CN115368275A - 一类基于氰基苯乙烯的聚集诱导发光材料及其制备方法和应用 - Google Patents
一类基于氰基苯乙烯的聚集诱导发光材料及其制备方法和应用 Download PDFInfo
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Abstract
Description
技术领域
本发明属于有机光功能材料合成领域,特别涉及一类基于氰基苯乙烯的聚集诱导发光材料及其制备方法和在化学易挥发有毒气体传感检测领域中的应用。
背景技术
盐酸作为重要的工业化学品,在金属冶炼、酸洗钢材和工业高分子材料制备等领域具有重要的应用。此外,氨水在农业制造化肥、工业洗涤和印染以及军事消毒液等领域具有广泛的应用价值。然而,工业生产盐酸和氨水制剂时往往面临着危险化学品泄漏的问题,对生命安全造成巨大的潜在风险。荧光传感器对于早期警示氯化氢和氨气有毒气体泄漏具有显著优点,如:灵敏度高、响应速度快、操作简单、成本低、易携带和光学性能易调控等。然而,目前用于制备氯化氢和氨气传感器的染料大多只能实现单一的颜色或荧光变化,具有可见颜色和荧光双重响应变化的传感器仍然十分稀有。此外,已报道的氯化氢气体荧光传感器以荧光猝灭型(turn off)为主,该类型荧光传感器的灵敏性不高。
相反,具有荧光“点亮”(turn on)特性的新型比色-荧光双重响应的气体传感器具有灵敏度和精准度高的优势。例如,湖南大学Jiang教授团队基于含醛基的四苯乙烯荧光单体和对苯二胺成功构筑一类新型共价有机框架(COF)传感器,成功实现氯化氢和氨气的比色-荧光双重传感效果,但该类COF荧光传感材料需要严格控制反应条件和反应底物摩尔当量比方可实现,且原材料需要经过复杂的合成过程。此外,由于材料结构含有大量的碳氮双键,导致材料结构稳定性较差,不利于实际工业场景的应用。(A gaseous hydrogenchloride chemosensor based on a 2D covalent organic framework,Chem.Commun.,2019,55,4550-4553)
因此,通过简单的合成方法高效率地制备具有良好稳定性的氯化氢和氨气比色-荧光双重传感材料具有重要意义。
发明内容
本发明的目的是提供一类基于氰基苯乙烯的具有聚集诱导发光性质的荧光材料,其可以用于检测易挥发的氯化氢和氨气有毒气体。
本发明的又一目的是提供上述基于氰基苯乙烯的聚集诱导发光性质的荧光材料的制备方法及其应用。
本发明目的基于如下技术方案实现:
一类基于氰基苯乙烯的具有聚集诱导发光性质的荧光材料,具有如下式(I)所示结构:
其中,R1独立地为C1-18烷基胺基、C1-18烷基氧基中的一种;R2独立地为氢、C1-3烷基、卤素、羟基中的一种;R3独立地为卤素、芳基、杂芳基、氨基、硝基、烷基氧基中的一种。
所述的烷基可为直链或支链烷基;例如,甲基、乙基、丙基、丁基、异丁基、叔丁基等。
所述的芳基指具有6-20个碳原子的单环或多环芳族基团,代表性的芳基包括:苯基、萘基、联苯基等。
所述的杂芳基指具有1-20个碳原子、1-4个选自N、S、O杂原子的单环或多环杂芳族基团,代表性的杂芳基包括:吡咯基、吡啶基、噻吩基、噻唑基、氮杂蒽基等。
在本发明的一个实施方式中,R1独立地为C1-6烷基胺基、C1-6烷基氧基。
在本发明的另一个实施方式中,R2独立地为氢、卤素、甲基、羟基。
在本发明的又一个实施方式中,R3独立地为卤素、芳基、氨基、硝基。
优选的,本发明提供的一类基于氰基苯乙烯的具有聚集诱导发光性质的荧光材料,具有如下式(Ia)所示结构:
其中,R1独立地为C1-18烷基胺基、C1-18烷基氧基中的一种;R2独立地为氢、C1-3烷基、卤素、羟基中的一种;R3独立地为卤素、芳基、杂芳基、氨基、硝基、烷基氧基中的一种。
优选的,式(Ia)中,R1为二甲基胺基,R2为氢,R3为溴。此时式(Ia)的化合物为(Z)-2-(4-溴苯基)-3-(4-(二甲基胺基)苯基)氰基乙烯,结构式如下所示:
本发明还提供了一种上述式(I)所示的一类基于氰基苯乙烯的具有聚集诱导发光性质的荧光材料的制备方法,将化合物(II)与化合物(III)在有机碱催化下,反应得到式(I)所示结构的化合物,合成路线如下所示:
其中,R1独立地为C1-18烷基胺基、C1-18烷基氧基中的一种;R2独立地为氢、C1-3烷基、卤素、羟基中的一种;R3独立地为卤素、芳基、杂芳基、氨基、硝基、烷基氧基中的一种。
具体制备步骤如下:
在有机碱催化条件下将化合物(II)和化合物(III)在溶剂中回流搅拌,反应完成后,过滤出沉淀并用乙醇洗涤,在真空下干燥得到式(I)所示结构的化合物。
进一步地,所述有机碱为四丁基氢氧化铵。
进一步地,所述溶剂为乙醇。
进一步地,所述化合物(II)和化合物(III)的摩尔比为1∶1~1∶5。
进一步地,所述回流搅拌的温度为80℃~100℃。
进一步地,所述回流搅拌的时间为8~12小时。
本发明基于调控分子内电荷转移效应的设计思路,合成了光学性质优异且在危险化学气体传感器领域具有良好应用前景的聚集诱导发光材料。具体为:
本发明所合成化合物具有聚集诱导发光(AIE)性质,其制备方法具有合成方法简单、原料易得、反应时间短、纯化过程简便等优势。本发明优选具有强给电子基团的芳基醛作为反应底物,所合成的化合物具有转子结构,在溶液态下分子剧烈运动,化合物不发光;当所合成的化合物聚集时,分子运动受限,导致荧光信号显著放大。此外,本发明所合成化合物结构中强的给电子基团与酸性气体具有较强的酸碱作用,当与酸性气体接触时,化合物结构中的碱性基团易被质子化,从而大大削弱其给电子能力,导致分子内电荷转移效应被破坏,最终导致化合物的颜色和荧光光色及强度均产生极大变化。进一步利用碱性气体熏蒸酸质子化的荧光化合物,有效破坏化合物与酸的结合作用,从而恢复本发明所合成化合物的本征性能。
进而,本发明还提供了所合成化合物在制备氯化氢或氨气两类毒性气体荧光传感器中的应用,实现了比色-荧光的双重荧光传感用途。
根据本发明,所述的酸性气体可为二氧化碳、二氧化硫、硫化氢和氯化氢;所述的碱性气体为氨气。
进一步地,本发明提供了所合成化合物对氯化氢气体具有特异性响应的传感应用。具体为,将本发明所合成化合物制备成便携式滤纸后,放置于含有氯化氢气体的环境中,根据滤纸颜色、荧光光色和强度的变化,即可判断是否实现氯化氢气体的传感作用。
进一步地,本发明提供了所合成化合物对氨气具有特异性响应的传感应用。具体为,利用氯化氢熏蒸后的滤纸放置于含有氨气的环境中,根据滤纸颜色、荧光光色和强度的变化,即可判断是否实现氨气的传感作用。
本发明还提供了所合成化合物在氯化氢气体和氨气刺激下可以实现信息的加密和解密。具体为,利用本发明所合成材料在滤纸上涂写数字信息,通过氯化氢气体熏蒸,实现肉眼可见的数字信息擦除效果,但在紫外光照射下只显示部分数字。进一步利用氨气熏蒸,实现快速的数字信息恢复。
本发明所合成化合物即使经过氯化氢气体——氨气反复熏蒸5次后仍然可以保持原始材料的性能,具有良好的稳定性。
相比现有技术,本发明至少具有以下有益效果:
(1)本发明所合成化合物具有聚集诱导发光(AIE)性质,其合成方法简单、原料易得、反应时间短、纯化过程简便。
(2)本发明所合成化合物可以反复用于氯化氢气体和氨气的荧光传感,具有良好的稳定性,传感次数可以实现5次以上仍然保持良好的性能。
(3)本发明所合成化合物可以对氯化氢气体和氨气进行特异性传感识别,具有良好的稳定性和快速响应性。该材料制备的试纸条响应速度快、易携带,可以在几秒内释放明显的传感信号。
(4)本发明所合成化合物还可以实现信息的加密和解密,在信息加密和快速解密领域也具有良好的应用潜力。
附图说明
图1为NEBN-Br和NEBN-NO2在THF溶液中的归一化的紫外吸收光谱;以及NEBN-Br和NEBN-NO2在THF溶液中的归一化的荧光发射光谱;样品浓度测试浓度均为10μM。
图2为NEBN-Br在不同有机溶剂中的归一化的荧光发射光谱,λex=400nm;以及NEBN-NO2在不同有机溶剂中的归一化的荧光发射光谱,λex=450nm;样品浓度测试浓度均为10μM。
图3为随着H2O含量增加NEBN-Br(10μM)在H2O/THF(v/v)混合溶剂中的荧光发射谱图,λex=400nm;以及随着H2O含量增加NEBN-NO2(10μM)在H2O/THF(v/v)混合溶剂中的荧光发射谱图,λex=450nm。
图4为NEBN-Br在THF溶液中不同时间下的荧光光谱图,λex=365nm,样品浓度测试浓度为10μM;以及NEBN-Br的荧光强度与时间的线性关系图。
图5为NEBN-Br在不同pH值下的荧光光谱图,λex=400nm,样品浓度测试浓度为10μM。
图6为NEBN-Br在不同酸性气体熏蒸后的荧光光谱图,λex=400nm;以及NEBN-Br在不同酸性气体熏蒸后荧光强度变化图。
图7为NEBN-Br薄膜经过氯化氢气体和氨气熏蒸后的荧光光谱图,λex=400nm;以及NEBN-Br薄膜经过氯化氢气体和氨气5次循环熏蒸后的荧光强度变化图,λex=400nm。
图8为NEBN-Br和NEBN-NO2在数字信息加密和解密中的应用效果图。
具体实施方式
下面结合具体实施例和附图,对本发明作进一步详细的阐述。
实施例1
按照如下合成路线,具体合成以下化合物:
(Z)-2-(4-溴苯基)-3-(4-(二甲基胺基)苯基)氰基乙烯(NEBN-Br)的合成
在TBAH催化条件下将二甲胺基苯甲醛(740mg,5mmol)和对溴苯乙腈(970mg,5mmol)在乙醇溶剂(20mL)于80℃回流搅拌8小时。在反应完成后,过滤出沉淀并用乙醇洗涤(10mL×3),在真空下干燥得到黄色固体产物,产率为87%(1.41g)。
1H NMR(CD2Cl2,500MHz):δ7.84(d,J=15Hz,2H),7.55-7.49(m,4H),7.40(s,1H),6.72(d,J=10Hz,2H),3.46-3.40(m,4H),1.22-1.18(t,J=20Hz,6H);13C NMR(CD2Cl2,125MHz):144.08,135.29,132.98,128.13,122.17,120.44,112.43,45.88,13.62。
实施例2
按照如下合成路线,具体合成以下化合物:
(Z)-2-(4-硝基苯基)-3-(4-(二甲基胺基)苯基)氰基乙烯(NEBN-NO2)的合成
在TBAH催化下将二甲胺基苯甲醛(740mg,5mmol)和对硝基苯乙腈(810mg,6mmol)在乙醇溶剂(20mL)于90℃回流搅拌10小时。在反应完成后,过滤出沉淀并用乙醇洗涤(10mL×3),在真空下干燥得到暗红色固体产物,产率为93%(1.36g)。
1H NMR(CD2Cl2,500MHz):δ8.25(d,J=15Hz,2H),7.91(d,J=10Hz,2H),7.79(d,J=15Hz,2H),7.57(s,1H),6.78(d,J=15Hz,2H),3.48-3.43(m,4H),1.24-1.20(t,J=20Hz,6H);13C NMR(CD2Cl2,125MHz):148.01,145.44,143.62,133.78,125.87,125.43,120.12,112.87,46.19.13.57。
实施例3
按照如下合成路线,具体合成以下化合物:
(Z)-2-(4-氨基苯基)-3-(4-(二甲基胺基)苯基)氰基乙烯(NEBN-NH2)的合成
在TBAH催化下将二甲胺基苯甲醛(740mg,5mmol)和对氨基苯乙腈(660mg,7.5mmol)在乙醇溶剂(20mL)于100℃回流搅拌12小时。在反应完成后,过滤出沉淀并用乙醇洗涤(10mL×3),在真空下干燥得到暗红色固体产物,产率为81%(1.06g)。
1H NMR(CD2Cl2,500MHz)δ=7.79(d,J=10Hz,2H),7.43(d,J=10Hz,2H),7.22(s,1H),6.71(t,J=10Hz,4H),3.78(s,2H),3.42-3.38(m,4H),1.22-1.18(t,J=20Hz,6H)。
实施例4
按照如下合成路线,具体合成以下化合物:
(Z)-3-(4-乙氧基苯基)-2-(4-(硝基)苯基)氰基乙烯(OEBN-NO2)的合成
在TBAH催化下将对乙氧基苯甲醛(750mg,5mmol)和对硝基苯乙腈(810mg,7mmol)在乙醇溶剂(20mL)于90℃回流搅拌10小时。在反应完成后,过滤出沉淀并用乙醇洗涤(10mL×3),在真空下干燥得到暗红色固体产物,产率为93%(1.36g)。
1H NMR(500MHz,CD2Cl2)δ=8.29(d,J=10Hz,2H),7.97(d,J=15Hz,2H),7.84(d,J=10Hz,2H),7.65(s,1H),7.01(d,J=5Hz,2H),4.15-4.10(m,2H),1.46-1.42(t,J=20Hz,3H).13C NMR(125MHz,CD2Cl2):163.20,148.83,146.42,142.59,133.23,127.69,126.97,125.55,119.08,116.32,107.38,65.31,15.78。
实施例5
按照如下合成路线,具体合成以下化合物:
(Z)-2-(4-溴苯基)-3-(4-(乙氧基苯基)-氰基乙烯(OEBN-Br)的合成
在TBAH催化下将对乙氧基苯甲醛(750mg,5mmol)和对溴苯乙腈(810mg,6mmol)在乙醇溶剂(20mL)于90℃回流搅拌12小时。在反应完成后,过滤出沉淀并用乙醇洗涤(10mL×3),在真空下干燥得到暗红色固体产物,产率为90%(1.47g)。
1H NMR(500MHz,CD2Cl2)δ=7.89(d,J=15Hz,2H),7.58-7.48(m,5H),6.98(d,J=10Hz,2H),4.12-4.07(m,2H),1.44-1.40(t,J=15Hz,3H).13C NMR(125MHz,CD2Cl2):162.46,143.40,135.35,133.39,132.59,128.56,127.40,123.90,119.41,65.16,15.80.
图1中的A为NEBN-Br和NEBN-NO2在THF溶液中的归一化的紫外吸收光谱,可以看出,在溶液态下,NEBN-Br的最大吸收峰值为400nm。而NEBN-NO2最大吸收峰值为450nm,NEBN-NO2具有更红的吸收峰主要归因于分子内电荷转移效应更强。图1中的B为NEBN-Br和NEBN-NO2在THF溶液中的归一化的荧光发射光谱,显示NEBN-Br在溶液态下最大发射峰为474nm,表现出一种蓝光发射;而NEBN-NO2在同样条件下测出的最大发射峰为596nm,源于NEBN-NO2具有较强的分子内电荷转移激发态性质。
图2中的A为NEBN-Br在不同极性溶剂中的荧光发射光谱图,可以看出,随着溶剂极性增大,NEBN-Br的最大发射峰逐渐红移,在低极性的正己烷溶剂中最大发射峰为459nm,而在高极性的N,N-二甲基甲酰胺溶剂中最大发射峰为494nm,红移了35nm。图2中的B为NEBN-NO2在不同极性溶剂中的荧光发射光谱图,可以看出,在低极性的正己烷溶剂中,NEBN-NO2的最大发射峰为478nm,而在高极性的N,N-二甲基甲酰胺溶剂中最大发射峰为619nm,红移了141nm,证明NEBN-NO2具有更强的分子内电荷转移激发态效应。
图3中的A为随着H2O含量增加NEBN-Br在H2O/THF(v/v)混合溶剂中的荧光发射谱图,可以看出,随着水含量的不断提升,NEBN-Br的荧光强度逐渐增大,且发光蓝移。图3中的B为随着H2O含量增加NEBN-NO2在H2O/THF(v/v)混合溶剂中的荧光发射谱图,可以看出,NEBN-NO2随着聚集体的形成,荧光强度先降低后增高,主要归因于分子内电荷转移效应和聚集诱导发光效应的协同作用。
图4中的A为NEBN-Br在THF溶液中不同时间下的荧光光谱图;图4中的B为NEBN-Br的荧光强度与时间的线性关系图。由图中可以看出,样品溶液在30天内,荧光强度几乎没有发生大幅度变化,仅仅轻微地下降少许,表明NEBN-Br具有良好的稳定性。
应用例1
实施例1所合成的化合物NEBN-Br对酸性气体和碱性气体的传感检测
图5为NEBN-Br在不同pH值下的荧光光谱图。由图可以看出,pH为3~14条件下,荧光强度几乎没有发生显著变化;当pH为1时,荧光强度大大提高,主要归因于NEBN-Br中碱性基团与强质子酸发生作用,大大削弱了碱性基团的供电子能力,破坏了分子内的电荷转移效应。
图6中的A为NEBN-Br在不同酸性气体熏蒸后的荧光光谱图;图6中的B为NEBN-Br在不同酸性气体熏蒸后荧光强度变化图。由图可以看出,NEBN-Br薄膜发出比较微弱的荧光,且最大发射峰为515nm,相较于其在四氢呋喃中的最大发射峰位置,薄膜态下荧光峰出现一定程度的红移,主要归因于聚集态下分子环境极性变大。当NEBN-Br薄膜受到硫化氢H2S和二氧化碳气体CO2熏蒸后,荧光强度有一定提高,且发光轻微蓝移,表明NEBN-Br与硫化氢和二氧化碳气体有一定作用。当与氯化氢气体HCl熏蒸后,荧光强度大幅度提高,且明显蓝移至433nm,表明NEBN-Br与氯化氢具有更强的结合力,有利于实现氯化氢气体的特异性传感。
应用例2
实施例1所合成的化合物NEBN-Br在氯化氢气体和氨气循环传感检测中的应用
图7中的A为NEBN-Br薄膜经过氯化氢气体和氨气熏蒸后的荧光光谱图,可以看出,当NEBN-Br薄膜受到氯化氢气体熏蒸后,薄膜的最大发射峰蓝移至433nm,当进一步受到氨气熏蒸后,薄膜荧光最大发射峰又恢复至初始峰515nm,表明NEBN-Br具有良好的氯化氢气体和氨气的可逆双重响应性质。图7中的B为NEBN-Br薄膜经过氯化氢气体和氨气5次循环熏蒸后的荧光强度变化图,可以看出,NEBN-Br薄膜即使经过5次氯化氢气体和氨气循环熏蒸,其荧光强度并未发生明显变化,显示出NEBN-Br良好的稳定性。将NEBN-Br制备成检测试纸条,试纸条在日光灯下为黄色,在紫外灯下发出明显的绿色荧光。当受到氯化氢气体熏蒸后,试纸条的颜色迅速褪去,变为白色,同时在紫外灯下发出明亮的蓝光。进一步用氨气熏蒸试纸条,颜色和荧光光色又得以恢复。
应用例3
实施例1所合成的化合物NEBN-Br和实施例2所合成的化合物NEBN-NO2在数字信息加密与解密中的应用
图8为NEBN-Br和NEBN-NO2在数字信息加密和解密中的应用效果图。图中的数字“17”是由化合物NEBN-NO2涂写而成,数字“6”是由化合物NEBN-Br涂写而成。两种化合物组合成数字“18”,在紫外灯照射下,只显示“6”的黄色荧光信号;当该数字“18”受到氯化氢气体熏蒸后,在日光灯下观察到数字“18”的颜色迅速褪去直至消失,在紫外灯下只能看到数字“6”的蓝色荧光信号;当进一步用氨气熏蒸时,数字“18”迅速恢复至初始颜色,且紫外灯下的荧光信号也和初始现象一致,表明本发明合成的化合物在信息加密和快速解密领域也具有良好的应用潜力。
尽管结合优选实施例对本发明进行了说明,但本发明并不局限于上述实施例,应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解,在阅读了本发明讲授的内容之后,本领域的技术人员可以对本发明作各种不背离本发明宗旨的改动或修改,这些等价形式同样落于本申请所附权利要求书所限定的范围。
Claims (10)
4.根据权利要求3所述的基于氰基苯乙烯的聚集诱导发光材料的制备方法,其特征在于,具体制备步骤如下:
在有机碱催化条件下将化合物(II)和化合物(III)在溶剂中回流搅拌,反应完成后,过滤出沉淀并用乙醇洗涤,在真空下干燥得到式(I)所示结构的化合物。
5.根据权利要求4所述的基于氰基苯乙烯的聚集诱导发光材料的制备方法,其特征在于,所述有机碱为四丁基氢氧化铵。
6.根据权利要求4所述的基于氰基苯乙烯的聚集诱导发光材料的制备方法,其特征在于,所述溶剂为乙醇。
7.根据权利要求4所述的基于氰基苯乙烯的聚集诱导发光材料的制备方法,其特征在于,所述化合物(II)和化合物(III)的摩尔比为1∶1~1∶5。
8.根据权利要求4所述的基于氰基苯乙烯的聚集诱导发光材料的制备方法,其特征在于,所述回流搅拌的温度为80℃~100℃。
9.根据权利要求4所述的基于氰基苯乙烯的聚集诱导发光材料的制备方法,其特征在于,所述回流搅拌的时间为8~12小时。
10.权利要求1-2任一项所述的基于氰基苯乙烯的聚集诱导发光材料在制备氯化氢或氨气两类毒性气体荧光传感器中的应用。
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