Theoretical Prediction and Comprehensive Characterization of an All‐Nitrogenatomic Ring, Cyclo[18]Nitrogen (N18)

Abstract The cyclic molecule cyclo[18]carbon composed of 18 carbon atoms has been observed in condensed phase experiment in recent years and has attracted great attention. Through state‐of‐art quantum chemistry calculation, this study found that 18 nitrogen atoms can also form a macrocyclic system, cyclo[18]nitrogen (N 18 ), though its lifetime is very short at room temperature and can only exist for a relatively long time at very low temperatures. We comprehensively theoretically studied properties of N 18 , including geometric configurations, thermal decomposition mechanism and rate, molecular dynamics behavior, energetic properties, vibrational and electronic spectra. We also discussed in depth the electronic structure of N 18 , including nature of the N−N bonds, lone‐pairs, charge distribution characteristics, electronic delocalization, and aromaticity. This work is not only the first exploration of the macrocyclic N 18 molecule, but also the first time to systematically examine a very long‐chain substance fully composed of nitrogen atoms in isolated state.