Synthesis and disassembly of an organometallic polymer comprising redox-active Co₄S₄ clusters and Janus biscarbene linkers

Abstract

Here, we show for the first time that main-chain organometallic polymers (MCOPs) can be prepared from Janus N-heterocyclic carbene (NHC) linkers and polynuclear cluster nodes. The crosslinked framework Co₄S₄-MCOP is synthesized <i>via</i> ligand displacement reactions and undergoes reversible electron transfer in the solid state. Discrete molecular cluster species can be excised from the framework by digesting the solid in solutions of excess monocarbene. Finally, we demonstrate a synthetic route to monodisperse framework particles <i>via</i> coordination modulation.