The title compounds, including hybrids (n ≠ n’), were assembled on benzene core in a unified way based on only one starting material C 6 F 5 NH 2 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.