Two stable electron donor acceptor conjugates, that is, 3 and 5b, employing La-2@I-h-C-80 and Sc3N@I-h-C-80, on one hand, and zinc tetraphenylporphyrin, on the other hand, have been prepared via [1 + 2] cycloaddition reactions of a diazo precursor. Combined studies of crystallography and NMR suggest a common (6,6)-open addition pattern of 3 and 5b. Still, subtly different conformations, that is, a restricted and a comparatively more flexible topography, emerge for 3 and 5b, respectively. In line with this aforementioned difference are the electrochemical assays, which imply appreciably stronger I-h-C-80/ZnP interactions in 3 when compared to those in 5b. Density functional calculations reveal significant attractions between the two entities of these conjugates, as well as their separately localized HOMOs and LUMOs. The geometrical conformations and LUMO distributions of 3 and 5b, at our applied computational level, are slightly varied with their different endohedral clusters. The Clusters also exert different impact on the excited state reactivity of the conjugates. For example, 3 undergoes, upon photoexcitation, a fast charge separation process and yields a radical ion pair, whose nature, namely, (La-2@C-80)(center dot-)-(ZnP)(center dot+)) versus (La-2@C-80)(center dot+)-(ZnP)(center dot-)), varies with solvent polarity. 5b, on the other hand, afforded the same (Sc3N@C-80)(center dot-)-(ZnP)(center dot+)) radical ion pair regardless of the solvent.