Functional Polythioamides Derived from Thiocarbonyl Fluoride**

Abstract

AbstractPolythioamide is a unique type of sulfur‐containing polymer with advanced functionalities. Nonetheless, the elemental sulfur commonly used in their synthesis tends to react readily with unsaturated functional groups, thereby limiting the scope of eligible substrates. Inspired by the highly efficient sulfur‐fluoride exchange (SuFEx) polymerization through discrete hubs, we present herein a pioneering and versatile approach to the synthesis of polythioamides from diboronic acids, secondary diamines, and thiocarbonyl fluoride as the central connective hub. Well‐defined structures, including previously inaccessible unsaturated substrates, were realized. These newly devised polythioamides can efficiently and selectively bind to metal ions and were applied in precious‐metal recovery. Further development resulted in PdII‐crosslinked single‐chain nanoparticles serving as recyclable homogeneous catalysts, thus demonstrating the vast potential of these unprecedented polythioamides. We anticipate that thiocarbonyl fluoride could emerge as a potent hub for facilitating the intricate synthesis of sulfur‐containing polymers.