Identification of a prismatic P₃N₃ molecule formed from electron irradiated phosphine-nitrogen ices

Polyhedral nitrogen containing molecules such as prismatic P₃N₃ - a hitherto elusive isovalent species of prismane (C₆H₆) - have attracted particular attention from the theoretical, physical, and synthetic chemistry communities. Here we report on the preparation of prismatic P₃N₃ [1,2,3-triaza-4,5,6-triphosphatetracyclo[2.2.0.0^2,6.0^3,5]hexane] by exposing phosphine (PH₃) and nitrogen (N₂) ice mixtures to energetic electrons. Prismatic P₃N₃ was detected in the gas phase and discriminated from its isomers utilizing isomer selective, tunable soft photoionization reflectron time-of-flight mass spectrometry during sublimation of the ices along with an isomer-selective photochemical processing converting prismatic P₃N₃ to 1,2,4-triaza-3,5,6-triphosphabicyclo[2.2.0]hexa-2,5-diene (P₃N₃). In prismatic P₃N₃, the P-P, P-N, and N-N bonds are lengthened compared to those in, e.g., diphosphine (P₂H₄), di-anthracene stabilized phosphorus mononitride (PN), and hydrazine (N₂H₄), by typically 0.03-0.10 Å.  These findings advance our fundamental understanding of the chemical bonding of poly-nitrogen and poly-phosphorus systems and reveal a versatile pathway to produce exotic, ring-strained cage molecules.