Stepwise structural and fluorescent colour conversion in rhodamine analogues based on light and acid stimulations
Stepwise structural and fluorescent colour conversion in rhodamine analogues based on light and acid stimulations
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DOI：
10.1039/c9tc05054j
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发表时间：
2020-01
影响因子：
6.4
通讯作者：
Masaru Tanioka;Shinichiro Kamino;N. Koga;D. Sawada
中科院分区：
文献类型：
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作者：
Masaru Tanioka;Shinichiro Kamino;N. Koga;D. Sawada
多刺激、多响应分子的研究和开发在化学、生物学和材料科学中引起了相当大的关注。在此，我们提出了一个多刺激响应的多荧光系统在一个单一的分子。该系统是基于异构化，涉及开环/闭环反应的螺内酯的罗丹明类似物（ABPX），由我们的小组开发，它可以独立控制的光和化学刺激。UV光照射打开其中一种螺内酯，在溶液中得到热稳定的有色异构体（Z）。详细的合成和理论研究表明，ABPX的开环反应通过形成光诱导电荷分离态，然后通过双自由基的重组进行。此外，我们探索的结构动力学关系，并证明，给电子取代基的氧杂蒽环的引入可以调整光生异构体的寿命。酸的化学刺激进一步促进开环反应，得到红移异构体（D）。这些光和化学输入信号可以转换成不同颜色和荧光的输出信号。通过组合逻辑门可以区分多刺激响应的多色荧光。
The research and development of multi-stimuli, multi-responsive molecules have attracted considerable attention in chemistry, biology, and material science. Herein, we propose a multi-stimuli-responsive multi-fluorescence system in a single molecule. This system is based on the isomerization that involves ring-opening/closing reactions of spirolactones of rhodamine analogues (ABPXs), developed by our group, which can be independently controlled by light and chemical stimuli. UV light irradiation opens one of the spirolactones to give thermally stable coloured isomer (Z) in solution. Detailed synthetic and theoretical investigations reveal that the ring-opening reaction of ABPXs proceeds via the formation of a photo-induced charge separated state, followed by the recombination of the biradicals. Furthermore, we explore the structure–kinetic relationships and demonstrate that the introduction of electron-donating substituents into the xanthene ring can tune the lifetime of the photo-generated isomer. Chemical stimulation by an acid further promotes the ring-opening reaction to give a red-shifted isomer (D). These light and chemical input signals can be converted into output signals of distinct colour and fluorescence. The multi-stimuli-responsive multi-colour fluorescence could be distinctively expressed through the combinatorial logic gate.