A triply benzocrown-ether-functionalized trialkynylmesitylene derivative with C3 symmetry as well as its linear analogue have been synthesized and their optical properties have been studied by UV/Vis absorption, steady-state and time-resolved fluorescencece spectroscopy. The spectroscopic investigation of the uncomplexed compounds revealed the nature of the electronic and excitonic communication pathway in the ground and excited states of the all-meta-substituted chromophore system. Upon cation complexation, the octopolar character of the free trialkynyl compound becomes dipolar and finally returns to octopolar in the fully complexed species.