We elucidate the correlation between geometric structures and magnetic couplings in trinuclear iron(III) oxo acetate complexes [Fe₃O(OAc)₆(Py)_n]⁺ (n = 0, 1, 2, 3) when isolated and trapped as gaseous ions. Structural information arises from Infra Red-Multiple Photon Dissociation (IR-MPD) and Collision Induced Dissociation (CID) experiments in conjuction with Density Functional Theory (DFT) based calculations. We simulate the antiferromagnetic couplings between the Fe^III (d⁵) centers by employing a Broken Symmetry approach within our DFT calculations, and we extract the associated antiferromagnetic coupling constants. Coordination of one, two or three axial pyridine ligands to the [Fe₃O(OAc)₆]⁺ subunit distorts the geometry of the triangular Fe₃O core. The Fe–O_central bond lengths are enlarged or shortened depending on number of coordinated pyridine ligands. This significantly affects the antiferromagnetic coupling constants between the Fe^III centers ranging from −62 cm⁻¹ to −28 cm⁻¹ in [Fe₃O(OAc)₆(Py)_n]⁺ (n = 0, 1, 2, 3). A detailed analysis of the associated exchange couplings indicates a switching of magnetic ground states by pyridine coordination. The total spin S_T in the ground states of [Fe₃O(OAc)₆(Py)_n]⁺ raises from S_T = 1/2 (n = 0) to 3/2 (n = 1) and 5/2 (n = 2). Coordination of the third pyridine ligand (n = 3) re-establishes a spin ground state of S_T = 1/2. We thus identify a coordination controlled switching of magnetic ground states.