In this work, the properties of complexation of tetraphosphonate cavitands towards methylpyridinium guests were investigated via isothermal titration calorimetry (ITC). For this purpose, Tiiii [C3H7, CH3, Ph], Tiiii [C3H7, H, Ph], TSiiii [C3H7, H, Ph] hosts and three different methylpyridinium guests were synthesised. The role of the following parameters in the host–guest complexation was investigated:(i) solvation,(ii) nature of the guest ...