Trithiazolyl-1,3,5-triazines bearing decyloxybenzene moieties: synthesis, photophysical and electrochemical properties, as well as self-assembly behavior
Trithiazolyl-1,3,5-triazines bearing decyloxybenzene moieties: synthesis, photophysical and electrochemical properties, as well as self-assembly behavior
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带有癸氧基苯部分的三噻唑基-1,3,5-三嗪：合成、光物理和电化学性质以及自组装行为
DOI：
10.1039/c8ob00471d
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发表时间：
2018
影响因子：
3.2
通讯作者：
Y. Nakamura
中科院分区：
文献类型：
--
作者：
S.-i. Kato;S. Jin;T. Kimura;N. Yoshikawa;D. Nara;K. Imamura;Y. Shiota;K. Yoshizawa;R. Katoono;T. Yamanobe;H. Uehara;Y. Nakamura
本文报道了含去氧基苯环的盘状三唑并-1，3，5-三氮杂环化合物的合成、光物理性质、氧化还原特性和自组装行为。这些化合物是通过1，3，5-三氯三嗪与三种不同的三丁基锡(噻唑)的Migita-Kosugi-Stille偶联反应合成的。研究了结构-性质关系，即在三嗪单元中引入噻唑单元、噻唑单元与三嗪单元之间的共轭连接性以及在噻唑基团与环氧苯基团之间插入乙烯基间隔基对三氮唑基-1，3，5-三氮杂环性质的影响。将三嗪核结合在噻唑基团的5位，有效地延长了π的共轭，并提供了高的荧光量子产率。与HOMO水平相比，乙炔间隔物大大降低了LUMO水平。所制备的三噻唑基-1，3，5-三嗪在溶液中自组装，并在5位引入噻唑单元增强了这一行为。对自缔合行为进行了详细的热力学研究，揭示了自组装一维团簇的形成过程。
We report the synthesis, photophysical properties, redox characteristics, and self-assembly behavior of disk-shaped trithiazolyl-1,3,5-triazines that bear decyloxybenzene moieties. These compounds were synthesized by a Migita–Kosugi–Stille coupling reaction of 1,3,5-trichlorotriazine with three different tributyltin(thiazoles) as the key step. The structure–property relationships, namely the effects of the incorporation of thiazole units into the triazine unit, the conjugation connectivity between the thiazole and triazine units, and the insertion of ethynylene spacers between the thiazole and decyloxybenzene moieties on the properties of the trithiazolyl-1,3,5-triazines were comprehensively investigated. Binding of the triazine core at the 5-position of the thiazole moieties effectively extended the π-conjugation and afforded high fluorescence quantum yields. The ethynylene spacers substantially lowered the LUMO level relative to the HOMO level. The prepared trithiazolyl-1,3,5-triazines self-assembled in solution, and the introduction of thiazole units at the 5-position enhanced this behavior. Detailed thermodynamic studies on the self-association behavior were conducted, and the formation of self-assembled 1D clusters is disclosed.