Coupling between substituents as a function of cage structure: synthesis and valence ionized states of bridgehead disubstituted parent and hexafluorinated bicyclo[1.1.1]pentane derivatives C5X6Y2.

He(I) photoelectron spectroscopy was used to examine the valence-shell electronic structure of three new and seven previously known bicyclo[1.1.1]pentane derivatives, 1,3-Y2-C5X6 (for X = H, Y = H, Cl, Br, I, CN; for X = F, Y = H, Br, I, CN).