CN114890986A - 一种硫杂芴基聚集诱导发光化合物的制备方法及应用 - Google Patents
一种硫杂芴基聚集诱导发光化合物的制备方法及应用 Download PDFInfo
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Abstract
本发明提供了一种硫杂芴基聚集诱导发光化合物的制备方法及应用,涉及有机合成领域。本发明提供的硫杂芴基聚集诱导发光化合物具有式1所示结构,该化合物合成方法简单,分离纯化的操作工艺简便。本发明的产物分子具有聚集诱导发光性质,丰富了聚集诱导发光类化合物的品种,产品在有机功能材料领域具有广阔的应用前景。
Description
技术领域
本发明涉及有机合成技术领域,特别涉及一种硫杂芴基聚集诱导发光化合物的制备方法及应用。
背景技术
有机荧光材料是一类具有发光性质的化合物,在特定波长的光照射之后,光的能量使得化合物的一些电子由基态跃迁至激发态,而激发态是一种不稳定的状态,倾向于通过弛豫回到基态,在此过程中,化合物吸收的部分能量以光子形式释放,从而产生了荧光。一些荧光分子在溶液中具有良好的荧光性质,但在高浓度或者聚集态时,这种荧光分子的基态和激发态更容易相互碰撞形成激基复合物和激基缔合物,导致化合物吸收的能量更多的以非辐射跃迁的形式释放,从而导致荧光发生淬灭。这种发光材料在聚集态时荧光发生减弱甚至淬灭的现象称为聚集诱导荧光淬灭(Aggregation-Caused Quenching, ACQ),这极大地限制了有机发光材料的应用。
具有aggregation-induced emission(AIE)性质的荧光分子在溶液中无荧光或有弱荧光,但在聚集态下其发光能力会大大提高,这为有机发光材料的应用打开了新的大门。具有聚集诱导发光性质的化合物在生物、化学传感、智能材料、有机光电材料等领域有重要应用,因此,开发具有聚集诱导发光性质的化合物具有重要意义。三苯胺基团是一种重要的构建具有AIE性质化合物的基团,具有三苯胺基团的化合物在溶液中时可以通过自发旋转耗散能量,在聚集态时这种分子运动会受到抑制,从而发出荧光。在众多已被报道的AIE分子中,基于三苯胺取代的硫杂芴基AIE分子的报道还很少,在为数不多的例子中,其合成方法都十分繁琐,且分离及纯化等处理过程非常复杂。
发明内容
本发明的目的在于提供一种硫杂芴基聚集诱导发光化合物的制备方法及应用。本发明提供的化合物合成方法简单,分离纯化的操作工艺简便,目标产物具有聚集诱导发光性质。
本发明提供了一种硫杂芴基聚集诱导发光化合物的制备方法及应用,其特征在于,目标产物具有如下所示结构:
本发明提供了上述化合物的制备方法,包括以下合成步骤:
将一定量的2,8-二溴硫杂芴、4-(N,N-二苯基胺基)苯硼酸频哪醇酯、四(三苯基膦)钯、碳酸钾和一定量的甲苯在反应瓶中混合,加热到一定温度,在该温度下搅拌反应一定的时间,反应混合物经溶剂稀释、萃取、分离、干燥及回收溶剂等步骤得到粗产物,利用柱层析分离得到目标产物的溶液,回收溶剂后得到化合物1。
本发明提供的硫杂芴基聚集诱导发光化合物为给体-受体-给体结构,具有聚集诱导发光性质。在溶液中,两侧的三苯胺基团类似于螺旋桨结构,可自由旋转,激发态能量通过非辐射跃迁耗散,无荧光发射,当在聚集态时,苯环的旋转受到抑制,激发态能量通过辐射跃迁耗散,有荧光发射。本发明丰富了聚集诱导发光类化合物的种类。
本发明提供了所述化合物的制备方法,本发明提供的合成方法简单,分离纯化的操作工艺简便,原料易得,产率较高,适合放大量合成及今后的规模化生产。
附图说明
图1为化合物1的1H NMR图。
图2为化合物1的13C NMR图。
图3为化合物1在不同甲苯体积分数(f t )的二甲基亚砜/甲苯混合溶液中的荧光光谱。
图4为化合物1在二甲基亚砜/甲苯混合溶液中荧光发射波长和实时荧光强度随不同甲苯体积分数变化的曲线图。
具体实施方式
实施例
将181 mg 2,8-二溴硫杂芴、526 mg 4-(N,N-二苯基胺基)苯硼酸频哪醇酯、62 mg四(三苯基膦)钯、147 mg碳酸钾和7 mL甲苯在反应瓶中混合,搅拌5 min使原料充分溶解,在氮气的保护下,100 ℃条件下搅拌反应20 h。反应结束后降至室温,用30 mL二氯甲烷稀释反应液并转移到分液漏斗中,有机相用饱和氯化铵水溶液洗涤两次,每次40 mL,分离出有机相后,水相合并后用二氯甲烷萃取两次,每次20 mL,合并有机相用3 g无水硫酸钠干燥20 min,干燥后的有机相通过减压蒸馏回收溶剂后得到粗产物,用200-300目硅胶柱层析分离,所用洗脱剂为100:1的石油醚和二氯甲烷,收集第四带为目标产物溶液,减压蒸馏回收溶剂,得到213 mg黄色固体,产率为60%;
对所得黄色固体进行表征,具体数据如下:
1H NMR (500 MHz, CDCl3) δ 8.39 (d, J = 0.5 Hz, 2H), 7.91 (d, J = 8.3Hz, 2H), 7.71 (dd, J = 8.3, 1.3 Hz, 2H), 7.61 (d, J = 8.5 Hz, 4H), 7.30 (t, J= 7.9 Hz, 8H), 7.19 (dd, J = 16.0, 8.1 Hz, 12H), 7.06 (t, J = 7.3 Hz, 4H).13CNMR (126 MHz, CDCl3) δ 147.71, 147.26, 138.55, 137.48, 136.17, 135.08,129.35, 128.06, 125.92, 124.45, 124.11, 123.13, 123.00, 119.58.
根据上述表征数据可知,所得黄色固体为化合物1。
化合物1的AIE性质测试:在不同甲苯体积分数(f t )的二甲基亚砜/甲苯混合溶液中分别加入20 μL化合物1的二甲基亚砜溶液(2 mM),得到20 μM的化合物1溶液。分别测定不同甲苯体积分数的混合溶液中化合物1的荧光强度。
Claims (6)
2.一种硫杂芴基聚集诱导发光化合物的制备方法及应用,其特征在于:化合物1的制备方法中反应物的质量比为,2,8-二溴硫杂芴:4-(N,N-二苯基胺基)苯硼酸频哪醇酯:四(三苯基膦)钯:碳酸钾的质量比为1:2.906:0.343:0.812。
3.一种硫杂芴基聚集诱导发光化合物的制备方法及应用,其特征在于:化合物1的制备方法中反应用的溶剂是甲苯,用量为每克2,8-二溴硫杂芴用38.7 mL。
4.一种硫杂芴基聚集诱导发光化合物的制备方法及应用,其特征在于:化合物1的制备方法中反应温度为100 ℃。
5.一种硫杂芴基聚集诱导发光化合物的制备方法及应用,其特征在于:化合物1的制备方法中反应时间为20 h。
6.一种硫杂芴基聚集诱导发光化合物的制备方法及应用,其特征在于:化合物1具有聚集诱导发光性质。
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WO2019041847A1 (zh) * | 2017-08-30 | 2019-03-07 | 华南理工大学 | 一种基于萘并硫氧芴单元的蓝光聚合物发光材料及其制备方法与应用 |
CN109564972A (zh) * | 2017-03-09 | 2019-04-02 | 株式会社Lg化学 | 有机发光元件 |
CN114163338A (zh) * | 2020-09-11 | 2022-03-11 | 东进世美肯株式会社 | 反射性电极保护层用化合物以及包含所述化合物的背面发光元件 |
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CN109564972A (zh) * | 2017-03-09 | 2019-04-02 | 株式会社Lg化学 | 有机发光元件 |
WO2019041847A1 (zh) * | 2017-08-30 | 2019-03-07 | 华南理工大学 | 一种基于萘并硫氧芴单元的蓝光聚合物发光材料及其制备方法与应用 |
CN114163338A (zh) * | 2020-09-11 | 2022-03-11 | 东进世美肯株式会社 | 反射性电极保护层用化合物以及包含所述化合物的背面发光元件 |
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