Self‐Assembly, Rearrangement, and Disassembly of {Cr ₆ } Horseshoe Oligomers

Abstract

Abstract Molecular assemblies are commonly found in biological systems, and designing synthetic mimics of these is a challenge for modern chemistry. Here, we apply ion mobility mass spectrometry (IM‐MS), density functional theory (DFT), and mass‐selective electrospray ion beam deposition followed by low‐temperature scanning tunneling microscopy (STM) to decipher the self‐assembly, rearrangement, and disassembly processes of {Cr 6 } n horseshoe oligomers ( n  = 1–5). Activated tandem IM‐MS reveals the oligomer disassembly in detail, highlighting the stability of the dimer unit. When n  = 2 and n = 3 oligomers are deposited on surfaces, we observe the rearrangement of dimers and trimers to dimers of dimers, and at higher coverages, the formation of an unexpected hexagonal‐like network. In its entirety, the experimental and computational data provide a convincing framework for the analysis of supramolecular assembly processes in noncrystalline phases that could be used in future design strategies.