Fast and catalyst-free hetero-Diels–Alder chemistry for on demand cyclable bonding/debonding materials

Abstract

A new dithioester possessing a cyano Z-group (cyano-dithioester (CDTE)) has been synthesized via a 2-step, one-pot reaction. The cyano-substituted dithioester has been found to undergo fast reversible hetero-Diels–Alder (HDA) reactions at ambient temperature, without the need for a catalyst, as demonstrated by ESI-MS and UV-Vis experiments. To apply the bonding/debonding on demand system to materials science, a cyano-dithioester di-linker was synthesized and employed as a di-functional dienophile in a HDA-based polymerization reaction with a bis-cyclopentadiene polymer. The reversible bonding of the polymer systems were demonstrated by on-line UV-Vis spectroscopy, on-line NMR spectroscopy, and on-line high temperature DLS, as well as via GPC in situ trapping experiments and high-level ab initio molecular orbital calculations.