Journal article

Publication year: 2021

Pages: 5467-

Journal: Nature Communications

Volume number: 12

Issue number: 1

Open access status: Gold

DOI Link: https://doi.org/10.1038/s41467-021-25775-1

Publisher: Nature Research

Abstract: 
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 (N-2) 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 angstrom. 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.High-nitrogen content polyhedral molecules are of fundamental interest for theory and for synthesis applications. The authors, using isomer selective, tunable soft photoionization reflectron time-of-flight mass spectrometry, identify the formation of a hitherto elusive prismatic P3N3 molecule during sublimation of PH3 and N-2 ice mixtures exposed to energetic electrons.

Harvard Citation style: Zhu, C., Eckhardt, A., Chandra, S., Turner, A., Schreiner, P. and Kaiser, R. (2021) Identification of a prismatic P3N3 molecule formed from electron irradiated phosphine-nitrogen ices, Nature Communications, 12(1), p. 5467. https://doi.org/10.1038/s41467-021-25775-1

APA Citation style: Zhu, C., Eckhardt, A., Chandra, S., Turner, A., Schreiner, P., & Kaiser, R. (2021). Identification of a prismatic P3N3 molecule formed from electron irradiated phosphine-nitrogen ices. Nature Communications. 12(1), 5467. https://doi.org/10.1038/s41467-021-25775-1