CN115611875A - 一种三苯胺吡啶盐类aie光敏剂分子及其制备方法 - Google Patents
一种三苯胺吡啶盐类aie光敏剂分子及其制备方法 Download PDFInfo
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Abstract
本发明提供了一种三苯胺吡啶盐类AIE光敏剂分子,该光敏剂分子的核心骨架为三苯胺;同时还提供了该三苯胺吡啶盐类AIE光敏剂分子的制备方法,以4‑硼酸三苯胺为基础,依次加入5‑溴噻吩‑2‑甲醛、N‑溴代丁二酰亚胺、吡啶‑4‑硼酸、1,3‑茚满二酮和碘甲烷并通过一系列操作制备得三苯胺吡啶盐类AIE光敏剂分子,并对每一步合成的有机物都进行了核磁共振氢谱和核磁共振碳谱检测,确定其物理结构。本发明的三苯胺吡啶盐类AIE光敏剂分子在荧光成像领域具有良好的潜在应用价值,其制备方法简便,原料易得、成本低且每个步骤均有高的整体收率,能实现大规模合成。
Description
技术领域
本发明属于有机合成技术领域,具体涉及一种三苯胺吡啶盐类AIE光敏剂分子及其制备方法。
背景技术
因为荧光生物成像具有实时、高灵敏度、损伤小和操作简便等优点,所以被广泛应用于生物医学领域。近红外光(780-2526nm)相对于可见光(390-780nm),能减少光吸收和散射从而提高成像对比度以及穿透深度、降低光损伤。传统的光敏剂分子由于聚集荧光淬灭(Aggregation-Caused Quenching,ACQ)效应,在高浓度或聚集态下表现为荧光性能显著下降甚至消失,严重限制了其在荧光成像领域的应用。聚集诱导发光型(Aggregation-Induced Emission,AIE)光敏剂在聚集状态下其非辐射热耗散通道被禁阻,伴随着辐射跃迁通道和系间窜越过程的极大促进,使其荧光发射显著增强,具有AIE性质的光敏剂在生物医学领域展现出巨大的应用前景。高效的深红/近红外AIE光敏剂(发射波长>650nm),能够很大程度上克服生物底物的生物吸收、光学散射和自发荧光的干扰。
通过合理设计三苯胺吡啶盐类AIE光敏剂分子的电子给体-受体结构(D-A),利用分子内电荷转移效应使其吸收和发射波长红移,可实现在较大程度上克服生物底物的生物吸收、光学散射和自发荧光的干扰,从而制备具有较红发射波长、较高荧光量子产率、较大斯托克斯位移等性质的AIE光敏剂,提高荧光生物成像信噪比。
发明内容
本发明所要解决的技术问题在于针对上述现有技术的不足,提供一种三苯胺吡啶盐类AIE光敏剂分子,该三苯胺吡啶盐类AIE光敏剂分子在荧光生物成像领域具有良好的潜在应用价值,并提供了其制备方法,该制备方法降低了合成三苯胺吡啶盐类AIE光敏剂分子的成本和难度,反应的各步骤均具有高的整体收率,能实现大规模合成。
为解决上述技术问题,本发明采用的技术方案是:一种三苯胺吡啶盐类AIE光敏剂分子,所述三苯胺吡啶盐类AIE光敏剂分子的结构通式为:
所述结构通式中R为氢或杂芳环。
本发明还提供了一种制备上述三苯胺吡啶盐类AIE光敏剂分子的方法,该方法为:
S1、在N2保护下,将4-硼酸三苯胺、5-溴噻吩-2-甲醛、四三苯基膦钯、碳酸钾、四氢呋喃和水在三颈瓶中混合,从室温升温至80℃后,恒温反应12h,待反应溶液冷却至室温后,加入去离子水,用乙酸乙酯萃取,将得到的有机层用水洗涤后干燥,经减压旋蒸浓缩,得粗产物,然后经柱层析纯化,得到淡黄色固体化合物1;
S2、在N2保护下,将N-溴代丁二酰亚胺、四氢呋喃和S1中得到的化合物1加入三颈瓶中混合,在冰盐浴下反应2h,待反应溶液恢复至室温,加入去离子水,用乙酸乙酯萃取,将得到的有机层用水洗涤后干燥,经减压旋蒸浓缩,得到粗产物,然后经重结晶纯化,得到淡黄色固体化合物2;
S3、在N2保护下,将吡啶-4-硼酸、碳酸钾、1,4-二氧六环、水和S2中得到的化合物2在三颈瓶中混合,从室温升温至90℃后,恒温反应16h,待反应溶液冷却至室温后,加入去离子水,用乙酸乙酯萃取,将得到的有机层用水洗涤后干燥,经减压旋蒸浓缩,得到粗产物,然后经柱层析纯化,得到淡黄色固体化合物3;
S4、在N2保护下,将1,3-茚满二酮、三乙胺、三氯甲烷和S3中得到的化合物3在三颈瓶中混合,从室温升温至70℃后,恒温反应24h,待反应溶液冷却至室温后,加入去离子水,用二氯甲烷萃取,将得到的有机层用水洗涤后干燥,经减压旋蒸浓缩,得到粗产物,然后经柱层析纯化,得到红色固体化合物4;
S5、在N2保护下,将碘甲烷、乙腈和S4中得到的化合物4在三颈瓶中混合,从室温升温至90℃后,恒温反应24h,待反应溶液冷却至室温后,加入冷水,经减压旋蒸浓缩,得到粗产物,然后经重结晶纯化,得到三苯胺吡啶盐类AIE光敏剂分子;
优选地,S1中所述4-硼酸三苯胺、5-溴噻吩-2-甲醛、四三苯基膦钯、碳酸钾、四氢呋喃和水的质量体积比为2.89g:2.29g:0.58g:6.91g:45mL:5mL。
优选地,S1-S5中所述去离子水的温度为25℃。
优选地,S1中所述柱层析的条件为:硅胶柱中,以乙酸乙酯/石油醚作为洗脱剂,洗脱比例为1/20;
S2和S5中所述重结晶的条件为:在常温下,以三氯甲烷和甲醇为溶剂,重结晶时间为48h;
S3和S4中所述柱层析的条件为:硅胶柱中,以乙酸乙酯作为洗脱剂。
优选地,当R为氢时,S2中所述N-溴代丁二酰亚胺、四氢呋喃和S1中得到的化合物1的质量体积比为1.82g:100mL:3.55g;当R为杂芳环时,S2中所述N-溴代丁二酰亚胺、四氢呋喃和S1中得到的化合物1的质量体积比为3.65g:100mL:3.55g。
优选地,当R为氢时,S3中所述吡啶-4-硼酸、碳酸钾、1,4-二氧六环、水和S2中得到的化合物2的质量体积比为0.74g:2.76g:40mL:20mL:1.73g;当R为杂芳环时,S3中所述吡啶-4-硼酸、碳酸钾、1,4-二氧六环、水和S2中得到的化合物2的质量体积比为3.48g:6.50g:47mL:188mL:4.80g。
优选地,当R为氢时,S4中所述1,3-茚满二酮、三乙胺、三氯甲烷和S3中得到的化合物3的质量体积比为1.42g:0.66g:65mL:2.81g;当R为杂芳环时,S4中所述1,3-茚满二酮、三乙胺、三氯甲烷和S3中得到的化合物3的质量体积比为0.88g:0.51g:50mL:2.55g。
优选地,当R为氢时,S5中所述碘甲烷、乙腈和S4中得到的化合物4的质量体积比为2.84g:40mL:1.12g;当R为杂芳环时,S5中所述碘甲烷、乙腈和S4中得到的化合物4的质量体积比为5.68g:40mL:1.28g。
本发明每个步骤用到的原料易得,均为分析纯,每一步合成的化合物都有高的整体收率,能顺利实现大规模合成,且对每个步骤制备得到的有机化合物进行核磁共振氢谱(1H NMR)和核磁共振碳谱(13C NMR)的检测,对制备得到的有机化合物进行结构鉴定。
三苯胺吡啶盐类AIE光敏剂分子在聚集状态下其非辐射热耗散通道被禁阻,伴随着辐射跃迁通道和系间窜越过程的极大促进,导致其荧光发射,利用结构中三苯胺基团导致荧光成像。
本发明与现有技术相比具有以下优点:
1、本发明新型的三苯胺吡啶盐类AIE光敏剂分子,利用结构中三苯胺基团导致荧光成像,在荧光成像领域具有良好的潜在应用价值。
2、本发明的三苯胺吡啶盐类AIE光敏剂分子制备难度小、原料易得且成本低,每个步骤均有高的整体收率,能实现大规模合成。
下面结合附图和实施例对本发明作进一步详细说明。
附图说明
图1为本发明实施例1中制备的TPA-Py-1的核磁共振氢谱图。
图2为本发明实施例1中制备的TPA-Py-1的核磁共振碳谱图。
图3为本发明实施例2中制备的TPA-Py-2的核磁共振氢谱图。
图4为本发明实施例2中制备的TPA-Py-2的核磁共振碳谱图。
具体实施方式
实施例1
本实施例制备的三苯胺吡啶盐类AIE光敏剂分子的结构式为:
本实施例提供了上述三苯胺吡啶盐类AIE光敏剂分子的制备方法,该方法为:
S1、在N2保护下,将2.89g4-硼酸三苯胺、2.29g5-溴噻吩-2-甲醛、0.58g四三苯基膦钯、6.91g碳酸钾、45mL四氢呋喃和5mL水加入250mL的三颈瓶中混合,从室温升温至80℃后,恒温反应12h,待反应溶液冷却至室温后,加入温度为25℃的去离子水,用乙酸乙酯萃取,将得到的有机层用水洗涤后干燥,经减压旋蒸浓缩,得到粗产物,然后经柱层析纯化,得到2.74g淡黄色固体化合物1,收率为77%;
所述柱层析的条件为:硅胶柱中,以乙酸乙酯/石油醚作为洗脱剂,洗脱比例为1/20;
所述化合物1的测试结果:1H NMR(400MHz,CDCl3)δ=9.85(s,1H),7.70(d,1H),7.51(d,2H),7.32-7.28(m,5H),7.15-7.13(m,4H),7.11-7.05(m,4H);13C NMR(100MHz,CDCl3)δ=182.52,154.54,149.13,146.96,141.33,137.64,129.46,127.23,126.14,125.16,123.86,122.84,122.35;
S2、在N2保护下,将1.82gN-溴代丁二酰亚胺、100mL四氢呋喃和3.55gS1中得到的化合物1加入250mL的三颈瓶中混合,在冰盐浴下搅拌反应2h,待反应溶液恢复至室温,加入温度为25℃的冷水,用乙酸乙酯萃取,将得到的有机层用水洗涤后干燥,经减压旋蒸浓缩,得到粗产物,然后经重结晶纯化,得到3.91g淡黄色固体化合物2,收率为90%;
所述重结晶的条件为:在常温下,以三氯甲烷和甲醇为溶剂,重结晶时间为48h;
所述化合物2的测试结果:1H NMR(400MHz,CDCl3)δ=9.86(s,1H),7.70(d,1H),7.55-7.51(m,2H),7.40-7.36(m,2H),7.33-7.29(m,3H),7.13-7.09(m,3H),7.08-7.04(m,2H),7.02-6.96(m,2H);13C NMR(100MHz,CDCl3)δ=182.56,154.23,148.61,146.58,146.18,141.59,137.59,132.47,129.64,127.37,126.83,126.16,125.25,124.29,123.07,122.85,116.18,77.32,77.00,76.68;
S3、在N2保护下,将0.74g吡啶-4-硼酸、2.76g碳酸钾、40mL 1,4-二氧六环、20mL水和1.73gS2中得到的化合物2加入250mL的三颈瓶中混合,从室温升温至90℃,恒温反应16h,待反应溶液冷却至室温后,加入温度为25℃的去离子水,用乙酸乙酯萃取,将得到的有机层用水洗涤后干燥,经减压旋蒸浓缩,得到粗产物,然后经柱层析纯化,得到0.735g淡黄色固体化合物3,收率为85%;
所述柱层析的条件为:硅胶柱中,以乙酸乙酯作为洗脱剂;
所述化合物3的测试结果:1H NMR(400MHz,CDCl3)δ=9.87(s,1H),8.64(s,2H),7.71(d,2H),7.58-7.55(m,4H),7.49-7.48(m,2H),7.36-7.32(m,3H),7.22-7.12(m,7H);13CNMR(100MHz,CDCl3)δ=182.56,154.14,150.23,148.51,148.06,147.43,146.56,141.65,137.58,132.34,129.68,127.89,127.39,127.14,125.65,124.53,124.19,123.44,123.14,120.98;
S4、在N2保护下,将1.42g1,3-茚满二酮、0.66g三乙胺、65mL三氯甲烷和2.81gS3中得到的化合物3加入250mL的三颈瓶中混合,从室温升温至70℃,恒温反应24h,待反应溶液冷却至室温后,加入温度为25℃的去离子水,用二氯甲烷萃取,将得到的有机层用水洗涤后干燥,经减压旋蒸浓缩,得到粗产物,然后经柱层析纯化,得到3.39g红色固体化合物4,收率为93%;
所述柱层析的条件为:硅胶柱中,以乙酸乙酯作为洗脱剂;
所述化合物4的测试结果:1H NMR(400MHz,CDCl3)δ=8.64(s,2H),7.95-7.91(m,4H),7.75-7.72(m,2H),7.63(d,2H),7.55(d,2H),7.48(d,2H),7.36-7.32(m,3H),7.21-7.11(m,7H);13C NMR(100MHz,CDCl3)δ=190.30,189.58,157.21,150.19,148.56,147.92,147.33,146.44,143.71,141.96,140.39,136.04,135.98,134.83,134.62,132.37,129.66,127.85,127.53,127.26,125.68,124.56,124.26,123.90,123.43,123.20,122.84,122.66,120.97;
S5、在N2保护下,将2.84g碘甲烷、40mL的乙腈和1.12gS4中得到的化合物4加入250mL的三颈瓶中混合,从室温升温至90℃,恒温反应24h,待反应溶液冷却至室温后,加入温度为25℃的去离子水,经减压旋蒸浓缩,得到粗产物,然后经重结晶纯化,得到1.33g红色固体三苯胺吡啶盐类AIE光敏剂分子(命名为TPA-Py-1),收率为95%;
所述重结晶的条件为:在常温下,以三氯甲烷和甲醇为溶剂,重结晶时间为48h;
图1为本实施例制备的三苯胺吡啶盐类AIE光敏剂分子TPA-Py-1的核磁共振氢谱图;
图2为本实施例制备的三苯胺吡啶盐类AIE光敏剂分子TPA-Py-1的核磁共振碳谱图;
所述三苯胺吡啶盐类AIE光敏剂分子TPA-Py-1的测试结果:1H NMR(400MHz,CDCl3)δ=9.11(d,2H),8.13(d,2H),7.96-7.91(m,4H),7.77-7.69(m,6H),7.41-7.36(m,3H),7.25-7.22(t,1H),7.19-7.15(m,6H),4.59(s,3H);13C NMR(100MHz,CDCl3)δ=190.23,189.60,156.28,154.88,151.39,147.11,145.39,144.95,143.59,141.99,140.43,136.48,135.97,135.00,134.80,130.06,129.24,129.20,127.81,126.53,125.93,125.32,125.16,124.47,123.89,123.08,122.96,122.78,121.85,48.24。
本实施例制备了一个新型的三苯胺吡啶盐类AIE光敏剂分子,其在荧光生物成像领域具有良好的潜在应用价值,本实施例的制备方法降低了三苯胺吡啶盐类AIE光敏剂分子的制备成本和难度,反应各步骤具有较高的整体收率,均能顺利实现大规模制备。
实施例2
本实施例制备的三苯胺吡啶盐类AIE光敏剂分子的结构式为:
本实施例提供了上述三苯胺吡啶盐类AIE光敏剂分子的制备方法,该方法为:
S1、在N2保护下,将2.89g4-硼酸三苯胺、2.29g5-溴噻吩-2-甲醛、0.58g四三苯基膦钯、6.91g碳酸钾、45mL四氢呋喃和5mL水加入250mL的三颈瓶中混合,从室温升温至80℃后,恒温反应12h,待反应溶液冷却至室温后,加入温度为25℃的去离子水,用乙酸乙酯萃取,将得到的有机层用水洗涤后干燥,经减压旋蒸浓缩,得到粗产物,然后经柱层析纯化,得到2.74g淡黄色固体化合物1,收率为77%;
所述柱层析的条件为:硅胶柱中,以乙酸乙酯/石油醚作为洗脱剂,洗脱比例为1/20;
所述化合物1的测试结果:1H NMR(400MHz,CDCl3)δ=9.85(s,1H),7.70(d,1H),7.51(d,2H),7.32-7.28(m,5H),7.15-7.13(m,4H),7.11-7.05(m,4H);13C NMR(100MHz,CDCl3)δ=182.52,154.54,149.13,146.96,141.33,137.64,129.46,127.23,126.14,125.16,123.86,122.84,122.35;
S2、在N2保护下,将3.65gN-溴代丁二酰亚胺、100mL四氢呋喃和3.55gS1中得到的化合物1加入250mL的三颈瓶中混合,在冰盐浴下搅拌反应2h,待反应溶液恢复至室温,加入温度为25℃的去离子水,用乙酸乙酯萃取,将得到的有机层用水洗涤后干燥,经减压旋蒸浓缩,得到粗产物,然后经重结晶纯化,得到4.93g淡黄色固体化合物2,收率为96%;
所述重结晶的条件为:在常温下,以三氯甲烷和甲醇为溶剂,重结晶时间为48h;
所述化合物2的测试结果:1H NMR(400MHz,CDCl3)δ=9.86(s,1H),7.71(d,1H),7.53(d,2H),7.41-7.37(m,4H),7.31(d,1H),7.07-7.04(m,2H),7.00-6.96(m,4H);13C NMR(100MHz,CDCl3)δ=182.54,153.86,148.05,145.73,141.77,137.52,132.63,127.48,127.43,126.24,123.27,123.23,116.67;
S3、在N2保护下,将3.48g吡啶-4-硼酸、6.50g碳酸钾、47mL1,4-二氧六环、188mL水和4.80gS2中得到的化合物2加入250mL的三颈瓶中混合,从室温升温至90℃,恒温反应16h,待反应溶液冷却至室温后,加入温度为25℃的去离子水,用乙酸乙酯萃取,将得到的有机层用水洗涤后干燥,经减压旋蒸浓缩,得到粗产物,然后经柱层析纯化,得到3.98g淡黄色固体化合物3,收率为83%;
所述柱层析的条件为:硅胶柱中,以乙酸乙酯作为洗脱剂;
所述化合物3的测试结果:1H NMR(400MHz,CDCl3)δ=9.86(s,1H),8.64(d,4H),7.71(d,2H),7.60(d,6H),7.50-7.48(m,4H),7.34(d,1H),7.25(d,4H),7.19(d,2H);13C NMR(100MHz,CDCl3)δ=182.54,153.74,150.29,147.97,147.56,147.22,141.84,137.58,133.09,128.08,127.90,127.53,124.84,124.20,123.41,120.99;
S4、在N2保护下,将0.88g1,3-茚满二酮、0.51g三乙胺、50mL三氯甲烷和2.55gS3中得到的化合物3加入250mL的三颈瓶中混合,从室温升温至70℃,恒温反应24h,待反应溶液冷却至室温后,加入温度为25℃的去离子水,用二氯甲烷萃取,将得到的有机层用水洗涤后干燥,经减压旋蒸浓缩,得到粗产物,然后经柱层析纯化,得到2.77g红色固体化合物4,收率为87%;
所述柱层析的条件为:硅胶柱中,以乙酸乙酯作为洗脱剂;
所述化合物4的测试结果:1H NMR(400MHz,CDCl3)δ=8.65(d,4H),7.98-7.95(m,4H),7.79-7.74(m,2H),7.70(d,2H),7.63-7.57(m,4H),7.50(d,4H),7.40(d,1H),7.28-7.25(m,4H),7.19(d,2H);13C NMR(100MHz,CDCl3)δ=190.31,189.66,156.80,150.26,148.06,147.53,147.26,143.68,141.98,140.42,136.22,136.05,134.94,134.74,133.17,128.13,128.09,127.70,124.92,124.84,124.12,124.06,123.66,122.93,122.73,121.03;
S5、在N2保护下,将5.68g碘甲烷、40mL乙腈和1.28gS4中得到的化合物4加入250mL的三颈瓶中混合,从室温升温至90℃,恒温反应24h,待反应溶液冷却至室温后,加入温度为25℃的去离子水,经减压旋蒸浓缩,得到粗产物,然后经重结晶纯化,得到1.70g红色固体三苯胺吡啶盐类AIE光敏剂分子(命名为TPA-Py-2),收率为92%;
所述重结晶的条件为:在常温下,以三氯甲烷和甲醇为溶剂,重结晶时间为48h;
图3为本实施例制备的三苯胺吡啶盐类AIE光敏剂分子TPA-Py-2的核磁共振氢谱图;
图4为本实施例制备的三苯胺吡啶盐类AIE光敏剂分子TPA-Py-2的核磁共振碳谱图;
所述三苯胺吡啶盐类AIE光敏剂分子TPA-Py-2的测试结果:1H NMR(400MHz,CDCl3)δ=8.95(d,4H),8.45(d,4H),8.25(d,1H),8.12(d,4H),8.03(s,1H),7.92-7.90(m,6H),7.78(d,1H),7.32-7.26(m,6H),4.32(s,2H);13C NMR(100MHz,DMSO-d6)δ=189.34,188.97,155.07,152.99,149.19,146.43,145.50,145.31,141.29,139.79,135.86,135.54,135.46,129.76,129.32,128.04,127.98,126.05,125.54,124.11,123.42,123.08,122.72,46.91。
以上所述,仅是本发明的较佳实施例,并非对本发明作任何限制。凡是根据发明技术实质对以上实施例所作的任何简单修改、变更以及等效变化,均仍属于本发明技术方案的保护范围内。
Claims (9)
2.一种如权利要求1所述的三苯胺吡啶盐类AIE光敏剂分子的制备方法,其特征在于,该方法为:
S1、在N2保护下,将4-硼酸三苯胺、5-溴噻吩-2-甲醛、四三苯基膦钯、碳酸钾、四氢呋喃和水混合,从室温升温至80℃后,恒温反应12h,待反应溶液冷却至室温,加入去离子水,用乙酸乙酯萃取,将得到的有机层用水洗涤后干燥,经减压旋蒸浓缩,得粗产物,然后经柱层析纯化,得到化合物1;
S2、在N2保护下,将N-溴代丁二酰亚胺、四氢呋喃和S1中得到的化合物1混合,在冰盐浴下反应2h,待反应溶液冷却至室温,加入去离子水,用乙酸乙酯萃取,将得到的有机层用水洗涤后干燥,经减压旋蒸浓缩,得到粗产物,然后经重结晶纯化,得到化合物2;
S3、在N2保护下,将吡啶-4-硼酸、碳酸钾、1,4-二氧六环、水和S2中得到的化合物2混合,从室温升温至90℃后,恒温反应16h,待反应溶液冷却至室温,加入去离子水,用乙酸乙酯萃取,将得到的有机层用水洗涤后干燥,经减压旋蒸浓缩,得到粗产物,然后经柱层析纯化,得到化合物3;
S4、在N2保护下,将1,3-茚满二酮、三乙胺、三氯甲烷和S3中得到的化合物3混合,从室温升温至70℃后,恒温反应24h,待反应溶液冷却至室温,加入去离子水,用二氯甲烷萃取,将得到的有机层用水洗涤后干燥,经减压旋蒸浓缩,得到粗产物,然后经柱层析纯化,得到化合物4;
S5、在N2保护下,将碘甲烷、乙腈和S4中得到的化合物4混合,从室温升温至90℃后,恒温反应24h,待反应溶液冷却至室温,加入去离子水,经减压旋蒸浓缩,得到粗产物,然后经重结晶纯化,得到三苯胺吡啶盐类AIE光敏剂分子;
3.根据权利要求2所述的一种如权利要求1所述的三苯胺吡啶盐类AIE光敏剂分子的制备方法,其特征在于,S1中所述4-硼酸三苯胺、5-溴噻吩-2-甲醛、四三苯基膦钯、碳酸钾、四氢呋喃和水的质量体积比为2.89g:2.29g:0.58g:6.91g:45mL:5mL。
4.根据权利要求2所述的一种如权利要求1所述的三苯胺吡啶盐类AIE光敏剂分子的制备方法,其特征在于,S1-S5中所述去离子水的温度为25℃。
5.根据权利要求2所述的一种如权利要求1所述的三苯胺吡啶盐类AIE光敏剂分子的制备方法,其特征在于,S1中所述柱层析的条件为:硅胶柱中,以乙酸乙酯/石油醚作为洗脱剂,洗脱比例为1/20;
S2和S5中所述重结晶的条件为:在常温下,以三氯甲烷和甲醇为溶剂,重结晶时间为48h;
S3和S4中所述柱层析的条件为:硅胶柱中,以乙酸乙酯作为洗脱剂。
6.根据权利要求2所述的一种如权利要求1所述的三苯胺吡啶盐类AIE光敏剂分子的制备方法,其特征在于,当R为氢时,S2中所述N-溴代丁二酰亚胺、四氢呋喃和S1中得到的化合物1的质量体积比为1.82g:100mL:3.55g;当R为杂芳环时,S2中所述N-溴代丁二酰亚胺、四氢呋喃和S1中得到的化合物1的质量体积比为3.65g:100mL:3.55g。
7.根据权利要求2所述的一种如权利要求1所述的三苯胺吡啶盐类AIE光敏剂分子的制备方法,其特征在于,当R为氢时,S3中所述吡啶-4-硼酸、碳酸钾、1,4-二氧六环、水和S2中得到的化合物2的质量体积比为0.74g:2.76g:40mL:20mL:1.73g;当R为杂芳环时,S3中所述吡啶-4-硼酸、碳酸钾、1,4-二氧六环、水和S2中得到的化合物2的质量体积比为3.48g:6.50g:47mL:188mL:4.80g。
8.根据权利要求2所述的一种如权利要求1所述的三苯胺吡啶盐类AIE光敏剂分子的制备方法,其特征在于,当R为氢时,S4中所述1,3-茚满二酮、三乙胺、三氯甲烷和S3中得到的化合物3的质量体积比为1.42g:0.66g:65mL:2.81g;当R为杂芳环时,S4中所述1,3-茚满二酮、三乙胺、三氯甲烷和S3中得到的化合物3的质量体积比为0.88g:0.51g:50mL:2.55g。
9.根据权利要求2所述的一种如权利要求1所述的三苯胺吡啶盐类AIE光敏剂分子的制备方法,其特征在于,当R为氢时,S5中所述碘甲烷、乙腈和S4中得到的化合物4的质量体积比为2.84g:40mL:1.12g;当R为杂芳环时,S5中所述碘甲烷、乙腈和S4中得到的化合物4的质量体积比为5.68g:40mL:1.28g。
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