The sensitivity of the indole chromophore and it excited state properties to solvent perturbations is assessed through the use of substituted indole derivatives in solution and complexed within a fis-cyclodextrin cavity. This system is presumed to be a prototype to study the effect of static perturbations of the indole chromophore on its' excited state relaxation mechanisms. A hypothesis is presented relating the electronic resonance structures of the indole molecule to its exciplex forming capabilities. Two locations on the indole ring are proposed to provide the most stable exciplex forming sites. One location, C-3, has long been recognized as a location for exciplex formation. However, a second site on the benzyl component of indole, C-5, may also provide a site for exciplex formation due to a different resonance structure. We postulate that this site, C-5, gains a negative charge through a resonance structure making it capable of forming an exciplex with polar molecules. This resonance structure involves the indole nitrogen donating it lone pair electrons to form a double bond with the six member ring of indole. Substitutions of the indole molecule that facilitate this resonance structure either through induction or resonance effects will produce an excited state indole molecule that will have the largest Stokes shift and will have enhanced susceptibility to solvent induced radiationless decay processes.