The optical properties of phenazine derivative probe solutions involving intersystem crossing from singlet to triplet states were investigated by time resolved spectroscopy. The room temperature phosphorescence emission presented different time responses when Cd2+ ions were bound to the probe chemical structure. The complex exciplex formation observed to occur in this case was not directly responsible for the change in the phosphorescence lifetime. This was more influenced by the new molecular conformation and modified spin–orbit coupling imposed by the binding of the Cd2+ ions to the phenazine molecules.