This manuscript focuses on the influence that the addition of Fe2+ as electron donor quencher exerts on the photophysics of 2,4,6-triphenylpyrylium (TP+) depending on the formation or not of supramolecular inclusion complexes with cucurbit[n]uril (n: 7 or 8). H-1-NMR spectroscopy does not provide evidence supporting the formation of a ternary TP+@CB[n]-Fe2+ complex. Emission quenching studies indicate that the prevalent deactivation mechanism for the quenching of TP+ emission by Fe2+ is by increasing the ionic strength of the solution, with no evidence for the occurrence of dynamic quenching. Laser flash photolysis indicates that while the triplet excited state of TP+ is instantaneously quenched by Fe2+ in the absence of CB[n], formation of the TP+@CB[n] inclusion complex protects TP+ triplet excited state from quenching, an effect that is more pronounced in the case of CB[8] due to the deeper penetration and more complete encapsulation of the heterocyclic pyrylium core inside the larger CB[8] capsule. (C) 2013 Elsevier Inc. All rights reserved.