CN113929656A - 一种基于茚酮烯的发光材料及其制备方法和应用 - Google Patents

一种基于茚酮烯的发光材料及其制备方法和应用 Download PDF

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CN113929656A
CN113929656A CN202111144845.4A CN202111144845A CN113929656A CN 113929656 A CN113929656 A CN 113929656A CN 202111144845 A CN202111144845 A CN 202111144845A CN 113929656 A CN113929656 A CN 113929656A
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indenone
alkene
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孙晓龙
吴田宏
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Xian Jiaotong University
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Abstract

本发明公开了一种基于茚酮烯的新型发光材料及其制备方法，属于有机化合物合成和发光材料技术领域。该类化合物是通过在含有不同取代基的茚酮烯母体结构上修饰的二甲硫醚键与含有不同亲核基团的底物制备得到的，且其原料廉价易得、制备方法简单、转换率高，可用于分子荧光探针、生物分子标记及环境分析等领域。

Description

一种基于茚酮烯的发光材料及其制备方法和应用
技术领域
本发明属于有机化合物合成和发光材料技术领域，具体涉及一种基于茚酮烯的发光材料及其制备方法和应用。
背景技术
荧光传感具有高灵敏度、高选择性和原位成像等优势，其中，以有机荧光染料为基础的生物分子标记和分子荧光探针具有操作简便、重现性好等优点，可方便用于实现生物分子的原位、实时无损伤检测以及生物分子及其生物过程的追踪，已广泛应用于环境分析和生物医学等领域，而具有更加丰富应用场景的新型荧光传感器的设计依赖于性能优越的荧光染料的开发。
小分子染料的光学性能与其结构密切相关，为了独特的研究目的，特定的改造方式对于构建功能化染料具有至关重要的作用。现有染料改造案例多基于香豆素、萘酰亚胺、荧光素、罗丹明和菁类染料等传统染料的改性，如通过对染料电子供体-受体的改造调控染料分子整体的“推-拉”结构和增加分子的刚性，进而调控发光波长等性能，但这些传统染料改造方案在达到染料改造目的的同时，也伴随着复杂的制备过程，大大限制了改造方案的普适性。因此，简捷高效的染料改造方案对于开发一系列多种性能的功能染料具有重要的意义。
发明内容
为了克服上述现有技术的缺点，本发明的目的在于提供一种基于茚酮烯的发光材料及其制备方法和应用，并通过多种测试手段对其发光性质进行研究，为设计合成新的发光材料提供了新的思路。
为了达到上述目的，本发明采用以下技术方案予以实现：
本发明公开了一种基于茚酮烯的发光材料，该发光材料包括以下三类：茚酮烯受体与亲核底物制备的环化产物，茚酮烯受体与亲核底物制备的开环产物，以及含有不同取代基的茚酮烯受体与巯基乙醇制备的产物；
所述基于茚酮烯的发光材料的结构通式如下：
Figure BDA0003285044920000021
其中，R0'＝R0＝H；R0'＝H，R0＝Cl；R0'＝H，R0＝Br；R0'＝H，R0＝NO2；R0'＝H，R0＝NH2，或R0'＝R0＝CH3O。
优选地，所述茚酮烯受体与亲核底物制备的环化产物包含五元环化合物和六元环化合物，结构式如下：
Figure BDA0003285044920000022
其中，R3＝NH、S或CH3N；R4＝NH、O、S或CH3N；
Figure BDA0003285044920000027
所述茚酮烯受体与亲核底物制备的开环产物包含单取代脂肪胺化合物、双取代脂肪胺化合物、单取代芳香胺化合物和双取代芳香胺化合物；其中：
所述单取代脂肪胺化合物的结构式如下：
Figure BDA0003285044920000025
式中，R0＝H；
Figure BDA0003285044920000028
所述双取代脂肪胺化合物的结构式如下：
Figure BDA0003285044920000031
式中，R0＝H或NO2；
Figure BDA0003285044920000038
所述单取代芳香胺化合物的结构式如下：
Figure BDA0003285044920000033
式中，
Figure BDA0003285044920000039
所述双取代芳香胺化合物的结构式如下：
Figure BDA0003285044920000035
式中，
Figure BDA00032850449200000310
所述含有不同取代基的茚酮烯受体与巯基乙醇制备的产物包含如下化合物：
Figure BDA0003285044920000037
式中，R5＝NO2、Br或Cl；或者为：
Figure BDA0003285044920000041
所述含有不同取代基的茚酮烯受体B/C/D/E结构是如下：
Figure BDA0003285044920000042
式中，R5＝NO2、Br或Cl分别对应受体B/C/D。
本发明还公开了基于上述的茚酮烯的发光材料的制备方法，当所述发光材料为茚酮烯受体与亲核底物制备的环化产物时，其制备方法包括：
以茚酮烯受体A为原料，分别与含有端氨基、端巯基或端羟基的亲核底物在反应溶剂及三乙胺存在的情况下反应30min，反应结束后去除溶剂，然后通过柱层析的方法提纯，分别得到五元环化合物和六元环化合物。
优选地，反应是以二氯甲烷作为反应溶剂，茚酮烯受体A与亲核底物的反应摩尔比为1:1，亲核底物与三乙胺的摩尔比为1:1。
优选地，当所述发光材料为茚酮烯受体与亲核底物制备的开环产物时，其制备方法包括：
以茚酮烯受体A为原料，与脂肪胺反应10min，反应结束后去除溶剂，通过柱层析提纯，分别得到单取代脂肪胺化合物和双取代脂肪胺化合物；
或者包括：
以茚酮烯受体A为原料，与芳香胺反应过夜，反应结束后去除溶剂，然后通过柱层析的方法提纯，分别得到单取代芳香胺化合物和双取代芳香胺化合物。
优选地，茚酮烯受体A与脂肪胺的反应以二氯甲烷作为反应溶剂，反应温度为室温，茚酮烯受体A与脂肪胺的摩尔比为1:1；
茚酮烯受体A与芳香胺以氯仿作为反应溶剂，茚酮烯受体A与芳香胺的摩尔比为1:1～2。
优选地，含有不同取代基的茚酮烯受体与巯基乙醇制备的产物的制备方法，包括：
以含有不同取代基的茚酮烯受体B/C/D/E为原料，将茚酮烯受体B/C/D/E分别与巯基乙醇反应30min，反应结束后去除溶剂，然后通过柱层析的方法提纯，分别得到化合物8-10和化合物12；
化合物8-10的结构式如下：
Figure BDA0003285044920000051
化合物8，R5＝NO2；化合物9，R5＝Br；化合物10，R5＝Cl；
化合物12的结构式如下：
Figure BDA0003285044920000052
优选地，以化合物8为原料，将化合物8溶于无水乙醇中，将氯化亚锡溶于浓盐酸后加入上述溶液，然后升温至80℃反应10～30min，加水淬灭反应后用萃取、有机相干燥后通过柱层析提纯得到化合物11；
化合物8与氯化亚锡的摩尔比为1:5；
化合物11的结构式如下：
Figure BDA0003285044920000053
优选地，含有茚酮烯受体B/C/D/E与巯基乙醇在二氯甲烷中反应，反应温度为室温；茚酮烯受体B/C/D/E与巯基乙醇的摩尔比均为1:1。
本发明还公开了上述基于茚酮烯的发光材料在制备荧光传感器中的应用。
与现有技术相比，本发明具有以下有益效果：
本发明公开的基于茚酮烯的新型小分子发光化合物，是通过在含有不同取代基的茚酮烯母体结构上修饰的二甲硫醚键与含有不同亲核基团的底物制备得到的，通过受体与亲核试剂的一步反应可得到多种基于茚酮烯的发光染料，该反应类型具备和“Click”反应一样的高效率，副产物以气体形式释放，故其优点在于原料廉价易得，制备简单，转换率高。
本发明通过固态粉末和不同溶剂体系中的稳态光谱、寿命、绝对量子产率以及水溶液中的紫外/可见光谱探究了化合物的光学性质，结果发现该类化合物具有优异的荧光特性，能够广泛应用于荧光传感器的制备。
附图说明
图1为12种化合物在水溶液中的浓度滴定荧光光谱图；其中，(a)～(l)分别为化合物1～化合物12的浓度滴定荧光光谱图；
图2为化合物11和1在不同水含量的体系中的荧光光谱变化和在紫外灯照射下的荧光照片；其中，(a)为化合物1；(b)为化合物11；(c)为化合物1的荧光照片；(d)为化合物11的荧光照片；
图3为化合物11和1在不同浓度甘油体系中的荧光光谱变化；其中，(a)为化合物1；(b)为化合物11；
图4为化合物11和1在不同温度下的荧光光谱变化；其中，(a)为化合物1；(b)为化合物11；
图5为开环化合物7,14-1,14-2,16分别在固态和水溶液中的荧光光谱；其中，(a)为在固态中的荧光广谱；(b)为在水溶液中的荧光光谱；
图6为五元环化合物1,3-5,35,15分别在固态和水溶液中的荧光光谱；其中，(a)为在固态中的荧光光谱；(b)为在水溶液中的荧光光谱；
图7为六元环化合物31,32,33和34分别在固态和水溶液中的荧光光谱；其中，(a)为化合物33和34在固态中的荧光光谱；(b)为化合物31,32,33和34在水溶液中的荧光光谱；
图8为芳香基五元环化合物27-30分别在固态和水溶液中的荧光光谱；其中，(a)为化合物28-30在固态中的荧光光谱；(b)化合物27-30为在水溶液中的荧光光谱；
图9为含不同取代基的五元环化合物8-12分别在固态和水溶液中的荧光光谱；其中，(a)为化合物8-12在固态中的荧光光谱；(b)为化合物9-12在水溶液中的荧光光谱。
具体实施方式
为了使本技术领域的人员更好地理解本发明方案，下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分的实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都应当属于本发明保护的范围。
需要说明的是，本发明的说明书和权利要求书及上述附图中的术语“第一”、“第二”等是用于区别类似的对象，而不必用于描述特定的顺序或先后次序。应该理解这样使用的数据在适当情况下可以互换，以便这里描述的本发明的实施例能够以除了在这里图示或描述的那些以外的顺序实施。此外，术语“包括”和“具有”以及他们的任何变形，意图在于覆盖不排他的包含，例如，包含了一系列步骤或单元的过程、方法、***、产品或设备不必限于清楚地列出的那些步骤或单元，而是可包括没有清楚地列出的或对于这些过程、方法、产品或设备固有的其它步骤或单元。
下面结合附图对本发明做进一步详细描述：
茚酮烯受体A的制备：将1，3-氢化茚二酮和氢化钠溶于DMF中，加入二硫化碳室温反应1h，在冰浴下缓慢加入碘甲烷，逐渐升温至室温继续反应18h。反应方程式如下：
Figure BDA0003285044920000071
茚酮烯受体B/C/D的制备：①将B-1/C-1/D-1溶于乙酸酐和三乙胺溶液中，快速加入乙酰乙酸乙酯，室温搅拌22h，加入冰水和浓盐酸，搅拌10min，再加入5M盐酸，并加热至80℃搅拌15min，冷却至室温后用二氯甲烷萃取，用无水硫酸钠干燥后将溶剂通过旋转蒸发仪除去，最后通过柱层析提纯得到B-2/C-2/D-2；②将B-2/C-2/D-2溶于二甲亚砜中，依次加入三乙胺和二硫化碳，室温搅拌1h，加入碘甲烷室温搅拌14h后，加入碎冰，得到的沉淀经抽滤、干燥和柱层析提纯后得到受体B/C/D。反应方程式如下：
Figure BDA0003285044920000081
茚酮烯受体受体E的制备：①在冰浴的条件下，将E-1溶于甲醇和水的混合液中，分批加入三氧化铬固体后，室温搅拌72h，加入异丙醇再搅拌1h后，减压蒸馏，然后将残渣溶于水中，用二氯甲烷反复萃取，最后用无水硫酸钠干燥并除去溶剂得到的固体E-2可直接用于下一步反应；②将E-2溶于二甲亚砜，依次加入氟化铯和二硫化碳，室温搅拌2h后，加入碘甲烷继续搅拌10min，将得到的沉淀抽滤后干燥，最后经柱层析提纯后得到受体E。反应方程式如下：
Figure BDA0003285044920000082
实施例1
以化合物1为例，将茚酮烯受体A(100mg,1eq.)为原料，与亲核底物巯基乙醇(28μL,1eq.)在三乙胺(56μL,1eq.)存在的情况下，在二氯甲烷(5mL)中室温反应30min，反应结束后将溶剂旋干，然后通过柱层析的方法提纯，得到化合物1。化合物1的结构式如下：
Figure BDA0003285044920000091
化合物1：白色固体(85mg,产率为91％).1H NMR(600MHz,Chloroform-d)δ7.87(t,1H),7.83(t,1H),7.69–7.64(m,2H),4.86(t,J＝7.3Hz,2H),3.44(t,J＝7.3Hz,2H).13C NMR(151MHz,Chloroform-d)δ190.81,186.37,178.69,140.13,134.15,133.82,122.80,122.06,107.20,75.33,30.16.HRMS(ES+)m/z:calcd for C12H8O3S[M+H]+233.02669found233.02652.
同理，五元环化合物2-5,35,15,27-30,37和六元环化合物31-34均按照上述反应比例和条件通过茚酮烯受体A与对应的亲核底物反应得到。
化合物2-5的结构以及核磁数据如下：
Figure BDA0003285044920000092
化合物2：白色固体(90mg,产率为82％).1H NMR(400MHz,DMSO-d6)δ9.78(s,1H),7.72–7.58(m,4H),4.86(dd,J＝9.6,4.3Hz,1H),3.66(dd,J＝11.7,9.6Hz,1H),3.52(dd,J＝11.7,4.3Hz,1H),3.07(q,J＝7.3Hz,1H).13C NMR(101MHz,DMSO-D6)δ171.57,168.92,133.82,121.58,100.69,62.51,46.02,32.19,9.08.HRMS(ES+)m/z:calcd for C13H9NO4S[M+H]+276.03250found 276.03269.
化合物3：白色固体(87mg,产率为87％).1H NMR(600MHz,DMSO-d6)δ7.79(s,4H),3.65(s,4H).13C NMR(151MHz,DMSO-d6)δ187.57,177.34,139.89,135.09,122.77,118.03,38.08.HRMS(ES+)m/z:calcd for C12H8O2S2[M+H]+249.00385found 249.00386.
化合物4：白色固体(80mg,产率为87％).1H NMR(600MHz,Chloroform-d)δ9.39(s,1H),7.77–7.68(m,2H),7.63–7.53(m,2H),3.99(t,J＝8.2Hz,2H),3.39(t,J＝8.0Hz,2H).13C NMR(151MHz,DMSO-d6)δ188.22,187.72,167.93,138.33,137.96,132.48,120.31,120.23,99.28,48.69,27.74.HRMS(ES+)m/z:calcd for C12H9NO2S[M+H]+232.04268found232.04192.
化合物5：黄色固体(80mg,产率为93％).1H NMR(400MHz,DMSO-d6)δ8.26(s,1H),7.64–7.32(m,4H),3.62(s,2H).13C NMR(151MHz,DMSO-d6)δ189.74,159.55,139.40,132.55,120.39,91.02,43.18.HRMS(ES+)m/z:calcd for C12H10N2O2[M+H]+215.08150found215.08068.
实施例2
以茚酮烯受体A为原料，称取茚酮烯受体A(100mg,1eq.)，室温下分别与脂肪胺(二甲胺46μL,1eq.40％水溶液；苄胺45μL,1eq.)在二氯甲烷(5mL)中反应10min，反应结束后将溶剂旋干，然后通过柱层析的方法提纯，分别得到单取代脂肪胺化合物14-1和16；
化合物14-1和16的结构式如下：
Figure BDA0003285044920000101
化合物14-1：淡黄色固体(90mg,产率为91％).1H NMR(600MHz,Chloroform-d)δ7.65(dd,J＝5.3,3.0Hz,2H),7.52(dd,J＝5.3,3.0Hz,2H),3.40(s,6H),2.52(s,3H).13CNMR(151MHz,Chloroform-d)δ187.89,179.21,139.57,132.18,120.75,103.01,18.91.HRMS(ES+)m/z:calcd for C13H13NO2S[M+Na]+270.05592found 270.05539.
化合物16：淡黄色固体(110mg,产率为89％).1H NMR(600MHz,CDCl3)δ11.00(s,1H),7.68(dd,J＝5.4,3.1Hz,2H),7.56(dd,J＝5.5,3.0Hz,2H),7.38(t,J＝7.5Hz,2H),7.34–7.31(m,3H),4.87(d,J＝5.8Hz,2H),2.70(s,3H).13C NMR(151MHz,CDCl3)δ171.65,136.13,133.00,129.10,128.14,127.40,121.30,104.01,49.06,18.95.HRMS(ES+)m/z:calcd for C18H15NO2S[M+H]+310.08963found 310.08966.
称取茚酮烯受体A(100mg,1eq.)，室温下分别与脂肪胺(苄胺90μL,2eq.；二甲胺92μL,2eq.40％水溶液；乙醇胺26μL,2eq.)在二氯甲烷中反应30min，反应结束后将溶剂旋干，然后通过柱层析的方法提纯，分别得到双取代脂肪胺化合物7,14-2,6。称取受体B(100mg,1eq.)室温下与苄胺(74μL,2eq.)在二氯甲烷(5mL)中反应30min，反应结束后将溶剂旋干，然后通过柱层析的方法提纯，得到双取代脂肪胺化合物21。
化合物6、化合物7、化合物14-2的结构式如下：
Figure BDA0003285044920000111
化合物6：黄色固体(78mg,产率为91％).1H NMR(400MHz,DMSO-d6)δ9.01(s,2H),7.53(dd,J＝5.1,3.1Hz,2H),7.44(dd,J＝5.0,3.1Hz,2H),5.07(t,J＝4.1Hz,2H),3.60(q,J＝6.8,5.8Hz,8H).13C NMR(151MHz,DMSO-d6)δ190.65,160.10,138.71,132.59,120.22,93.41,60.28,46.62.HRMS(ES+)m/z:calcd for C14H16N2O4[M+H]+277.11828found277.11771.
化合物7：黄色固体(125mg,产率为85％).1H NMR(400MHz,DMSO-d6)δ9.17(s,2H),7.54(d,J＝8.3Hz,2H),7.46(d,J＝5.3Hz,2H),7.40(s,4H),7.33(t,J＝6.3Hz,6H),4.76(d,J＝5.7Hz,4H).13C NMR(151MHz,DMSO-d6)δ190.78,159.81,138.66,138.11,132.78,129.34,128.19,127.57,120.43,93.50,47.57.HRMS(ES+)m/z:calcd for C24H20N2O2[M+H]+369.15975found 369.16017.
化合物14-2：黄色固体(68mg,产率为69％).1H NMR(400MHz,Chloroform-d)δ7.60(dd,J＝5.4,3.1Hz,2H),7.48(dd,J＝5.4,3.1Hz,2H),3.06(s,12H).13C NMR(101MHz,Chloroform-d)δ190.03,165.19,139.86,131.73,120.12,97.96,42.19,41.65.HRMS(ES+)m/z:calcd for C14H16N2O2[M+H]+245.12845found 245.12792.
实施例3
以上述得到的受体A为原料，称取A(100mg,1eq.)分别与芳香胺(苯胺38μL,1eq.；对甲氧基苯胺49mg,1eq.)在在氯仿(5mL)中反应过夜，反应结束后将溶剂旋干，然后通过柱层析的方法提纯，分别得到单取代芳香胺化合物17-1；称取A(100mg,1eq.)，分别与苯胺(苯胺76μL,2eq.)在氯仿中反应过夜，反应结束后将溶剂旋干，然后通过柱层析的方法提纯，得到双取代芳香胺化合物17-2。
化合物17-1、化合物17-2的结构式如下：
Figure BDA0003285044920000121
化合物17-1：黄绿色固体(75mg,产率为63％).1H NMR(600MHz,Chloroform-d)δ12.33(s,1H),7.76–7.71(m,2H),7.60(dd,J＝5.2,2.8Hz,2H),7.44(t,J＝7.8Hz,2H),7.37–7.31(m,3H),2.29(s,3H).13C NMR(101MHz,Chloroform-d)δ169.20,137.88,133.36,129.57,127.39,125.01,123.54,121.70,106.28,18.14.HRMS(ES+)m/z:calcd forC17H13NO2S[M+Na]+318.05592found 318.05535.
化合物17-2：亮黄色固体(89mg,产率为65％).1H NMR(400MHz,Chloroform-d)δ10.89(s,2H),7.68(dd,J＝5.4,3.1Hz,2H),7.56(dd,J＝5.3,3.0Hz,2H),7.02(t,J＝7.6Hz,4H),6.96–6.86(m,6H).13C NMR(101MHz,Chloroform-d)δ192.74,155.18,139.17,136.26,132.77,128.71,125.85,123.59,121.02,94.71.HRMS(ES+)m/z:calcd forC22H16N2O2[M+H]+341.12845found 341.12817.
实施例4
以上述得到的受体B/C/D/E为原料，称取受体B(95mg,1eq.)、C(105mg,1eq.)、D(91mg,1eq.)、E(99mg,1eq.)，室温下分别与巯基乙醇(23μL,1eq.)在二氯甲烷中反应30min，反应结束后将溶剂旋干，然后通过柱层析的方法提纯，分别得到化合物8-10和化合物12。
化合物8-10、化合物12的结构式如下：
Figure BDA0003285044920000131
化合物8：淡黄色固体(84mg,产率为89％).1H NMR(600MHz,DMSO-d6)δ8.54(d,J＝8.1Hz,1H),8.33(s,1H),7.97(d,J＝9.8Hz,1H),4.97(t,J＝7.5Hz,2H),3.62(t,J＝7.5Hz,2H).13C NMR(151MHz,DMSO-d6)δ187.60(d,J＝54.4Hz),183.17(s),182.74(d,J＝50.5Hz),151.10(d,J＝28.7Hz),143.03(d,J＝11.0Hz),139.96(d,J＝6.7Hz),129.14(d,J＝41.0Hz),123.25(d,J＝84.0Hz),116.47(d,J＝88.1Hz),106.20(d,J＝5.7Hz),76.87(s),30.15(s).HRMS(ES+)m/z:calcd for C12H7NO5S[M+H]+278.01177found 278.01175.
化合物9：淡黄色固体(80mg,产率为84％).1H NMR(600MHz,DMSO-d6)δ8.01–7.83(m,2H),7.69(d,J＝4.1Hz,1H),4.92(t,J＝7.3Hz,2H),3.58(t,J＝7.3Hz,2H).13C NMR(151MHz,DMSO-d6)δ188.99(d,J＝71.5Hz),184.19(d,J＝83.3Hz),182.03(s),141.43(s),138.44(d,J＝4.9Hz),137.36(d,J＝44.5Hz),128.44(d,J＝35.3Hz),125.15(d,J＝89.2Hz),124.36(d,J＝87.1Hz),105.89(d,J＝6.6Hz),77.01(d,J＝3.5Hz),30.54(s).HRMS(ES+)m/z:calcd for C12H7BrO3S[M+H]+310.9372found 310.93706.
化合物10：淡黄色固体(77mg,产率为82％).1H NMR(600MHz,DMSO-d6)δ7.85–7.71(m,3H),4.91(t,J＝7.4Hz,2H),3.57(t,J＝7.4Hz,2H).13C NMR(151MHz,DMSO-d6)δ186.66(d,J＝39.7Hz),181.87(d,J＝51.9Hz),179.75(d,J＝3.3Hz),139.20(d,J＝5.4Hz),137.26(d,J＝34.4Hz),135.85(d,J＝5.6Hz),132.20(d,J＝44.2Hz),121.96(d,J＝85.2Hz),120.02(d,J＝87.4Hz),103.82(d,J＝5.6Hz),74.74(d,J＝3.3Hz),28.28(s).HRMS(ES+)m/z:calcd for C12H7ClO3S[M+H]+266.98772found 266.98710.
化合物12：黄色固体(70mg,产率为74％).1H NMR(600MHz,Chloroform-d)δ7.32(s,1H),7.28(s,1H),4.85–4.77(m,2H),4.00(d,J＝4.1Hz,6H),3.40(t,J＝7.0Hz,2H).13CNMR(151MHz,Chloroform-d)δ190.18,186.07,175.49,154.33,154.16,134.76,134.71,107.10,104.23,103.60,74.95,56.63,30.12.HRMS(ES+)m/z:calcd for C14H12O5S[M+H]+293.04782found 293.04699.
实施例5
以上述得到的化合物8为原料，称取100mg化合物8溶于2mL无水乙醇中，将204mg氯化亚锡溶于320μL浓盐酸后加入上述溶液，然后升至80℃反应20min，加水淬灭反应后用二氯甲烷萃取三次，合并有机相，干燥后通过柱层析提纯得到化合物11。
化合物11的结构式如下：
Figure BDA0003285044920000141
化合物11：黄色固体(35mg,产率为78％).1H NMR(600MHz,DMSO-d6)δ7.44(t,J＝6.9Hz,1H),6.84–6.78(m,2H),6.41(s,2H),4.78(q,J＝7.1Hz,2H),3.47(q,J＝7.9Hz,2H).13C NMR(151MHz,DMSO-d6)δ189.89(d,J＝324.8Hz),185.41(d,J＝220.7Hz),176.74(d,J＝32.1Hz),155.43(d,J＝46.2Hz),142.89(d,J＝18.0Hz),127.52(d,J＝21.8Hz),124.37(d,J＝77.4Hz),118.55(d,J＝57.8Hz),107.02(d,J＝30.0Hz),105.04(d,J＝72.9Hz),75.85(d,J＝15.4Hz),30.14(s).HRMS(ES+)m/z:calcd for C12H9NO3S[M+H]+248.03759found 248.03680.
实施例1至5所得到的化合物的制备通式如下所示：
所述五元环和六元环化合物的制备通式为：
Figure BDA0003285044920000151
所述单取代和双取代脂肪胺化合物的制备通式为：
Figure BDA0003285044920000152
所述单取代和双取代芳香胺取代化合物的制备通式为：
Figure BDA0003285044920000161
所述化合物8-10的制备通式为：
Figure BDA0003285044920000162
所述化合物11的制备通式为：
Figure BDA0003285044920000163
所述化合物12的制备通式为：
Figure BDA0003285044920000164
其余化合物结构及表征数据如下：
化合物15：
Figure BDA0003285044920000171
黄色固体(92mg,产率为95％).1H NMR(400MHz,Chloroform-d)δ7.58(dd,J＝5.3,3.0Hz,2H),7.47(dd,J＝5.3,3.1Hz,2H),3.79(s,4H),3.07(s,6H).13C NMR(101MHz,Chloroform-d)δ189.08,164.86,139.49,131.55,120.02,50.17,36.86.HRMS(ES+)m/z:calcd for C14H14N2O2[M+H]+243.1128found 243.11227.
化合物21：
Figure BDA0003285044920000172
黄色固体(120mg,产率为85％).1H NMR(400MHz,Chloroform-d)δ9.58(t,J＝5.3Hz,2H),8.41–8.33(m,2H),7.70(d,J＝7.9Hz,1H),7.44–7.32(m,6H),7.27(d,J＝1.3Hz,2H),7.25(s,2H),4.63(d,J＝6.3Hz,4H).13C NMR(101MHz,Chloroform-d)δ188.88,188.74,159.67,150.32,143.13,139.40,136.18,128.85,127.87,127.40,125.91,120.54,115.19,95.17,47.35.HRMS(ES+)m/z:calcd for C24H19N3O4[M+H]+414.14483found414.14471.
化合物27：
Figure BDA0003285044920000181
黄色固体(80mg,产率为76％).1H NMR(400MHz,Trifluoroacetic acid-d)δ7.60(d,J＝8.6Hz,2H),7.46–7.34(m,5H),7.32–7.25(m,1H).13C NMR(101MHz,Trifluoroacetic acid-d)δ191.94,137.32,136.78,134.14,128.43,126.26,126.00,122.24,122.02,114.70,99.87.HRMS(ES+)m/z:calcd for C16H10N2O2[M+H]+263.0815found 263.05637.
化合物28：
Figure BDA0003285044920000182
黄色固体(83mg,产率为79％).1H NMR(400MHz,Trifluoroacetic acid-d)δ7.67–7.55(m,4H),7.50(d,J＝3.4Hz,2H),7.41(d,J＝7.0Hz,2H).13C NMR(101MHz,Trifluoroacetic acid-d)δ193.02,144.99,137.40,136.83,131.58,128.72,125.27.HRMS(ES+)m/z:calcd for C16H9NO2S[M+H]+280.04268found 280.04273.
化合物29：
Figure BDA0003285044920000183
淡黄色固体(93mg,产率为83％).1H NMR(400MHz,Chloroform-d)δ7.95–7.82(m,2H),7.74–7.64(m,4H),7.51–7.45(m,1H),7.39(t,J＝7.7Hz,1H).13C NMR(101MHz,Chloroform-d)δ189.92,184.89,172.69,151.99,139.89,139.79,133.81,133.44,127.83,125.78,122.43,122.02,121.92,121.61,112.74.HRMS(ES+)m/z:calcd for C16H8O3S[M+H]+281.02669found 281.02656.
化合物30：
Figure BDA0003285044920000191
亮黄色固体(88mg,产率为74％).1H NMR(400MHz,Trifluoroacetic acid-d)δ7.72–7.63(m,1H),7.60–7.45(m,2H),7.40–7.29(m,1H).13C NMR(101MHz,Trifluoroacetic acid-d)δ193.17,175.13,140.77,138.43,137.43,130.42,125.47,125.34.HRMS(ES+)m/z:calcd for C16H8O2S2[M+H]+297.00385found 297.00417.
化合物31：
Figure BDA0003285044920000192
黄色固体(96mg,产率为91％).1H NMR(400MHz,Chloroform-d)δ7.79(dd,J＝5.5,3.0Hz,2H),7.64(dd,J＝5.5,3.1Hz,2H),3.10(t,J＝6.6Hz 4H),2.36(p,J＝6.6Hz,2H).13CNMR(101MHz,Chloroform-d)δ188.36,175.33,140.06,134.00,122.49,28.71,22.58.HRMS(ES+)m/z:calcd for C13H10O2S2[M+H]+263.0195found 263.01907.
化合物32：
Figure BDA0003285044920000193
黄色固体(90mg,产率为91％).1H NMR(400MHz,Chloroform-d)δ7.82–7.71(m,2H),7.65–7.57(m,2H),4.61(t,J＝5.2Hz,2H),3.17(t,J＝6.4Hz,2H),2.36–2.27(m,2H).13C NMR(101MHz,Chloroform-d)δ190.46,186.56,176.49,139.56,139.37,133.23,133.04,121.83,121.24,110.16,68.58,24.61,21.09.HRMS(ES+)m/z:calcd for C13H10O3S[M+Na]+269.02429found 269.02429.
化合物33：
Figure BDA0003285044920000201
黄色固体(87mg,产率为95％).1H NMR(400MHz,Chloroform-d)δ8.68(s,2H),7.54(dd,J＝5.3,3.0Hz,2H),7.45(dd,J＝5.3,3.1Hz,2H),3.46(td,J＝5.9,2.5Hz,4H),2.05(p,J＝5.8Hz,2H).13C NMR(101MHz,DMSO-d6)δ190.57,155.99,139.00,132.50,120.23,91.82,38.17,19.80.HRMS(ES+)m/z:calcd for C13H12N2O2[M+H]+229.09715found229.09679.
化合物34：
Figure BDA0003285044920000202
黄色固体(89mg,产率为90％).1H NMR(400MHz,Chloroform-d)δ10.32(s,1H),7.72–7.45(m,4H),4.55(t,2H),3.55(td,J＝6.2,2.6Hz,2H),2.21(p,J＝5.9Hz,2H).13CNMR(101MHz,Chloroform-d)δ164.66,139.15,132.49,121.16,93.49,66.46,37.43,20.64.HRMS(ES+)m/z:calcd for C13H11NO3[M+Na]+252.06311found 252.06248.
化合物35：
Figure BDA0003285044920000211
淡黄色固体(75mg,产率为87％).1H NMR(400MHz,DMSO-d6)δ9.67(s,1H),7.60–7.53(m,4H),4.67(t,J＝9.0Hz,2H),3.75(t,2H).13C NMR(101MHz,DMSO-d6)δ165.63,139.49,133.24,121.03,90.44,69.87,43.25,29.56.HRMS(ES+)m/z:calcd for C12H9NO3[M+Na]+238.04746found 238.04699.
化合物37：
Figure BDA0003285044920000212
淡黄色固体(64mg,产率为60％).1H NMR(400MHz,Trifluoroacetic acid-d)δ7.60–7.56(m,1H),7.48(t,J＝6.7Hz,2H),7.37(p,J＝7.5Hz,1H).13C NMR(101MHz,Trifluoroacetic acid-d)δ195.15,195.10,161.01,148.49,139.30,136.58,129.24,128.89,128.58,124.47,113.30,93.82.HRMS(ES+)m/z:calcd for C16H9NO3[M+H]+264.06552found 264.06526.
表1.已制备化合物在固态及水溶液中的激发波长、发射波长、斯托克斯位移、摩尔消光系数(吸光度A≤0.05)荧光寿命和荧光量子产率等光学性质。
Figure BDA0003285044920000213
Figure BDA0003285044920000221
Figure BDA0003285044920000231
将上述得到的化合物1-12分别溶于二甲亚砜中，制备成浓度为1mM的储备液待用。图1为10μM 12种化合物在含有1％DMSO的PBS溶液中的浓度滴定荧光光谱图，可以看出所有化合物的荧光强度均随着浓度的增加而增强，其中，化合物1、11和12在水溶液中具有较高的量子产率。
图2为10μM化合物11和100μM化合物1在不同水含量中的荧光光谱和在紫外灯下的照片，可以看出两种化合物的荧光强度均随着水含量的变化而变化，其中化合物1的荧光强度随着水含量的增加而增加，且波长发生微弱的红移；化合物11的荧光强度随着水含量的增加表现为先增强后降低的现象，且最大发射波长逐渐红移。
图3为10μM化合物11和1在不同浓度甘油溶液(0％-50％)中的荧光光谱，两者的荧光强度均随着粘度的增加而增加，并且波长均保持不变。
图4为10μM化合物11和1分别在二氯甲烷和甲醇溶液中的荧光光谱随温度的变化；两者的荧光光谱表现出随着温度的降低强度增强，波长红移的现象。
图5为开环化合物7,14-1,14-2,16分别在固态和10μM水溶液中以以各化合物最适激发波长激发下的荧光光谱。
图6为五元环化合物1,3-5,35,15分别在固态以365nm的激发波长和10μM水溶液中以各化合物最适激发波长得到的荧光光谱。
图7为六元环化合物33和34分别在固态以365nm的激发波长和10μM水溶液中以各化合物最适激发波长得到的荧光光谱。
图8为芳香基五元环化合物28-30分别在固态以365nm的激发波长和10μM水溶液中以各化合物最适激发波长得到的荧光光谱。
图9为含不同取代基的五元环化合物9-12分别在固态以365nm的激发波长和10μM水溶液中以各化合物最适激发波长得到的荧光光谱。
以上内容仅为说明本发明的技术思想，不能以此限定本发明的保护范围，凡是按照本发明提出的技术思想，在技术方案基础上所做的任何改动，均落入本发明权利要求书的保护范围之内。

Claims (10)

1.一种基于茚酮烯的发光材料，其特征在于，该发光材料包括以下三类：茚酮烯受体与亲核底物制备的环化产物，茚酮烯受体与亲核底物制备的开环产物，以及含有不同取代基的茚酮烯受体与巯基乙醇制备的产物；
所述基于茚酮烯的发光材料的结构通式如下：
Figure FDA0003285044910000011
其中，R0'＝R0＝H；R0'＝H，R0＝Cl；R0'＝H，R0＝Br；R0'＝H，R0＝NO2；R0'＝H，R0＝NH2，或R0'＝R0＝CH3O。
2.根据权利要求1所述的基于茚酮烯的发光材料，其特征在于，所述茚酮烯受体与亲核底物制备的环化产物包含五元环化合物和六元环化合物，结构式如下：
Figure FDA0003285044910000012
其中，R3＝NH、S或CH3N；R4＝NH、O、S或CH3N；
Figure FDA0003285044910000013
所述茚酮烯受体与亲核底物制备的开环产物包含单取代脂肪胺化合物、双取代脂肪胺化合物、单取代芳香胺化合物和双取代芳香胺化合物；其中：
所述单取代脂肪胺化合物的结构式如下：
Figure FDA0003285044910000014
式中，R0＝H；
Figure FDA0003285044910000021
所述双取代脂肪胺化合物的结构式如下：
Figure FDA0003285044910000022
式中，R0＝H或NO2；
Figure FDA0003285044910000023
所述单取代芳香胺化合物的结构式如下：
Figure FDA0003285044910000024
式中，
Figure FDA0003285044910000025
所述双取代芳香胺化合物的结构式如下：
Figure FDA0003285044910000026
式中，
Figure FDA0003285044910000027
所述含有不同取代基的茚酮烯受体与巯基乙醇制备的产物包含如下化合物：
Figure FDA0003285044910000028
式中，R5＝NO2、Br或Cl；或者为：
Figure FDA0003285044910000031
所述含有不同取代基的茚酮烯受体B/C/D/E结构式如下：
Figure FDA0003285044910000032
式中，R5＝NO2、Br或Cl分别对应受体B/C/D。
3.权利要求2所述的基于茚酮烯的发光材料的制备方法，其特征在于，当所述发光材料为茚酮烯受体与亲核底物制备的环化产物时，其制备方法包括：
以茚酮烯受体A为原料，分别与含有端氨基、端巯基或端羟基的亲核底物在反应溶剂及三乙胺存在的情况下反应30min，反应结束后去除溶剂，然后通过柱层析的方法提纯，分别得到五元环化合物和六元环化合物。
4.根据权利要求3所述的基于茚酮烯的发光材料的制备方法，其特征在于，反应是以二氯甲烷作为反应溶剂，茚酮烯受体A与亲核底物的反应摩尔比为1:1，亲核底物与三乙胺的摩尔比为1:1。
5.权利要求2所述的基于茚酮烯的发光材料的制备方法，其特征在于，当所述发光材料为茚酮烯受体与亲核底物制备的开环产物时，其制备方法包括：
以茚酮烯受体A为原料，与脂肪胺反应10min，反应结束后去除溶剂，通过柱层析提纯，分别得到单取代脂肪胺化合物和双取代脂肪胺化合物；
或者包括：
以茚酮烯受体A为原料，与芳香胺反应过夜，反应结束后去除溶剂，然后通过柱层析的方法提纯，分别得到单取代芳香胺化合物和双取代芳香胺化合物。
6.根据权利要求5所述的基于茚酮烯的发光材料的制备方法，其特征在于，
茚酮烯受体A与脂肪胺的反应以二氯甲烷作为反应溶剂，反应温度为室温，茚酮烯受体A与脂肪胺的摩尔比为1:1；
茚酮烯受体A与芳香胺以氯仿作为反应溶剂，茚酮烯受体A与芳香胺的摩尔比为1:1～2。
7.权利要求2所述的基于茚酮烯的发光材料的制备方法，其特征在于，含有不同取代基的茚酮烯受体与巯基乙醇制备的产物的制备方法，包括：
以含有不同取代基的茚酮烯受体B/C/D/E为原料，将茚酮烯受体B/C/D/E分别与巯基乙醇反应30min，反应结束后去除溶剂，然后通过柱层析的方法提纯，分别得到化合物8-10和化合物12；
化合物8-10的结构式如下：
Figure FDA0003285044910000041
化合物8，R5＝NO2；化合物9，R5＝Br；化合物10，R5＝Cl；
化合物12的结构式如下：
Figure FDA0003285044910000042
8.根据权利要求7所述的基于茚酮烯的发光材料的制备方法，其特征在于，以化合物8为原料，将化合物8溶于无水乙醇中，将氯化亚锡溶于浓盐酸后加入上述溶液，然后升温至80℃反应10～30min，加水淬灭反应后用萃取、有机相干燥后通过柱层析提纯得到化合物11；化合物8与氯化亚锡的摩尔比为1:5；
化合物11的结构式如下：
Figure FDA0003285044910000051
9.根据权利要求7所述的基于茚酮烯的发光材料的制备方法，其特征在于，含有茚酮烯受体B/C/D/E与巯基乙醇在二氯甲烷中反应，反应温度为室温；茚酮烯受体B/C/D/E与巯基乙醇的摩尔比均为1:1。
10.权利要求1或2所述的基于茚酮烯的发光材料在制备荧光传感器中的应用。
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