CN113307727A - 一种压致变色的四苯乙烯基化合物及其制备方法和应用 - Google Patents
一种压致变色的四苯乙烯基化合物及其制备方法和应用 Download PDFInfo
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Abstract
本发明涉及荧光材料技术领域,尤其涉及一种压致变色的四苯乙烯基化合物及其制备方法和应用。该四苯乙烯基化合物具备优异的压致变色性和分子聚集诱导荧光性,无需溶剂熏蒸和加热即可变色,并具有快速恢复性质。其制备方法为,将二苯乙炔与联硼酸频那醇酯反应制备二苯乙烯基硼酸频那醇酯,再与对溴苯取代基进行反应得到终产物。本发明中的压致变色的四苯乙烯基化合物的压致变色效应和快速恢复性质使其能够应用于制备室温下压致变色材料,并进一步应用于脑瘤成像技术、近红外探针技术以及光电器件等领域。
Description
技术领域
本发明属于荧光材料技术领域,具体涉及一种压致变色的四苯乙烯基化合物及其制备方法和应用。
背景技术
传统的有机染料在高浓度下会发生猝灭,这种聚集猝灭(ACQ)效应限制了其应用。基于分子内运动(RIM)机制的限制,具有聚集诱导发射(AIE)现象的新型压致荧光变色(MFC)材料克服了ACQ的缺点。
MFC材料因其独特的分子聚集诱导发光性、高发光效率、力致变色性、溶剂变色等优良特性使其在信息安全、记忆装置、传感器、荧光开关等方面有巨大的应用前景。作为一种新型智能材料,该类材料会随着研磨、按压等机械力的增加其发色团作出响应,进而使其颜色发生变化。
压致荧光变色材料的发光性质主要依赖于分子的排列顺序以及分子间的相互作用,所以可以通过各种外部刺激来改变分子堆积模式从而改变其发光特性。压致荧光变色化合物种类有待进一步丰富,以拓展荧光材料在光电器件等领域的应用。
四苯基乙烯(TPE)是典型的AIE模块,TPE基荧光聚合物的发光机理是由于周围芳环的分子内旋转受到限制。单个分子在溶液中通过分子内旋转激发态衰减;相反,在聚集态,分子内的旋转受到限制,聚集物阻塞了非辐射路径,导致高发射。因此,外围芳环的功能化可能触发TPE聚合物的发射行为变化。芳环上的取代基影响分子内的旋转,导致TPE基聚合物不寻常的发射现象。
然而目前已报道的四苯乙烯压致变色材料的合成工艺复杂,耗费时间较长,合成条件苛刻,因此,需要研发更多工艺简单的压致变色材料。
发明内容
针对以上技术问题,本发明提供一种压致变色的四苯乙烯基化合物及其制备方法和应用。该四苯乙烯基化合物具有优异的分子聚集诱导荧光效应,同时兼具有压致变色性,波长范围移动较宽等优异特性,且具有快速恢复的性质,可用于制备压致变色材料,从而能够进一步应用于脑瘤成像技术、近红外探针技术以及光电器件等领域。本发明提供的四苯乙烯基化合物的制备方法步骤简单,易于操作,适用于大规模生产。
为达到上述发明目的,本发明实施例采用了如下技术方案:
第一方面,本发明实施例提供了一种压致变色的四苯乙烯基化合物,其结构式如式(Ⅰ)所示:
其中R=OCH3、CH3、COOCH3、CN或NO2。
本发明所提供的四苯乙烯基化合物具备优异的压致变色性和分子聚集诱导荧光性,无需溶剂熏蒸和加热即可变色,并具有快速恢复性质,无需外界刺激即可恢复,在溶剂熏蒸或加热的条件下也能够恢复,故该化合物能够制成室温下压致变色染料,应用于脑瘤成像技术、近红外探针技术以及光电器件等领域。
第二方面,本发明还提供上述压致变色的四苯乙烯基化合物的制备方法,包括以下步骤:
步骤a、将二苯乙炔与联硼酸频那醇酯反应,制备二苯乙烯基硼酸频那醇酯;
步骤b、将所述二苯乙烯基硼酸频那醇酯与对溴苯取代基进行反应制备得到所述四苯乙烯基化合物,所述对溴苯取代基为对溴苯醚、对溴甲苯、对溴苯甲酸甲酯、对溴苯腈或对溴硝基苯。
其中,二苯乙烯基硼酸频那醇酯的结构式如式(II)所示:
本发明通过二苯乙炔与联硼酸频那醇酯反应,首先制备出了顺位的二苯乙烯硼酸频那醇酯,所得二苯乙烯硼酸频那醇酯再与不同对溴苯取代基进行铃木反应,即可得到上述不同取代基且取代基为顺位的四苯乙烯基化合物。该制备方法原料价格低廉,合成工艺简单,反应周期短,提高了反应效率。
优选地,步骤a中所述反应的温度为70~110℃,反应时间为8~10h,反应催化剂为四三苯基膦铂,溶剂为N,N-二甲基甲酰胺。四三苯基膦铂的摩尔量采用联硼酸频那醇酯摩尔量的1/200左右即可。在该反应条件下,8~10h即可完成反应。在实际操作中可通过薄层色谱等方式进行反应过程的监控,当二苯乙炔或联硼酸频那醇酯中至少一种基本完全消耗,即视为反应完成。
优选地,步骤b中所述反应的温度90~110℃,反应时间20~30h,反应催化剂为四三苯基膦钯、碳酸钾和四丁基溴化铵,所述四三苯基膦钯:碳酸钾:四丁基溴化铵的摩尔比为(0.1~0.2):(3~10):(3~10)。
优选地,步骤b中所述反应的溶剂为甲苯与水,体积比为(3~4):(1~1.5)。
优选地,所述制备方法还包括将步骤a所得产物进行精制,该精制的方法可选用以石油醚:二氯甲烷=2:1进行柱层析。
优选地,所述制备方法还包括将步骤a所得产物进行精制,该精制的方法可选用以石油醚:二氯甲烷=1:1进行柱层析。
第三方面,本发明实施例还提供了上述压致变色的四苯乙烯基化合物在制备室温下压致变色性荧光材料的应用。
本发明的有益效果在于:本发明提供的一系列四苯乙烯基化合物均具有较强的分子聚集诱导发光效应,以及优良的压致变色效应和快速恢复性质,能够拓宽该类染料在发光器件相关领域的应用市场。本发明所提供的该四苯乙烯基化合物的制备方法步骤简单易于实施,极大缩短了反应时间,提高了反应效率,且原料价格低廉,所得产物变色灵敏,并且具有自恢复性,无需外界刺激。因此,该制备方法能够推动和促进该四苯乙烯基化合物在有机光电、传感器及信息安全等领域的研究和应用进程。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合具体实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用于解释本发明,并不用于限定本发明。
下述实施例中,如无特殊说明,所使用的实验方法均为常规方法,所用材料、试剂等均可按常规商业途径获得。
实施例1
本实施例提供了一种四苯乙烯基顺位二醚的制备方法,具体包括以下步骤:
步骤a、将10.2g(40mmol)联硼酸频那醇酯与0.25g(0.2mmol)四三苯基膦铂加入到含50ml N,N-二甲基甲酰胺并且通有氮气的干燥反应容器中,再将3.6g(20mmol)二苯乙炔溶于50ml N,N-二甲基甲酰胺,配成溶液,滴入上述反应容器中,升温至90℃,在90℃条件下反应9h,冷却至室温,减压旋蒸得到二苯乙烯基硼酸频那醇酯的粗产物溶液,以石油醚:二氯甲烷=2:1为淋洗剂进行柱层析(固定相为硅胶)后,将洗脱液通过减压旋蒸去除溶剂,得到5.95g白色针状固体,即精制后的二苯乙烯基硼酸频那醇酯,产率85%,纯度为98%。所得白色针状固体的核磁共振氢谱数据1HNMRδH(400MHz,CDCl3):7.254-7.002(m,6H),6.952-6.937(m,4H),1.319-1.268(tttt,24H)。
步骤b、取3.50g(10mmol)步骤a得到的精制后的二苯乙烯基硼酸频那醇酯、3.74g(20mmol)对溴苯醚以及0.12g(0.1mmol)四三苯基膦钯溶解在160ml甲苯中,将1.38g(10mmol)碳酸钾和3.22g(10mmol)四丁基溴化铵溶解在40ml水中,将上述两种混合溶液加入到通有氮气的干燥反应容器中,升温至100℃,并在100℃条件下反应24小时(反应过程中利用回流装置以确保甲苯与水的体积比不变),冷却至室温,利用二氯甲烷萃取出合成粗产物,以石油醚:二氯甲烷=1:1为淋洗剂进行柱层析(固定相为硅胶),将洗脱液通过减压旋蒸去除溶剂,得到2.3g白色固体,产率60%,纯度为99%。
步骤b所得白色固体的定性检测数据为:
1HNMRδH(400MHz,CDCl3):7.079-7.055(m,6H),7.018-6.999(m,4H),6.953-6.936(m,4H),6.665-6.642(m,4H),3.744(tt,6H);
13CNMR(400MHz,CDCl3,TMS):158.029,144.28,139.745,136.500,132.577,131.479,127.745,127.632,126.252,55.148;
熔点(M.p):136-140℃;
MS(ESI):测得m/z为393.1[M+H](通过计算得到C28H24O2的m/z为392.18)。
由以上结果可知,步骤b所得白色固体为四苯乙烯基顺位二醚,结构式如式(I-I)所示。
实施例2
本实施例提供了一种四苯乙烯基二甲基的制备方法,具体包括以下步骤:
步骤a、将10.2g(40mmol)联硼酸频那醇酯与0.25g(0.2mmol)四三苯基膦铂加入到含50ml N,N-二甲基甲酰胺并且通有氮气的干燥反应容器中,再将3.6g(20mmol)二苯乙炔溶于50ml N,N-二甲基甲酰胺,配成溶液,滴入上述反应容器中,升温至85℃,在85℃条件下反应9.5h,冷却至室温,减压旋蒸得到二苯乙烯基硼酸频那醇酯的粗产物溶液,以石油醚:二氯甲烷=2:1为淋洗剂进行柱层析(固定相为硅胶)后,将洗脱液通过减压旋蒸去除溶剂,得到5.6g白色针状固体,产率80%。
步骤b、取3.50g(10mmol)步骤a得到的精制后的二苯乙烯基硼酸频那醇酯、3.42g(20mmol)4-溴甲苯以及0.12g(0.1mmol)四三苯基膦钯溶解在150ml甲苯中,将1.38g(10mmol)碳酸钾和3.22g(10mmol)四丁基溴化铵溶解在50ml水中,将上述两种混合溶液加入到通有氮气的干燥反应容器中,升温至110℃,并在110℃条件下反应20小时(反应过程中利用回流装置以确保甲苯与水的体积比不变),冷却至室温,利用二氯甲烷萃取出合成粗产物,以石油醚:二氯甲烷=1:1为淋洗剂进行柱层析(固定相为硅胶),将洗脱液通过减压旋蒸去除溶剂,得到1.8g白色固体,产率50%,纯度为99%。
步骤b所得白色固体的定性检测数据为:
1HNMRδH(400MHz,CDCl3):7.078-7.057(m,6H),7.015-6.996(m,4H),6.911(m,8H),2.261(tt,6H);
13CNMR(400MHz,CDCl3,TMS):144.278,141.085,140.547,136.017,131.510,131.334,128.547,127.701,126.345,21.359;
M.p:149-150℃;
MS(ESI):测得m/z为361.1[M+H](通过计算得到C28H24的m/z为360.18)。
由以上结果可知,步骤b所得白色固体为四苯乙烯基顺位二甲基,结构式如式(Ⅰ-Ⅱ)所示。
实施例3
本实施例提供了一种四苯乙烯基顺位二酯的制备方法,具体包括以下步骤:
步骤a、将10.2g(40mmol)联硼酸频那醇酯与0.25g(0.2mmol)四三苯基膦铂加入到含50ml N,N-二甲基甲酰胺并且通有氮气的干燥反应容器中,再将3.6g(20mmol)二苯乙炔溶于50ml N,N-二甲基甲酰胺,配成溶液,滴入上述反应容器中,升温至70℃,在70℃条件下反应10h,冷却至室温,减压旋蒸得到二苯乙烯基硼酸频那醇酯的粗产物,以石油醚:二氯甲烷=2:1为淋洗剂进行柱层析(固定相为硅胶)后,将洗脱液通过减压旋蒸去除溶剂,得到4.9g白色针状固体,产率70%。
步骤b、取2.43g(6.94mmol)步骤a得到的精制后的二苯乙烯基硼酸频那醇酯、3.06g(14.25mmol)4-溴苯甲酸甲酯以及0.15g(0.13mmol)四三苯基膦钯溶解在140ml甲苯中,将1g(6.94mmol)碳酸钾和1.2g(3.47mmol)四丁基溴化铵溶解在60ml水中,将上述两种混合溶液加入到通有氮气的干燥反应容器中,升温至100℃,并在100℃条件下反应28小时(反应过程中利用回流装置以确保甲苯与水的体积比不变),冷却至室温,利用二氯甲烷萃取出合成粗产物,以石油醚:二氯甲烷=1:1为淋洗剂进行柱层析(固定相为硅胶),将洗脱液通过减压旋蒸去除溶剂,得到2g白色固体,产率66%,纯度为99%。
步骤b所得白色固体的定性检测数据为:
1HNMRδH(400MHz,CDCl3):7.781-7.764(m,4H),7.130-7.078(m,10H),7.005-6.986(m,4H),3.869(tt,6H);
13CNMR(400MHz,CDCl3,TMS):166.839,148.178,142.617,141.412,131.308,131.229,129.200,128.414,127.949,127.095,52.069;
M.p:154-166℃;
MS(ESI):测得m/z为471.2(M+Na)(通过计算得到C30H24O4的m/z为448.17)。
由以上结果可知,步骤b所得白色固体为四苯乙烯基顺位二酯,结构式如式(Ⅰ-Ⅲ)所示。
实施例4
本实施例提供了一种四苯乙烯基顺位氰基的制备方法,具体包括以下步骤:
步骤a、将10.2g(40mmol)联硼酸频那醇酯与0.25g(0.2mmol)四三苯基膦铂加入到含50ml N,N-二甲基甲酰胺并且通有氮气的干燥反应容器中,再将3.6g(20mmol)二苯乙炔溶于50ml N,N-二甲基甲酰胺,配成溶液,滴入上述反应容器中,升温至100℃,在100℃条件下反应8h,冷却至室温,减压旋蒸得到二苯乙烯基硼酸频那醇酯的粗产物,以石油醚:二氯甲烷=2:1为淋洗剂进行柱层析(固定相为硅胶)后,将洗脱液通过减压旋蒸去除溶剂,得到5.74g白色针状固体,产率82%。
步骤b、取1.05g(3mmol)步骤a得到的精制后的二苯乙烯基硼酸频那醇酯、1.09g(6mmol)对溴苯氰以及0.11g(0.1mmol)四三苯基膦钯溶解在145ml甲苯中,将0.4g(3mmol)碳酸钾和0.97g(3mmol)四丁基溴化铵溶解在55ml水中,将上述两种混合溶液加入到通有氮气的干燥反应容器中,升温至100℃并在100℃条件下反应22小时(反应过程中利用回流装置以确保甲苯与水的体积比不变),冷却至室温,利用二氯甲烷萃取出合成粗产物,以石油醚:二氯甲烷=1:1为淋洗剂进行柱层析(固定相为硅胶),将洗脱液通过减压旋蒸去除溶剂,得到0.7g白色固体,产率63%,纯度为99%。
步骤b所得白色固体的定性检测数据为:
1HNMRδH(400MHz,CDCl3):7.435-7.384(m,4H),7.182-7.104(m,10H),6.975-6.956(m,4H);
13CNMR(400MHz,CDCl3,TMS):147.762,141.811,141.395,131.920,131.878,131.099,128.194,127.601,118.646,110.799;
M.p:249-251℃;
MS(ESI):测得m/z为383.1[M+H](通过计算得到C28H18N2的m/z为382.15)。
由以上结果可知,步骤b所得白色固体为四苯乙烯基顺位氰基,结构式如式(Ⅰ-Ⅳ)所示。
实施例5
本实施例提供了一种四苯乙烯基顺位硝基的制备方法,具体包括以下步骤:
步骤a、将10.2g(40mmol)联硼酸频那醇酯与0.25g(0.2mmol)四三苯基膦铂加入到含50ml N,N-二甲基甲酰胺并且通有氮气的干燥反应容器中,再将3.6g(20mmol)二苯乙炔溶于50ml N,N-二甲基甲酰胺,配成溶液,滴入上述反应容器中,升温至110℃,在110℃条件下反应9h,冷却至室温,减压旋蒸得到二苯乙烯基硼酸频那醇酯的粗产物,以石油醚:二氯甲烷=2:1为淋洗剂进行柱层析(固定相为硅胶)后,将洗脱液通过减压旋蒸去除溶剂,得到5.53g白色针状固体,产率79%。
步骤b、取3.50g(10mmol)步骤a得到的精制后的二苯乙烯基硼酸频那醇酯与4.04g(20mmol)对溴硝基苯以及0.11g(0.1mmol)四三苯基膦钯溶解155ml在甲苯中,将1.38g(10mmol)碳酸钾和3.22g(10mmol)四丁基溴化铵溶解在45ml水中,将上述两种混合溶液加入到通有氮气的干燥反应容器中,升温至90℃并在90℃条件下反应30小时(反应过程中利用回流装置以确保甲苯与水的体积比不变),冷却至室温,利用二氯甲烷萃取出合成粗产物,以石油醚:二氯甲烷=1:1为淋洗剂进行柱层析(固定相为硅胶),将洗脱液通过减压旋蒸去除溶剂,得到2.8g白色固体,产率68%,纯度为99%。
步骤b所得白色固体的定性检测数据为:
1HNMRδH(400MHz,CDCl3):8..016-7.969(m,4H),7.201-7.145(m,10H),6.991-6.975(m,4H);
13CNMR(400MHz,CDCl3,TMS):149.722,146.630,141.637,141.461,132.050,131.067,128.566,128.273,127.777,123.450,123.176;
M.p:236-239℃;
MS(ESI):测得m/z为423.1[M+H](通过计算得到C26H18N2O4的m/z为422.13)。
由以上结果可知,步骤b所得白色固体为四苯乙烯基顺位硝基,结构式如式(I-V)所示。
效果例1
实施例1-5制备的四苯乙烯基化合物检测结果如下表1。
表1实施例1-5的产率及产品性能
实施例 | 产率/% | 熔点/℃ | 产品性能 | 分子聚集诱导荧光效应 |
1 | 50 | 141 | 白色结晶状固体 | 有 |
2 | 60 | 150 | 白色结晶状固体 | 有 |
3 | 66 | 167 | 白色结晶状固体 | 有 |
4 | 63 | 251 | 白色结晶状固体 | 有 |
5 | 68 | 236 | 浅黄色结晶状固体 | 有 |
效果例2
检测实施例1-5制备的四苯乙烯基化合物的荧光发射波长,室温下压致后再次检测荧光发射波长,结果如下表2。
表2压致前后荧光发射波长
实施例 | 未研磨波长/nm | 压致后波长/nm |
1 | 444 | 450 |
2 | 438 | 446 |
3 | 445 | 461 |
4 | 452 | 454 |
5 | 490 | 519 |
由表2可知,研磨会导致该产品的最大发射波长发生红移。该表中的数据详细地阐明了本发明所提供的四苯乙烯基化合物的室温下压致变色特性,有望在脑瘤成像技术、近红外探针技术以及光电器件等领域得到应用。
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换或改进等,均应包含在本发明的保护范围之内。
Claims (8)
2.权利要求1所述压致变色的四苯乙烯基化合物的制备方法,其特征在于,包括以下步骤:
步骤a、将二苯乙炔与联硼酸频那醇酯反应,制备二苯乙烯基硼酸频那醇酯;
步骤b、将所述二苯乙烯基硼酸频那醇酯与对溴苯取代基进行反应制备得到所述四苯乙烯基化合物,所述对溴苯取代基为对溴苯醚、对溴甲苯、对溴苯甲酸甲酯、对溴苯腈或对溴硝基苯。
3.根据权利要求2所述压致变色的四苯乙烯基化合物的制备方法,其特征在于,步骤a中所述反应的温度为70~110℃,反应催化剂为四三苯基膦铂,溶剂为N,N-二甲基甲酰胺。
4.根据权利要求2所述压致变色的四苯乙烯基化合物的制备方法,其特征在于,步骤b中所述反应的温度90~110℃,反应时间20~30h,反应催化剂为四三苯基膦钯、碳酸钾和四丁基溴化铵,所述四三苯基膦钯:碳酸钾:四丁基溴化铵的摩尔比为(0.1~0.2):(3~10):(3~10)。
5.根据权利要求4所述压致变色的四苯乙烯基化合物的制备方法,其特征在于,步骤b中所述反应的溶剂为甲苯与水,体积比为(3~4):(1~1.5)。
6.根据权利要求2~5任一项所述压致变色的四苯乙烯基化合物的制备方法,其特征在于,所述制备方法还包括将步骤a所得产物进行精制,所述精制的方法包括以石油醚:二氯甲烷=2:1进行柱层析。
7.根据权利要求2~5任一项所述压致变色的四苯乙烯基化合物的制备方法,其特征在于,所述制备方法还包括将步骤a所得产物进行精制,所述精制的方法包括以石油醚:二氯甲烷=1:1进行柱层析。
8.权利要求1所述压致变色的四苯乙烯基化合物在制备室温下压致变色性荧光材料的应用。
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