Collision cross‐section analysis of self‐assembled metallomacrocycle isomers and isobars via ion mobility mass spectrometry

Complete structural identification could be accomplished using ESI-IM-MS. Our results affirm that self-assembly with Cd²⁺ and Zn²⁺ proceeds through reversible equilibria that generate the thermodynamically most stable structures, encompassing exclusively macrocyclic architectures that readily accommodate the 60^o ligand used. In contrast, complexation with Ni²⁺ and Fe²⁺ , which form stronger coordinative bonds, proceeds through kinetic control, leading to more complex mixtures and kinetically trapped less stable architectures, such as macrocyclic pentamers and linear isomers.