Naked and self-clickable propargylic-decorated single-chain nanoparticle precursors via redox-initiated RAFT polymerization

摘要

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, M? _wM? _n = 1.12 -1.37 up to M? _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. Redox-initiated RAFT polymerization allows the synthesis of well-defined naked, propargylic-decorated precursors that can be self-clicked to single-chain nanoparticles at room temperature under normal air atmosphere in a facile and highly efficient fashion via metal-catalyzed carbon-carbon coupling.