Synthesis and characterization of a polyisocyanide with thioether pendant caused an oxidation-triggered helix-to-helix transition

Abstract

AbstractStimuli responsive helical polymers have attracted wide attention and many polymers responsive to the external stimuli have been synthesized. But, only a few examples have been reported regarding the redox-induced helicity inversion helical polymers. The polyisocyanide including thioether pendant (poly-MBTIP) was synthesized by polymerization of methyl (R)-3-(benzylthio)-2-isocyanopropanoate (MBTIP) monomer using NiCl2·6H2O as catalytic agent in dry DCM. The chiroptical and oxidation properties of the poly-MBTIP are investigated. The poly-MBTIPs exhibit intense specific optical rotations and Cotton effects compared to the monomer, strongly suggesting a helical conformation of the polymer backbone. Additionally, the thioether pendant of poly-MBTIP backbone was oxidized to sulfoxide group by H2O2. Interestingly, the specific optical rotations and Cotton effects of poly-MBTIP oxidized are reversed, probably suggesting a helical conformation inversion.