Chiroptical and colorimetric switches based on helical polymer-metal nanocomposites prepared via redox metal translocation of helical polymer metal complexes

Abstract

A helical copoly(phenylacetylene) that follows a dynamic chiral accord effect has been designed to further synthesize dynamic chiral nanocomposites. Its two pendants are benzamides of (L)-methionine methyl ester [(L)-1, 20%] and (L)-alanine methyl ester [(L)-2, 80%], the former being responsible for binding the copolymer to metallic nanoparticles (MNPs, M = Au, Ag) via the thioether. The two chiral comonomers have analogous dynamic behavior, and therefore, the copolymer—poly-[(L)-1_0.2-co-(L)-2_0.8]—adopts a preferred helical sense that can be amplified or inverted by stimuli acting simultaneously on both pendants. The formation of nanocomposites can be followed by different sequential chiroptical responses of the copolymer once the helical polymer metal-complexes are formed—M to P helix inversion by the formation of poly-[(L)-1_0.2-co-(L)-2_0.8]/Au³⁺ or poly-[(L)-1_0.2-co-(L)-2_0.8]/Ag⁺—and further reduction with NaBH₄ to generate the corresponding nanocomposites—P to M helix inversion by the formation of poly-[(L)-1_0.2-co-(L)-2_0.8]-AuNPs (6 nm) and poly-[(L)-1_0.2-co-(L)-2_0.8]-AgNPs (5 nm). These nanocomposites exhibit the properties of both components, helix inversion in the PPA and a colorimetric response in the MNPs triggered by metal ions.