Click Synthesis of Fluorine-Rich Cyclotriphosphazene Hydrazones. Synthesis and Supramolecular Structures of N3P3(N(Me)NCHC6F5)6, spiro-N3P3(C12H8O2)(N(Me)NCHC6F5)4, and dispiro-N3P3(C12H8O2)2(N(Me)NCHC6F5)2

The cyclophosphazene hydrazides N3P3(N(Me)NH2)6 (1), spiro-N3P3(C12H8O2)(N(Me)NH2)4 (2), and dispiro-N3P3(C12H8O2)2(N(Me)NH2)2 (3) have been readily elaborated by a click synthesis involving condensation with pentafluorobenzaldehyde to afford the fluorine-rich cyclophosphazene hydrazones N3P3(N(Me)NCHC6F5)6 (4), spiro-N3P3(C12H8O2)(N(Me)NCHC6F5)4 (5), and dispiro-N3P3(C12H8O2)2(N(Me)NCHC6F5)2 (6) in excellent yields. The molecular and crystal structures of 4−6 are reported. The crystal structures of 4−6 reveal a rich interplay of various intermolecular secondary interactions generating novel supramolecular architectures. The dependence of the molecular symmetry on the eventual supramolecular structures is also revealed. The crystal structure of 6 shows the selective entrapment of guest dioxane molecules.