The 308 nm photoexcitation of intrasilicalite I-2 results in emission in the near-infrared that is characteristic of caged electronic states of I-2. This is the first observation of such emission in a zeolite environment. A first order model is developed which adequately describes the repulsive interactions between iodine and the zeolite cage that leads to "caging." However, state specific interactions between the intrazeolite species and the zeolite can occur. States with vacant bonding orbitals can be stabilized as a result of donation of electron density from the zeolite cage into these vacancies. These state-specific chemical interactions between I-2 and the zeolite cage can lead to a shift in the energies of the relevant states and correspondingly a shift in the energy of optical transitions involving these states. The magnitude of the change in energy of the affected state correlates with the electron donating ability of the caging environment. Within the context of this correlation, silicalite has an effective ionization energy of approximately 11.8 eV. The absorption band of intrasilicalite I-2, which has been excited in this study at 308 nm, is attributed to promotion of the system to an ion pair state. An ion pair model of the excited state potential qualitatively describes the observed ultraviolet-visible emission from this system.