Chemical Transformation of H₂S within the Pores of Metal–Organic Frameworks: Formation of Polysulfides

The chemical transformation of H2S inside the micropores of metal–organic frameworks (MOFs) to generate, in situ, polysulfides is an exciting novel strategy for the permanent sequestration of toxic H2S with promising implications for the design of novel sulfur battery electrodes. Herein, we discuss how this unexpected MOF-catalyzed polysulfide formation involves mechanisms that diverge radically from conventional coordination chemistry in MOFs. Long-held assumptions that MOF metal-linker bonds are rigid and static must be challenged to explain catalysis at MOF metal nodes that nominally lack open metal sites. Instead, this perspective highlights the importance of dynamic metal-linker bonding in designing future MOF catalysts. Embracing the long-overlooked hemilabile coordination chemistry of MOF nodes will inspire explorations into fundamentally new landscapes of heterogeneous reactivity.