m-Phenylene linked macrocycle composed of electron-rich dithienogermole and electron-deficient tricoordinate boron units
m-Phenylene linked macrocycle composed of electron-rich dithienogermole and electron-deficient tricoordinate boron units
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由富电子二噻吩并摩尔和缺电子三配位硼单元组成的间亚苯基连接大环
DOI：
10.1016/j.polymer.2021.124404
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发表时间：
2022
期刊：
影响因子：
4.6
通讯作者：
Ohshita Joji
中科院分区：
文献类型：
--
作者：
Adachi Yohei;Kondo Keisuke;Yin Xiaodong;Jaekle Frieder;Ohshita Joji
在π共轭体系中引入非常规元素是控制电子结构的有力工具。在本工作中，缺电子的三配位硼单元与富电子的二噻吩并高分子单元相结合，得到了一种具有间苯连接基的元素杂化共轭大环。与不受溶剂极性影响的吸收光谱相反，该元素混合大环化合物在荧光光谱中表现出明显的溶剂化显色性，该荧光光谱源自二噻吩甲酮和三配位硼单元之间的电荷转移（CT）跃迁。在大环化合物溶液中加入氟化物，导致四配位硼酸盐物种的化学计量形成。有趣的是，荧光增强通过添加氟化物，并通过荧光光谱和TD-DFT计算证实了这一机制。
Incorporation of non-conventional elements into π-conjugated systems is a powerful tool to control the electronic structures. In this work, electron-deficient tricoordinate boron units were combined with electron-rich dithienogermole units to provide an element-hybrid conjugated macrocycle withm-phenylene linkers. In contrast to the absorption spectra which were unaffected by solvent polarity, the element-hybrid macrocycle exhibited clear solvatochromism in the fluorescence spectra originating from the charge transfer (CT) transition between the dithienogermole and tricoordinate boron units. The addition of fluoride to the solution of the macrocycle resulted in the stoichiometric formation of tetracoordinate borate species. Interestingly, the fluorescence was intensified by the addition of fluoride, and the mechanism was confirmed by fluorescence spectroscopy and TD-DFT calculations.