Lv Youming, Ye Hebo, You Lei
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences Fuzhou 350002 China
University of Chinese Academy of Sciences Beijing 100049 China.
Chem Sci. 2024 Jan 19;15(9):3290-3299. doi: 10.1039/d3sc05879d. eCollection 2024 Feb 28.
Multi-addressable molecular switches with high sophistication are creating intensive interest, but are challenging to control. Herein, we incorporated ring-chain dynamic covalent sites into azoquinoline scaffolds for the construction of multi-responsive and multi-state switching systems. The manipulation of ring-chain equilibrium by acid/base and dynamic covalent reactions with primary/secondary amines allowed the regulation of / photoisomerization. Moreover, the carboxyl and quinoline motifs provided recognition handles for the chelation of metal ions and turning off photoswitching, with otherwise inaccessible -isomer complexes obtained the change of stimulation sequence. Particularly, the distinct metal binding behaviors of primary amine and secondary amine products offered a facile way for modulating / switching and dynamic covalent reactivity. As a result, multiple control of azoarene photoswitches was accomplished, including light, pH, metal ions, and amine nucleophiles, with interplay between diverse stimuli further enabling addressable multi-state switching within reaction networks. The underlying structural and mechanistic insights were elucidated, paving the way for the creation of complex switching systems, molecular assemblies, and intelligent materials.
具有高度复杂性的多可寻址分子开关正引发广泛关注，但难以控制。在此，我们将环链动态共价位点引入偶氮喹啉支架中，用于构建多响应和多态切换系统。通过酸/碱以及与伯胺/仲胺的动态共价反应来操纵环链平衡，从而实现了/光异构化的调控。此外，羧基和喹啉基序为金属离子螯合以及关闭光开关提供了识别位点，通过改变刺激顺序可得到其他情况下难以获得的-异构体配合物。特别地，伯胺和仲胺产物独特的金属结合行为为调节/切换以及动态共价反应性提供了一种简便方法。结果，实现了对偶氮芳烃光开关的多重控制，包括光、pH值、金属离子和胺亲核试剂，不同刺激之间的相互作用进一步实现了反应网络内的可寻址多态切换。阐明了潜在的结构和机理，为创建复杂的切换系统、分子组装体和智能材料铺平了道路。
