Naphthalene derivatives have the capability of forming higher order complexes than the typical 1:1 stoichiometry with all three of the common cyclodextrins (alpha, beta, and gamma). The 2-acetylnaphthalene (2-AN)/gamma-cyclodextrin (gamma-CD) system exhibits a long wavelength fluorescence emission at higher gamma-CD concentrations, which has been assigned to an excimer band from bound 2-AN dimer. On the basis of the fact that only free 2-AN and the bound dimer fluoresce in this system, we have proposed mathematical models to decide whether the dimer formula is (2-AN)<sub>2</sub>/gamma-CD or (2-AN)<sub>2</sub>/(gamma-CD)<sub>2</sub>. Our analysis indicates that the latter formula is the correct one. This result is unanticipated, given the fact that a single gamma-CD cavity could accommodate two naphthalene rings.

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