AbstractThe ion pair of the stereolabile C3‐symmetric, i+o proton complex [1⋅H]+ of diaza‐macropentacycle 1 and the configurationally stable Δ‐TRISPHAT ([Δ‐3]−) anion exists in the form of two diastereomers, namely, [Δ‐(1⋅H)][Δ‐3] and [Λ‐(1⋅H)][Δ‐3], the ratio of which, in terms of diastereomeric excess (de) decreases in the order [D8]THF (28 %)>CD2Cl2 (22 %)>CDCl3 (20 %)>[D8]toluene (16 %)>C6D6 (7 %)>[D6]acetone (0 %) at thermodynamic equilibrium. Except in the case of [D6]acetone, the latter is reached after a period of time that increases from 1 h ([D8]THF) to 24 h (CDCl3). Moreover, the initial value of the de of [1⋅H][Δ‐3] in CDCl3, before the thermodynamic equilibrium is reached, depends on the solvent in which the sample has been previously equilibrated (sample “history”). This property has been used to show that the crystals of [1⋅H][Δ‐3] formed by slow evaporation of CH2Cl2/CH3OH mixtures had 100 % de, which indicates that [1⋅H][Δ‐3] has enjoyed a crystallization‐induced asymmetric transformation. Structural studies in solution (NMR spectroscopy) and in the gas phase by calculations at the semiempirical PM6 level of theory suggest that the optically active anion is docked on the i+ (endo) external side of the proton complex such that one of the aromatic rings of [Δ‐3]− is inserted into a groove of [1⋅H]+, a second aromatic ring being placed astride the outside i+ pocket. Solvent polarity controls the thermodynamics of inversion of the [1⋅H]+ propeller. However, both polarity and basicity control its kinetics. Therefore, the rate‐limiting steps correspond to the ion‐pair separation/recombination and [1⋅H]+/1 deprotonation/protonation processes, rather than the inversion of [1⋅H]+, the latter being likely to take place in the deprotonated form (1).