CN103524404B - 一种具有聚集诱导发光性质的吡啶-三苯胺-蒽共轭分子及其制备 - Google Patents

一种具有聚集诱导发光性质的吡啶-三苯胺-蒽共轭分子及其制备 Download PDF

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CN103524404B
CN103524404B CN201310505001.7A CN201310505001A CN103524404B CN 103524404 B CN103524404 B CN 103524404B CN 201310505001 A CN201310505001 A CN 201310505001A CN 103524404 B CN103524404 B CN 103524404B
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anthracene
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钱鹰
管成飞
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Southeast University
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    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
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    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
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Abstract

本发明公开了一种具有聚集诱导发光性质的吡啶-三苯胺-蒽共轭分子及其制备，它是由吡啶、三苯胺和蒽基团组成的共轭分子，基团组成比例为吡啶：三苯胺：蒽=4:2:1。本发明的吡啶-三苯胺-蒽共轭分子在固态时发射红光，在四氢呋喃稀溶液中发出绿色荧光，在水/四氢呋喃混合溶剂中随着不良溶剂水含量的增加，聚集态纳米粒子的发射波长覆盖从绿光到黄光的宽波段。本发明的吡啶-三苯胺-蒽共轭分子具有聚集诱导发光特性。

Description

一种具有聚集诱导发光性质的吡啶-三苯胺-蒽共轭分子及其制备
技术领域
本发明涉及蒽类聚集诱导发光分子，具体设计一种具有聚集诱导发光性质的吡啶-三苯胺-蒽共轭分子。
背景技术
聚集诱导发光是指一类荧光生色团在稀溶液中微弱发光或不发光，而在固态或聚集状态时荧光显著增强的一种光物理现象。大多数荧光生色团在稀溶液中具有很好的发光性能，但在聚集态时由于分子间相互作用导致了非辐射能量转换或形成不利于荧光发射的物种，产生荧光减弱甚至不发光即聚集荧光猝灭的现象。荧光分子的材料化急需解决聚集荧光猝灭的问题，研究开发具有聚集诱导发光性质的新型材料受到广泛关注。
发明内容
发明目的：本发明的目的是提供一种具有聚集诱导发光性质的吡啶-三苯胺-蒽类化合物。
技术方案：为了解决上述技术问题，本发明提供了一种吡啶-三苯胺-蒽共轭分子，由如下结构式构成：
制备所述的具有聚集诱导发光性质的吡啶-三苯胺-蒽共轭分子的方法，以9,10-双{4-[N,N-二(4-碘苯基)氨基]苯乙烯基}蒽、4-乙烯基吡啶为原料通过钯催化偶联反应得到。
反应时以无水磷酸钾、三(邻甲基苯基)膦和醋酸钯为催化剂。
反应在氮气保护及无水无氧环境下进行。
反应使用N,N-二甲基乙酰胺为溶剂。
以上所述的吡啶-三苯胺-蒽共轭分子是由吡啶、三苯胺和蒽3种基团通过双键共轭连接，优化组合而得到。基团组成比例为吡啶：三苯胺：蒽=4:2:1。
有益效果：
本发明的吡啶-三苯胺-蒽共轭分子9,10-双{4-{N,N-二[4-(4-吡啶乙烯基)苯基]氨基}苯乙烯基}蒽，是由3种基团吡啶、三苯胺和蒽通过双键共轭连接，优化组合而得到，基团组成比例为吡啶：三苯胺：蒽=4:2:1。本发明的吡啶-三苯胺-蒽共轭分子不溶于水，在甲苯、四氢呋喃、氯仿、二氯甲烷、乙酸乙酯等有机溶剂中溶解性良好，固态时发射红光，在四氢呋喃稀溶液中发出绿色荧光，在水/四氢呋喃混合溶剂中随着不良溶剂水含量的增加，聚集态纳米粒子的发射波长覆盖从绿光到黄光的宽波段，含水量70%的聚集态纳米粒子荧光最强，发出黄色荧光。本发明的吡啶-三苯胺-蒽共轭分子具有聚集诱导发光性质，在荧光开关和传感器、荧光探针、生物标记及荧光成像、有机发光器件等领域具有重要的应用价值。
附图说明
图1为本发明实施例1制备的吡啶-三苯胺-蒽共轭分子9,10-双{4-{N,N-二[4-(4-吡啶乙烯基)苯基]氨基}苯乙烯基}蒽（TM）的固体粉末的荧光照片及配制的溶液的荧光照片。左边固体态发的为红色荧光，溶液发的为淡绿色荧光。
图2为本发明实施例1制备的吡啶-三苯胺-蒽共轭分子9,10-双{4-{N,N-二[4-(4-吡啶乙烯基)苯基]氨基}苯乙烯基}蒽（TM）在不同含水量时聚集态纳米粒子的荧光发射强度及最大发射波长变化图。图中方块点曲线代表在不同含水量时聚集态纳米粒子的荧光发射强度变化图，三角形曲线代表在不同含水量时聚集态纳米粒子的最大发射波长变化图。
具体实施方式
以下通过实施例对本发明作进一步详细说明：
实施例1.吡啶-三苯胺-蒽共轭分子9,10-双{4-{N,N-二[4-(4-吡啶乙烯基)苯基]氨基}苯乙烯基}蒽的制备方法
（1）蒽-9,10-双（亚甲基磷酸乙酯）（按文献方法制备，参考文献：Angew.Chem.Int.Ed.2012,51,10782）与4-[N,N-二(4-碘苯基)氨基]苯甲醛（按文献方法制备，参考文献：Tetrahedron Letters,2007,48,5878）按摩尔比1：2.2反应，获得9,10-双{4-[N,N-二(4-碘苯基)氨基]苯乙烯基}蒽（SM）。
称取蒽-9,10-二（亚甲基磷酸乙酯）0.12g（0.25mmol）溶于5mL干燥THF中，氮气保护下滴加溶有4-[N,N-二(4-碘苯基)氨基]苯甲醛0.29g（0.55mmol）的10mL THF溶液。缓慢滴入溶有叔丁醇钾0.34g（3.00mmol）的10mL THF溶液，室温反应24h。抽滤，干燥，重结晶得到橙红色固体（SM），产率70%。
分析所得化合物SM：
1H NMR(300MHz,CDCl3)δ:8.39(d,J=8.70Hz,4H),7.87(d,J=16.30Hz,4H),7.58(d,J=7.30Hz,8H),7.47(d,J=6.60Hz,4H),7.14(d,J=7.90Hz,4H),6.91(d,J=7.70Hz,8H);
获得的化合物结构式为
（2）吡啶-三苯胺-蒽共轭分子9,10-双{4-{N,N-二[4-(4-吡啶乙烯基)苯基]氨基}苯乙烯基}蒽的合成路线如下：
具体制备方法为：氮气保护及无水无氧条件下，将9,10-双{4-[N,N-二(4-碘苯基)氨基]苯乙烯基}蒽SM1.22g(1.0mmol)溶于5mL无水N,N-二甲基乙酰胺中，滴加溶有无水磷酸钾0.17g(0.8mmol)，三(邻甲基苯基)膦0.24g(0.8mmol)和醋酸钯0.09g（0.4mmol）的10mL无水N,N-二甲基乙酰胺溶液，磁力搅拌下滴加4-乙烯基吡啶1mL，氮气鼓泡20分钟，缓慢升温至130℃，反应96h。反应结束后，将反应液滤入50mL甲醇中，析出棕色固体，抽滤，用二氯甲烷/甲醇混合溶剂重结晶，用柱层析方法提纯,梯度洗脱，得到暗红色固体（TM）,产率35%。
分析所得化合物TM：
1H NMR(300MHz,CDCl3)δ:8.57(s,8H),8.30～8.44(m,4H),7.86(d,2H,J=16.41Hz),7.62(d,4H,J=8.10Hz),7.45～7.57(m,12H),7.31～7.37(m,12H),7.13～7.20(m,12H),6.90(dd,6H,J=16.5,6.3Hz);IR(KBr)ν:3024,1630,1591,1501,1416,1317,1289,967,796cm－1;13C NMR(CDCl3,300MHz)δ149.96,147.35,144.61,132.26,130.90,130.84,129.47,128.03,127.58,125.12,124.93,124.47,123.90,123.84,120.54.HRMS-MALDI-TOF calcd for C82H61N6[M+H]+1129.4958,found1129.4959.
获得的化合物结构式为
本发明的吡啶-三苯胺-蒽共轭分子9,10-双{4-{N,N-二[4-(4-吡啶乙烯基)苯基]氨基}苯乙烯基}蒽（TM）不溶于水，在甲苯、四氢呋喃、氯仿、二氯甲烷、乙酸乙酯等有机溶剂中溶解性良好。化合物TM固态时发射红光，最大发射波长为642nm。化合物TM在四氢呋喃稀溶液中发出绿色荧光，最大发射波长为484nm。化合物A在水/四氢呋喃混合溶剂中随着不良溶剂水含量的增加，聚集态纳米粒子的发射波长覆盖从绿光到黄光的宽波段，在含水量70%的聚集态纳米粒子荧光最强，发出黄色荧光。本发明的吡啶-三苯胺-蒽共轭分子具有聚集诱导发光性质，在荧光开关和传感器、荧光探针、生物标记及荧光成像、有机发光器件等领域具有重要的应用价值。

Claims (5)

1.一种具有聚集诱导发光性质的吡啶-三苯胺-蒽共轭分子，其特征在于，由如下结构式构成：
2.制备权利要求1所述的具有聚集诱导发光性质的吡啶-三苯胺-蒽共轭分子的方法，其特征在于，以9,10-双{4-[N,N-二(4-碘苯基)氨基]苯乙烯基}蒽、4-乙烯基吡啶为原料通过钯催化偶联反应得到。
3.如权利要求2所述的制备具有聚集诱导发光性质的吡啶-三苯胺-蒽共轭分子的方法，其特征在于，反应时以无水磷酸钾、三(邻甲基苯基)膦和醋酸钯为催化剂。
4.如权利要求2所述的制备具有聚集诱导发光性质的吡啶-三苯胺-蒽共轭分子的方法，其特征在于，反应在氮气保护及无水无氧环境下进行。
5.如权利要求2所述的制备具有聚集诱导发光性质的吡啶-三苯胺-蒽共轭分子的方法，其特征在于，反应使用N,N-二甲基乙酰胺为溶剂。
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CN104830318B (zh) * 2015-05-15 2017-04-05 天津理工大学 一种高聚集态荧光发射的荧光标记分子及其制备方法
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CN110295040B (zh) * 2019-07-31 2022-05-24 江西科技师范大学 一种9,10-噻吩/呋喃基蒽聚集诱导发光化合物及其制备方法和应用
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