Previous NMR studies of MFI-type Silicalite-1 revealed a pronounced influence of the OSDA on the fluoride dynamics: Whereas samples containing tetrapropylammonium (TPA + ) exhibit dynamic disorder at RT, the dynamic behavior is frozen out when using methyltributylammonium (MTBA + ) as OSDA. AIMD simulations revealed that the more heterogeneous charge distribution of MTBA + leads to a stronger electrostatic interaction with the fluoride anions, resulting in a larger energetic penalty for a displacement from their initial position and, hence, a reduction of dynamic disorder. In an investigation of AST-type systems, the nature of the OSDA was found to have a significant impact on the ordering of fluoride displacements within the d4r cages in AlPO4 and GaPO4 zeotypes. In the view of these earlier findings, some further insights into the systems studied here can be expected from an analysis of the F-OSDA interactions. Assuming that the positive charge of the OSDA is primarily localized in the vicinity of the nitrogen atoms (and the Co atom in [Co(cp)2] + ), an analysis of the F-N/F-Co RDFs can be used to evaluate the role of interactions between the positively polarized part of the OSDA and the fluoride anions.