CN113292585B - 一种bodipy-苯并噻二唑-卟啉-咔唑四元体系线型化合物及其制备方法 - Google Patents
一种bodipy-苯并噻二唑-卟啉-咔唑四元体系线型化合物及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种BODIPY‑苯并噻二唑‑卟啉‑咔唑四元体系线型化合物及其制备方法,其化学结构如(I)所示,该化合物以5,15‑二(3,5‑二(十二烷氧基)苯基)‑10,20双溴锌卟啉衍生物(II)为起始原料,与对乙炔基苯基咔唑衍生物(III)发生Sonogashira反应得到咔唑基单溴卟啉衍生物(IV),然后再和乙炔基苯并噻二唑BODIPY衍生物(V)通过Sonogashira反应得到如式(I)所示的BODIPY‑苯并噻二唑‑卟啉‑咔唑四元体系线型化合物。该化合物制备方法简单、反应条件温和、操作简便,吸收范围广,且在分子内能发生有效的能量转移过程,可用于光储材料、太阳能电池、分子传感器等方面。
Description
技术领域
本发明属于有机合成技术领域,涉及一种BODIPY-苯并噻二唑-卟啉-咔唑四元体系线型化合物的制备方法。
背景技术
卟啉是一类具有高度π共轭结构的大环类化合物,它具有良好的配位性能、优异的光物理性质能及独特的自组装性能,在太阳能电池、催化、液晶材料和生物医学等方面有着广泛的应用。卟啉类衍生物是一种化学性质非常稳定的物质,可见光区域卟啉衍生物有很强的吸收,被适当波长的光子激发后,卟啉类化合物即可激活一系列氧化还原反应。当卟啉通过桥联其他荧光团形成聚合物后,可被应用于设计推-拉π共轭体系和具有光电应用的树枝状分子天线中。其中,苯并噻二唑类衍生物由于其缺电子性质常被作为体系中的受体部分
氟硼二吡咯(BODIPY)是一类常见的荧光染料,其母核上的3和5位是α-位,1,2,6,7位是β-位,8位是meso-位,由硼原子和亚甲基连接两个吡咯环,将中心骨架固定在同一平面上产生共轭平面,使分子具有较好的刚性结构。BODIPY类化合物的吸收波长在500nm左右,不仅具有较高的荧光量子产率和摩尔消光系数,而且还具有良好的光、电化学稳定性等,因此BODIPY类荧光染料被广泛用于荧光探针、生物医学、材料化学等领域。
咔唑分子是一种典型的含N芳香杂环化合物,具有多个化学反应的活性位点,由于其在紫外区有较强的吸收,其能隙约为3.2eV,常被用来设计合成蓝色的荧光材料。咔唑在具有良好的空穴传输能力同时也有较高的三线态能级,通过在不同位置修饰引入具有电子传输能力的基团,可以构建出具有双极性传输性质的主体发光材料。此外,咔唑还具有较强给电子能力,通过在不同位点引入吸电子基团来调节其HOMO和LUMO轨道的重叠程度,进而改变其能隙大小,可以合成出具有不同发光颜色的有机发光材料。
基于卟啉、咔唑及BODIPY类衍生物的优点,本发明设计合成了一种BODIPY-苯并噻二唑-卟啉-咔唑四元分子体系衍生物。将咔唑和苯并噻二唑类衍生物引入到体系中构建供体-受体型分子,而又与BODIPY衍生物偶联能够有效弥补卟啉分子在可见光内吸收的不足,无论从合成还是应用研究方面都值得开展更深入、更有成效的研究工作,而且关于这方面研究还很少有过报道。
发明内容
发明目的:针对现有技术中存在的不足,本发明的目的是提供一种BODIPY-苯并噻二唑-卟啉-咔唑四元体系线型化合物及其制备方法。
技术方案:为了实现上述发明目的,本发明采用的技术方案为:
本发明涉及的一种BODIPY-苯并噻二唑-卟啉-咔唑四元体系线型化合物的结构如下:
本发明涉及的一种BODIPY-苯并噻二唑-卟啉-咔唑四元体系线型化合物的合成路线为:
本发明涉及的一种BODIPY-苯并噻二唑-卟啉-咔唑四元体系线型化合物的制备过程包括以下步骤:
步骤1:在氩气保护条件下,将5,15-二(3,5-二(十二烷氧基)苯基)-10,20双溴锌卟啉衍生物(II)和对乙炔基苯基咔唑衍生物(III)溶解于四氢呋喃和三乙胺的混合溶剂中,并迅速于反应器中加入催化剂四(三苯基膦)钯和碘化亚铜,在70-80℃反应12~16小时,反应结束后冷至室温,蒸干有机溶剂后通过硅胶柱层析分离提纯得到咔唑基单溴卟啉衍生物(IV);
步骤2:在氩气保护条件下,将咔唑基单溴卟啉衍生物(IV)和乙炔基苯并噻二唑BODIPY衍生物溶解于四氢呋喃和三乙胺的混合溶剂中,并迅速于反应器中加入催化剂四(三苯基膦)钯和碘化亚铜,在70-80℃反应12~16小时,反应结束后冷至室温,蒸干有机溶剂后通过硅胶柱层析分离提纯得到BODIPY-苯并噻二唑-卟啉-咔唑四元体系线型化合物(I)。
上述反应步骤1中,5,15-二(3,5-二(十二烷氧基)苯基)-10,20双溴锌卟啉衍生物(H)与4-对乙炔基苯基咔唑衍生物(III)的物质的量之比为2.0~2.5∶1;
上述反应步骤1和步骤2中,催化剂四(三苯基膦)钯用量为反应物原料物质的量的10~20%;
上述反应步骤1和步骤2中,催化剂碘化亚铜的用量为反应物原料物质的量的10~20%;
上述反应步骤2中,咔唑基单溴卟啉衍生物(IV)与乙炔基苯并噻二唑BODIPY衍生物(V)的物质的量比为1∶1.1~1.2。
本发明的有益效果:
与现有技术相比,本发明中BODIPY-苯并噻二唑-卟啉-咔唑四元体系线型化合物及制备方法所具有的优点有:(1)BODIPY-苯并噻二唑-卟啉-咔唑四元体系线型物具有宽的吸收光谱,并在不同的荧光团之间能发生高效的能量转移过程,可用于太阳能电池和光吸收天线等方面;(2)合成路线简单、反应条件温和、反应选择性好、分离方法简易,具有普适性,可以推广应用到类似多功能基团化合物的合成。
附图说明
图1为本发明BODIPY-苯并噻二唑-卟啉-咔唑四元体系线型化合物(I)的紫外-可见吸收光谱;
图2为本发明BODIPY-苯并噻二唑-卟啉-咔唑四元体系线型化合物(I)在408nm激发波长下的荧光发射光谱;
图3为本发明BODIPY-苯并噻二唑-卟啉-咔唑四元体系线型化合物(I)在498nm激发波长下的荧光发射光谱。
具体实施方式
下面结合具体实例对本发明作进一步地解释,具体实施事例并不对本发明作任何限定。
用紫外-可见光谱和荧光光谱表征化合物的结构并研究化合物的光物理性质。检测所用仪器为:岛津UV-3100型紫外-可见分光光度计(扫描范围300~900nm,光路狭缝2nm),荧光光谱用美国Amico Bowman Series 2 Luminescence Spectrometer测试。
实施例1
在氩气保护条件下,将5,15-二(3,5-二(十二烷氧基)苯基)-10,20双溴锌卟啉衍生物(II)(0.524mmol)和对乙炔基苯基咔唑衍生物(III)(0.262mmol)溶解于四氢呋喃(20mL)和三乙胺(3mL)的混合溶剂中,并迅速于反应器中加入催化剂四(三苯基膦)钯(0.013mmol)和碘化亚铜(0.026mmol),在70℃反应12小时,反应结束后冷至室温,蒸干有机溶剂后,以二氯甲烷-石油醚为洗脱剂通过硅胶柱层析分离提纯得到咔唑基单溴卟啉衍生物(IV),产率34%。1H NMR(600MHz,CDCl3,ppm)δ9.75-9.74(d,J=4.2Hz,2H),9.68-9.67(d,J=4.2Hz,2H),9.09(d,J=4.8Hz,2H),9.04-9.03(d,J=4.8Hz,2H),8.20-8.17(m,4H),7.79-7.78(d,J=7.8Hz,2H),7.59-7.58(d,J=8.4Hz,2H),7.49-7.47(t,J=7.8Hz,2H),7.35-7.32(m,6H),6.89(t,J=1.8Hz,2H),4.14-4.12(d,J=6.6Hz,8H),1.89-1.86(m,8H),1.52-1.49(m,8H),1.38-1.35(m,8H),1.27-1.23(m,56H),0.85-0.83(t,J=6.6Hz,12H)。
实施例2
在氩气保护条件下,将咔唑基单溴卟啉衍生物(IV)(0.088mmol)和乙炔基苯并噻二唑BODIPY衍生物(V)(0.106mmol)溶解于四氢呋喃(15mL)和三乙胺(5mL)的混合溶剂中,并迅速于反应器中加入催化剂四(三苯基膦)钯(0.0176mmol)和碘化亚铜(0.0176mmol),在70℃反应12小时,反应结束后冷至室温,蒸干有机溶剂以二氯甲烷-石油醚为洗脱剂通过硅胶柱层析分离提纯得到BODIPY-苯并噻二唑-卟啉-咔唑四元体系线型化合物(I),产率17%。1H NMR(600MHz,CDCl3,ppm)δ9.26-9.25(m,2H),9.04-8.96(m,6H),8.24-8.23(d,J=6.6Hz,2H),8.09-8.07(d,J=7.2Hz,2H),7.67-7.66(d,J=7.8Hz,4H),7.59-7.57(d,J=7.8Hz,6H),7.48-7.46(m,6H),7.32-7.30(t,J=7.8Hz,2H),7.02(m,2H),5.99(m,2H),4.26-4.24(d,J=6.0Hz,8H),2.56-2.53(m,6H),198-1.95(m,8H),1.58-1.54(m,8H),1.44-1.41(m,8H),1.34-1.18(m,62H),0.81-0.79(t,J=6.6Hz,12H)。
UV-vis:313nm,464nm,501nm,655nm(图1);Emission Wavelength:666nm(λex=408nm)(图2)。
实施例3
在氩气保护条件下,将咔唑基单溴卟啉衍生物(IV)(0.088mmol)和乙炔基苯并噻二唑BODIPY衍生物(V)(0.097mmol)溶解于四氢呋喃(15mL)和三乙胺(5mL)的混合溶剂中,并迅速于反应器中加入催化剂四(三苯基膦)钯(0.017mmol)和碘化亚铜(0.035mmol),在80℃反应15小时,反应结束后冷至室温,蒸干有机溶剂以二氯甲烷-石油醚为洗脱剂通过硅胶柱层析分离提纯得到BODIPY-苯并噻二唑-卟啉-咔唑四元体系线型化合物(I),产率20%。
实施例4
将BODIPY-苯并噻二唑-卟啉-咔唑四元体系线型化合物(I)溶于二氯甲烷中,配置成浓度为1×10-5mol/L二氯甲烷溶液,测定其紫外-可见吸收光谱。图1为本发明实施例2制备的荧光染料(I)溶液紫外-可见吸收光谱。
实施例5
将BODIPY-苯并噻二唑-卟啉-咔唑四元体系线型化合物(I)溶于二氯甲烷中,配置成浓度为1×10-6mol/L二氯甲烷溶液,测定其荧光发射光谱。图2为本发明实施例2制备的荧光染料(I)溶液荧光光谱。
Claims (7)
3.如权利要求2所述的制备方法,其特征在于,所述制备方法包括以下步骤:
步骤1:在氩气保护条件下,将5,15-二(3,5-二(十二烷氧基)苯基)-10,20双溴锌卟啉衍生物(II)和对乙炔基苯基咔唑衍生物(III)溶解于四氢呋喃和三乙胺的混合溶剂中,并迅速于反应器中加入催化剂四(三苯基膦)钯和碘化亚铜,在70-80℃反应12~16小时,反应结束后冷至室温,蒸干有机溶剂后通过硅胶柱层析分离提纯得到咔唑基单溴卟啉衍生物(IV);
步骤2:在氩气保护条件下,将咔唑基单溴卟啉衍生物(IV)和乙炔基苯并噻二唑BODIPY衍生物(V)溶解于四氢呋喃和三乙胺的混合溶剂中,并迅速于反应器中加入催化剂四(三苯基膦)钯和碘化亚铜,在70-80℃反应12~16小时,反应结束后冷至室温,蒸干有机溶剂后通过硅胶柱层析分离提纯得到BODIPY-苯并噻二唑-卟啉-咔唑四元体系线型化合物(I)。
4.根据权利要求3所述的制备方法,其特征在所述步骤1中,5,15-二(3,5-二(十二烷氧基)苯基)-10,20双溴锌卟啉衍生物(II)与对乙炔基苯基咔唑衍生物(III)的物质的量之比为2.0~2.5∶1。
5.根据权利要求3所述的制备方法,其特征在所述步骤1和步骤2中,催化剂四(三苯基膦)钯用量为反应物原料物质的量的10~20%。
6.根据权利要求3所述的制备方法,其特征在所述步骤1和步骤2中,催化剂碘化亚铜的用量为反应物原料物质的量的10~20%。
7.根据权利要求3所述的制备方法,其特征在所述步骤2中,咔唑基单溴卟啉衍生物(IV)与乙炔基苯并噻二唑BODIPY衍生物(V)的物质的量比为1∶1.1~1.2。
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