Naked and Self-Clickable Propargylic-Decorated Single-Chain Nanoparticle Precursors via Redox-Initiated RAFT Polymerization.

Protection of acetylenic monomers is a common practice to avoid parasitic side reactions during polymerization. Herein, we report that redox-initiated RAFT polymerization allows the direct, room temperature synthesis of a variety of single-chain nanoparticle precursors (displaying narrow molecular weight dispersity, $\overline{M}_{\rm w}$/ $\overline{M}_{\rm n}$ = 1.12 -1.37 up to $\overline{M}_{\rm w}$ = 100 kDa) containing well-defined amounts of naked, unprotected acetylenic functional groups available for rapid and quantitative intrachain cross-linking via metal-catalyzed carbon-carbon coupling (i.e., C-C 'click' chemistry). To illustrate the useful 'self-clickable' character of the new unprotected acetylenic precursors, single-chain nanoparticles have been prepared for the first time in a facile and highly efficient manner by copper-catalyzed alkyne homocoupling (i.e., Glaser-Hay coupling) at room temperature under normal air atmosphere. [ABSTRACT FROM AUTHOR]