Intramolecular N···F Pnictogen Bond Mitigates the Explosive Behavior of Azido‐L‐Phenylalanines

Organic azides are versatile intermediates but are plagued by intrinsic instability and potential explosiveness. Here, it is shown that fluorinated azido-L-phenylalanines display unexpected stability, arising from adjacent fluorine atoms that enforce intramolecular pnictogen bonding. Single-crystal X-ray diffraction reveals an intramolecular N···F pnictogen bond that orients the azide group and enhances molecular stability. Comparison with nonfluorinated analogs underscores the stabilizing effect of fluorine substitution in mitigating explosive decomposition. Quantum chemical and bond critical point analyses corroborate the stabilizing role of the N···F pnictogen bond.