A series of pen-substituted phosphorus tellurium systems R-Te-Acenap-PR2 (R' = Ph, p-An, Nap, Mes, Tip; Acenap = acenaphthene-5,6-diyl (-C12H8); R = 'Pr, Ph) exhibiting large "through-space" spin spin coupling constants and the "onset" of three-center four-electron type interactions is presented. The influence of the substituents at the phosphorus and tellurium atoms as well as their behavior upon oxidation (with S, Se) or metal-coordination (Pt, Au) is discussed using NMR spectrostopy, single-crystal X-ray diffraction, and advanced density functional theory studies including NBO, AIM, and ELI-D analyses.