A set of stilbene-substituted octasilicates [p-RStilxPh a-xSiO1.5]8 (R = H, Me, MeO, Cl, NMe 2 and x= 5.3-8) and [o-MeStilSiO1.5]8 were prepared. Model compounds were also prepared including the corner and half cages; [p-MeStilSi(OEt)3]. [p-Me2NStilSi(OSiMe 3)3], and [p-Me2NStilSi(O)(OSiMe)]4. These compounds were characterized by MALDI-TOF, TGA, FTIR, and 1H NMR techniques. Their photophysical properties were characterized by UV-vis, two-photon absorption, and cathodoluminescence spectroscopy (on solid powders), Including studies on the effects of solvent polarity and changes In concentration, These molecules are typically soluble, easily purified, and robust, showing Td(5%) > 400°C in air. The full and partial cages all show UV-vis absorption spectra (in THF) identical to the spectrum of frans-stilbene, except for [o-MeStilSiO1.5]8, which exhibits an absorption spectrum blue-shifted from trans-stilbene, However, the partial cages show emissions that are red-shifted by ∼20 nm, as found for stilbene-siloxane macrocycles, suggesting some interaction of the silicon center(s) with the stilbene π* orbital in both the corner and half cages. In contrast, the emission spectra of the full cages show red-shifts of 60-100 nm. These large red-shifts are supported by density functional theoretical calculations and proposed to result from interactions of the stilbene π* orbitals with a LUMO centered within the cage that has 4A1 symmetry and involves contributions from all Si and oxygen atoms and the organic substituents, Given that this LUMO has 3-D symmetry, it appears that all of the stilbene units interact in the excited state, consistent with theoretical results, which show an increased red-shift with an increase in the functionalization of a single corner to functionalization of all eight corners with stilbene. In the case of the Me2N- derivatives, this interaction is primarily a charge-transfer interaction, as witnessed by the influence of solvent polarity on the emission behavior. More importantly, the two-photon absorption behavior is 2-3 times greater on a per p-Me2Nstilbene basis for the full cage than for the corner or half cages. Similar observations were made for p-NH2stilbenevinyl8OS cages, where the greater conjugation lengths led to even greater red-shifts (120 nm) and two-photon absorption cross sections, Cathodoluminescence studies done on [p-MeStilSiO1.5]8 or [p-MeStilOS]8 powders exhibit essentially the same emissions as seen in solution at high dilution. Given that only the emissions are greatly red-shifted in these molecules, whereas the ground-state UV-vis absorptions are not changed from trans-stilbene, except for the ortho derivative, which is blue-shifted 10 nm. It appears that the interactions are only in the excited state. Theoretical results show that the HOMO and LUMO states are always the π and π* states on the stilbene, which show very weak shifts with increasing degrees of functionalization, consistent with the small changes in the UV-vis spectra. The band gap between the lowest unoccupied 4a1 symmetry core state localized inside the silsesquioxane cage and the highest occupied state (π state on stilbene), however, is markedly decreased as the number of stilbene functional groups is increased. This is consistent with the significant red-shifts in the emission spectra. The results suggest that the emission occurs from the 4a1 state localized on the cage. Moreover, for the compounds [p-RStil6-7Ph 2-1OS]8, the emissions are blue-shifted compared to those of the fully substituted compounds, suggesting the molecular symmetry is reduced (from cubic), thereby reducing the potential for 3-D delocalization and raising the energy of the LUMO, The implications are that these octafunctional molecules exhibit some form of 3-D interaction in the excited state that might permit their use as molecular transistors as well as for energy collection and dispersion as molecular antennas, for example, and for nonlinear optical applications. © 2010 American Chemical Society.