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High-resolution electrospray ionization ion mobility mass spectrometry has revealed a gas-phase isomer of the ubiquitous, extremely well-studied Au 25 (SR) 18  cluster both in anionic and cationic form. The relative abundance of the isomeric structures can be controlled by in-source activation. The measured collision cross section of the new isomer agrees extremely well with a recent theoretical prediction (    Matus  M. F.   ; et al.  Chem. Commun.  2020 ,  56 ,  8087  ) corresponding to a Au 25 (SR) 18  –  isomer that is energetically close and topologically connected to the known ground-state structure via a simple rotation of the gold core without breaking any Au–S bonds. The results imply that the structural dynamics leading to isomerization of thiolate-protected gold clusters may play an important role in their gas-phase reactions and that isomerization could be controlled by external stimuli.

Experimental Confirmation of a Topological Isomer of the Ubiquitous Au25(SR)18 Cluster in the Gas Phase

Experimental Confirmation of a Topological Isomer of the Ubiquitous Au₂₅(SR)₁₈ Cluster in the Gas Phase