Structured emission in the gas phase to two weakly bound valence states that correlate with the third dissociation limit, I*(2P1/2)+I*(2P1/2), designated as (bb), from two third tier ion-pair states of I2 correlating with I-(1S0)+I+(1D2), the 1g(1D2), and F'0u+(1D2) states, has been observed for the first time. The 1u(bb) state is shown to be bound by 377+/-2 cm(-1) and molecular constants have been determined. Vibrational structure in the 0g+(bb) state could not be resolved but the spectrum is consistent with the state being bound by 435 cm(-1). The relative integrated intensities of the emissions from both ion-pair states to various valence states have also been measured, and some aspects are rationalized in terms of the electronic configurations of the upper and lower states. Bound levels of a previously uncharacterized 1g(ab) valence state have also been observed in emission from the gamma1u(3P2) ion-pair state. The lower state is shown to be bound by 270+/-2 cm(-1) and molecular constants have been determined.