Often, it is a non-trivial task to distinguish intertwined topologies as realized in rotaxanes and catenanes from non-intertwined isomers, such as simple host-guest complexes held together by non-covalent bonds or larger mono-macrocyclic analogues. This article discusses in detail the collision-induced fragmentations of the anions of catenanes, rotaxanes, and analogous compounds bearing tetralactam macrocycles. With these experiments, it is possible to distinguish intertwined from non-intertwined complexes through differences in the fragmentation pattern.