Trimethylsilanol Cleaves Stable Azaylides As Revealed by Unfolding of Robust “Staudinger” Single-Chain Nanoparticles

Abstract

Herein, we disclose a unique and selective reagent for the cleavage of stable azaylides prepared by the nonhydrolysis Staudinger reaction, enabling the on-demand unfolding of robust single-chain nanoparticles (SCNPs). SCNPs with promising use in catalysis, nanomedicine, and sensing are obtained through intrachain folding of discrete synthetic polymer chains. The unfolding of SCNPs involving reversible interactions triggered by a variety of external stimuli (e.g., pH, temperature, light, and redox potential) or substances (e.g., competitive reagents, solvents, and anions) is well known. Conversely, methods for the unfolding (i.e., intrachain disassembly) of SCNPs with stronger covalent interactions are scarce. We show that trimethylsilanol (Me₃SiOH) triggers the efficient unfolding of robust “Staudinger” SCNPs with stable azaylide (−N═P−) moieties as intrachain cross-linking units showing exceptional stability toward water, air, and CS₂, a standard reagent for azaylides. As a consequence, Me₃SiOH arises as a rare, exceptional, and valuable reagent for the cleavage of stable azaylides prepared by the nonhydrolysis Staudinger reaction.