Wavelength-Selective Folding of Single Polymer Chains with Different Colors of Visible Light

Abstract

Photochemistry allows chemists to exert control over chemical reactions with spatiotemporal precision. Furthermore, light holds the potential to not only gate when and where but also which reaction takes place. Herein, two photocycloaddition reactions-initiated by different colors of visible light-are utilized to control the intramolecular crosslinking of single polymer chains. Irradiation with blue light (λ_max = 470 nm) triggers a [2 + 2] photocycloaddition inducing an initial intramolecular crosslinking reaction, whereas subsequent irradiation with violet light (λ_max = 415 nm) induces a [4 + 4] photocycloaddition, fully compacting the dual photoreactive polymer into a single-chain nanoparticle. Importantly, both crosslinked states are accessible under ultra-mild conditions requiring nothing but two different colors of visible light. The reported strategy of wavelength-selective crosslinking degrees provides key potential to be translated into materials applications for the remote control of mechanical properties on the molecular level.

Keywords: photochemistry; photoligation; single-chain folding; single-chain nanoparticles.