Clicking 1,4-Dithiin Conjugated Dimaleimides for Chiroptical Evolution and Nanofabrication.

Abstract

The development of new click reactions is pivotal for materials science. Herein, we report a Michael addition-based click reaction and demonstrate its applications in chiral evolution and nanofabrication. Although the addition of maleimides to thiols has been widely exploited in biosensing and bioorthogonal chemistry, reaction between amines and maleimides proceeds at a slower rate. We find that 1,4-dithiin conjugated maleimides can undergo rapid addition reactions with organic amines (<i>t</i>_1/2 < 1 s) and they are quantitative and highly selective thanks to structural resonance, leading to pronounced changes in conjugation and optical properties. This reactivity extends to other nucleophilic inorganic anions, such as Na₂S₂O₃. Thus, controllable expression of supramolecular chirality is achieved, along with construction of chiral oligomers. Finally, in the aggregated state, this reaction enables modulation of the cocrystallization and coassembly of 1,4-dithiin conjugated maleimide and anthracene, promoting the growth of one-dimensional architectures and the formation of nanoscale chiral helical structures.