The azido oxide N3O

► The study reports the positive detection in the gas phase of the novel azido oxide N3O. ► It has been prepared by collisional electron transfer to the N3O+ ion and observed on a microsecond time scale. ► The oxide has been assigned a minimum lifetime of 0.7 μs and an open-chain structure of NNNO connectivity. ► The study examines the role of excited species in the formation of covalently bound ions suitable to neutralization.