AbstractThe title compounds, including hybrids (n ≠ n’), were assembled on benzene core in a unified way based on only one starting material C6F5NH2 and a limited number of simple substitution and condensation reactions. The heterocyclic moieties were 1,3‐diazoles, 1,2,3‐triazoles, 1,2,5‐thia(selena)diazoles, 1.4‐diazines and 1,5‐diazepines, as well as 1,3,2‐dioxaboroles. Representatives of all new scaffolds were characterized by XRD. Compounds synthesized are of biomedical interest in the context of apoptotic anticancer activity, and the 1,2,5‐thiadiazole/1,3,2‐dioxaborole hybrid also in that of neutron or/and proton capture therapy of cancer. New 1,2,5‐chalcogenadiazoles are protected forms of otherwise hardly accessible fluorine‐containing di‐ and tetra‐amines for further syntheses.