Temperature dependent luminescence studies were conducted on terbium based compounds that contain different ligands resulting in complex structural features. Herein we present synthesis, structural, and photoluminescence studies of several of these Tb3+ based compounds where variation of the counter anion results in a change in their photoluminescence properties. The effect of temperature on the intramolecular energy transfer (IET) mechanism will also be discussed in detail. The complexes show enhanced luminescence feature at liquid nitrogen temperature when compared with that of room temperature. The system also displays dual donor feature where both the organic ligand, terpridine and the platinum tetracyanide act as donors. Both species are directly coordinated to the acceptor cation. When the counter anion is changed to the acetate ion, the bonding interaction between the platinum tetracyanide and Tb3+ is removed, and the energy transfer pathway is blocked. As a result, the donor emits strongly, albeit totally quenched in the complexes with direct bonding interaction. Moreover, all of these complexes show interesting structural features that consist of channels capable of accommodating volatile organic compounds (VOC). Details of the photoluminescence studies will be presented. This study is part of our overall goal of developing materials for VOC (volatile organic compounds) sensing.