Shape-Persistent π-Conjugated Macrocycles with Aggregation-Induced Emission Property: Synthesis, Mechanofluorochromism, and Mercury(II) Detection
Shape-Persistent π-Conjugated Macrocycles with Aggregation-Induced Emission Property: Synthesis, Mechanofluorochromism, and Mercury(II) Detection
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具有聚集诱导发射特性的形状持久 π 共轭大环化合物：合成、机械荧光变色和汞 (II) 检测
DOI：
10.1021/acsami.9b10702
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发表时间：
2019-09-18
影响因子：
9.5
通讯作者：
Tang, Ben Zhong
中科院分区：
文献类型：
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作者：
Liu, Yi;Lin, Fa Xu;Tang, Ben Zhong
形状稳定的共轭大环化合物由于其独特的结构和性质而具有重要的意义。本文中，通过具有半环拓扑结构的乙炔封端的四苯乙烯前体的氧化偶联和随后从丁二烯亚基连接基转化为噻吩亚基连接基，合成了一系列具有形状持久结构、自适应主链和聚集诱导发射（AIE）性质的π-共轭大环。通过NMR光谱和基质辅助激光解吸/电离飞行时间质谱表征为大环结构提供了明确的证据。特别是，在刚性的大环骨架的芳香环的自由旋转进行了验证，通过二维NMR光谱，变温NMR测量，和理论计算。此外，这些形状持久的大环发色团都表现出明显的AIE现象和显着的机械荧光行为，在研磨和溶剂退火后的发射蓝移的红移。此外，S原子引入到大环框架赋予的大环发光团的能力，选择性地检测在其他金属离子之间的水介质中的汞（II）离子。
Shape-persistent conjugated macrocycles are fundamentally important because of their unique structure and properties. Herein, a series of pi-conjugated macrocycles with a shape-persistent architecture, an adaptive backbone, and aggregation-induced emission (AIE) properties are synthesized via oxidative coupling of acetylene-terminated tetraphenylethylene precursor with a half-ring topology and following transformation from butadiynylene linkers into thienylene ones. Characterization by NMR spectroscopy and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry provided unambiguous proofs for the macrocyclic structures. In particular, the free rotation of aromatic rings in the rigid macrocyclic backbone was validated by two-dimensional NMR spectroscopy, variable-temperature NMR measurements, and theoretical calculations. Moreover, these shape-persistent macrocyclic chromophores all exhibited obvious AIE phenomena and remarkable mechanofluorochromism behaviors with a red-shifted luminescence upon grinding and blue-shifted emission after solvent annealing. Also, the introduction of S atoms into the macrocyclic frameworks endowed the macrocyclic luminogen the capability to selectively detect mecury(II) ions in aqueous media among other metal ions.