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

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 via 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 via coordination modulation.

Automated summary

This study demonstrates the preparation of main-chain organometallic polymers using Janus NHC linkers and polynuclear cluster nodes for the first time. The crosslinked framework Co4S4-MCOP undergoes reversible electron transfer in the solid state and discrete molecular cluster species can be excised from the framework through digestion in solutions of excess monocarbene. Additionally, a synthetic route to monodisperse framework particles is shown via coordination modulation.