Topology Switching in Polymetallic Fragments Governed by Metal Encapsulation

High Resolution Image Download MS PowerPoint Slide Metallosupramolecular assemblies are promising platforms for selective extraction, catalysis, and molecular recognition, yet their solution-phase synthesis often relies on complex self-assembly pathways that can be difficult to control. Here, using ion mobility mass spectrometry supported by density functional theory calculations, we introduce a gas-phase approach for directing topology in polymetallic complexes based on the encapsulation of coordination metal cations within a homometallic {Cr 8 } ring. Upon inclusion, the resulting host–guest complexes undergo collision-induced dissociation to produce distinct polymetallic fragments whose topologies, ring, host–guest complex or open chain, depend on the identity of the guest cation. This topology switching enables the targeted synthesis of new polymetallic rings, host–guest complexes and open chains in vacuo and provides insight into the stoichiometric and conformational preferences of such assemblies.