This presentation details recent progress in our laboratory toward the synthesis and evaluation of underrepresented fluorinated functional groups that have been made more accessible using the TCICA/KF approach to oxidative fluorination. A major theme will be our recent merging of SF5 radical chemistry with strain-release functionalization of [1.1.1]propellane and [1.1.0]bicyclobutanes. Structural consequences of making these SF5-based "hybrid isosteres" and preliminary mechanistic insight will be discussed. Aside from being a topic of fundamental interest, we believe this work affords an unusual and subtle type of flexibility in molecular design that could prove useful in increasing availability of building blocks containing C(sp3)–SF5 bonds to medicinal chemists, agrochemists, and in the materials community.