噻二唑衍生物的热激活延迟材料的制备方法,按照如下路线制备:
其中R包含以下基团:
优选地,R包含以下基团:
优选地,R包含以下基团:
一种基于苯并噻二唑衍生物的热激活延迟材料在作为发光层制备的OLED器件中的应用。
本发明的有益效果是:苯并噻二唑具有吸电子能力很强的受体材料,而吖啶类、吩噁嗪、吩噻嗪是一类很好的给体材料,通过二者的结合构建了一系列新型的红光TADF材料,这类材料制备成本低、热稳定性好,由于产品结构对称性好,所以成膜性要好,效率高,解决了OLED红光材料制备成本高、热稳定性低、成膜性差及效率不高的技术问题。
附图说明
图1为本发明一较佳实施例1中样品1的核磁氢谱;
图2为本发明一较佳实施例2中样品2的核磁氢谱;
图3为本发明一较佳实施例3中OLED器件示意图。
其中:1、透明基板层;2、ITO阳极层;3、空穴注入层;4、空穴传输层;5、发光层;6、电子传输层;7、电子注入层;8、阴极金属层。
具体实施方式
下面结合附图对本发明的较佳实施例进行详细阐述,以使本发明的优点和特征能更易于被本领域技术人员理解,从而对本发明的保护范围做出更为清楚明确的界定。
实施例1:
样品1的合成,合成路线如下:
步骤1:中间体1b的合成
在带有温度计、搅拌、氮气保护装置的反应器中,称取4,7-二溴苯并噻二唑(5.0g,17mmol),2-噻吩硼酸(9.6g,74mmol),K2CO3(11.73g,85mmol),Ph(PPh3)4(1g,1.99mol),甲苯100ml,乙醇75ml,水50ml。将上述原料一起加入500ml圆底烧瓶中,回流反应,TLC监控。反应完毕,冷却,过滤,旋干柱层析纯化,展开剂为二氯甲烷:正己烷=1:1。柱层析纯化后得到3.2g中间体1b,收率62.7%。
步骤2:中间体1c的合成
在带有温度计、搅拌、氮气保护装置的反应器中,将中间体1b(3.2g,10.6mmol)加入250ml梨形瓶中,然后依次加入氯仿78ml、醋酸78ml,NBS(3.75g,14mmol)。室温搅拌过夜。然后析出红色针状结晶,过滤得到粗产品,粗产品用二氯甲烷重结晶,得到2.1g中间体1c,收率45.1%。
步骤3:中间体1e的合成
在带有温度计、搅拌、氮气保护装置的250ml反应器中,加入二甲基吖啶(6.6g,31.5mmol)、1,4-二溴苯(11g,47mmol)、醋酸钯(0.4g,1.8mmol)、三叔丁基膦(2.7g,13.4mmol)、叔丁醇钠(4.5g,47mol)、和甲苯130ml,加热反应回流,TLC检测反应完全。过滤,旋干滤液拌样柱层析,展开剂为石油醚,得到7g中间体1e,产率61%。
步骤4:中间体1f的合成
在带有温度计、搅拌、氮气保护装置的250ml反应器中,加入中间体1e(7g,19.3mmol)、联硼酸频哪醇酯(6g,23.6mmol)、乙酸钾(5g,51mmol)、Pd(dppf)Cl2(1g,1.4mmol)和DMSO 100ml,加热反应回流过夜。点板反应完全,抽滤,旋干滤液拌样柱层析,得产物6.5g,产率61%。
步骤5:样品1的合成
在带有温度计、搅拌、氮气保护装置的100ml反应器中,称取中间体1c(1g,2.18mmol),中间体1f(0.5g,1.22mmol),K2CO3(0.76g,5.5mmol),Pd(PPh3)4(0.13g,0.11mmol),甲苯100ml,乙醇75ml,水50ml,回流反应,TLC监控,反应完毕,冷却,过滤,甲醇洗涤。得到0.5g样品1,收率60%。
实施例2:
样品2的合成,合成路线如下:
步骤1:中间体2b的合成
在带有温度计、搅拌、氮气保护装置的250ml反应器中,加入吩噻嗪2a(6g,30mmol)、1,4-二溴苯(10g,42mmol)、醋酸钯(0.3g,1.3mmol)、三叔丁基膦(2g,10mmol)、叔丁醇钠(5g,52mmol)、和甲苯100ml,加热反应回流。TLC板检测反应完全。过滤反应液,旋干滤液拌样柱层析,PE为展开剂,得到6g中间体2b,产率60%。
步骤2:中间体2c的合成
在带有温度计、搅拌、氮气保护装置的250ml反应器中,加入中间体2b(6g,16.9mmol)、联硼酸频哪醇酯(5g,19.7mmol)、乙酸钾(5g、51mmol)、Pd(dppf)Cl2(1g,1.36mmol)和DMSO 100ml,加热反应回流过夜。TLC板检测反应完全,抽滤,旋干滤液拌样柱层析,得到5g中间体2c,产率71%。
步骤3:样品2的合成
在带有温度计、搅拌、氮气保护装置的100ml反应器中,称取中间体1c(0.43g,0.94mmol),中间体2c(0.5g,1.25mmol),K2CO3(0.76g,5.5mmol),Pd(PPh3)4(0.13g、0.11mmol),甲苯75ml,乙醇50ml,水25ml,回流反应,TLC监控。反应完毕,冷却,过滤,甲醇洗涤。得到0.4g样品2,收率50%。
实施例3
我们对样品1、样品2进行了性能测试,主要考察了热稳定性和发光性能,其结果如下表所示:
样品 | Tg(℃) | Td(℃) | λPLs(nm) | φf |
1 | 133 | 440 | 660 | 78 |
2 | 120 | 420 | 670 | 83 |
其中,Tg为玻璃化转变温度,通过差示扫描热法(DSC,德国耐驰公司DSC204FI差示扫描量热仪)测定,升温速率10℃/min;热失重Td是在氮气氛围中失重1%时的温度,在日本岛津公司的TGA-50H热重分析仪上进行测定,氮气流量为20ml/min;λPLs是样品固体粉末的的最大发射波长,用日本岛津公司的RF-5301PC荧光分光光度计测定;φf是固体粉末的荧光量子效率(利用美国海洋光学的Maya2000pro光纤光谱仪;美国蓝菲公司的C-701积分球和海洋光学LLS-LED光源组成的固体荧光量子效率测试系统,参照文献ADV.Mater.1997,9,230-232的方法进行测定)。
由上述表格数据可以看出,样品1和样品2的Td分别是440℃和420℃,均大于300℃,显示出非常好的热稳定性;样品结构均不含有贵金属,所以制备成本远远低于目前商用的红光材料铱配合物(如Ir(piq)3);另外样品结构对称性好,成膜性比较好;样品的量子效率均较高。故所述的热活延迟材料非常适合做OLED器件中的发光层材料。
本发明还提供了使用上述热活延迟材料作为发光层制备的OLED器件。其中1为透明基板层,2为ITO阳极层,3为空穴注入层,4为空穴传输层,5为发光层,6为电子传输层,7为电子注入层,8为阴极金属层。
以上实施方式只为说明本发明的技术构思及特点,其目的在于让熟悉此项技术的人了解本发明的内容并加以实施,并不能以此限制本发明的保护范围,凡根据本发明精神实质所做的等效变化或修饰,都应涵盖在本发明的保护范围内。
Claims (8)
1.一种基于苯并噻二唑衍生物的热激活延迟材料,其特征在于,具体结构如下:
其中R包含以下基团:
2.根据权利要求1所述的一种基于苯并噻二唑衍生物的热激活延迟材料,其特征在于,所述的苯并噻二唑衍生物的热激活延迟材料包括以下一种或者几种化合物:
3.根据权利要求2所述的一种基于苯并噻二唑衍生物的热激活延迟材料,其特征在于,所述的苯并噻二唑衍生物的热激活延迟材料包括以下一种或者几种化合物:
4.根据权利要求3所述的一种基于苯并噻二唑衍生物的热激活延迟材料,其特征在于,所述的苯并噻二唑衍生物的热激活延迟材料包括以下一种或者两种化合物:
5.一种基于苯并噻二唑衍生物的热激活延迟材料的制备方法,其特征在于,按照如下路线制备:
其中R包含以下基团:
6.根据权利要求5所述的基于苯并噻二唑衍生物的热激活延迟材料的制备方法,其特征在于,R包含以下基团:
7.根据权利要求6所述的基于苯并噻二唑衍生物的热激活延迟材料的制备方法,其特征在于,R包含以下基团:
8.一种根据权利要求1-4任一项所述的基于苯并噻二唑衍生物的热激活延迟材料在作为发光层制备的OLED器件中的应用。
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