Abstract
The spectroscopic behavior of a series of salts, comprising a macrocyclic bis-cyanine dication ( 1) and various anions, was studied in hydrocarbon and ethanol solution. In benzene solution, the nature of the anion controls the properties of the cyanine. Molecular modeling reveals that there are two nearly isoenergetic conformations for 1. The calculations show that in benzene solution anions are positioned above and below the mean plane of 1. When the anion is small, for example trifluoroacetate, it does not perturb the structure of the cyanine. In contrast, when the anion is large, for example, tetrakis-perfluorophenyl borate, it distorts the structure of the cyanine and modifies its spectroscopic properties due to a change in excitonic interaction.
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