High-pressure synthesis of K_{4}N_{6} compound entirely composed of aromatic hexazine [N_{6}]^{4-} anion

Abstract

The synthesis of hexazine N_{6} ring is another milestone in nitrogen chemistry after that of aromatic [N_{5}]^{-} anion. However, due to the diversity of carried charges, realizing compounds entirely composed of aromatic hexazine N_{6} ring potentially with high-stability is a challenge. The first reported hexazine N_{6} ring is [N_{6}]^{2-} anion in K_{2}N_{6} [Nat. Chem. 14, 794 (2022)] that does not adhere to H\''uckel's rule, and subsequently, the aromatic hexazine [N_{6}]^{4-} anion mixed with [N_{5}]^{-} anion and N_{2} dimers is realized in the complex compound K_{9}N_{56} [Nat. Chem. 15, 641 (2023)], where 5.36\% of N atoms form aromatic N_{6} ring. Here, we theoretically predict that all N atoms form aromatic hexazine [N_{6}]^{4-} anion in K_{4}N_{6}, which becomes stable at 60 GPa and can stably exist up to 600 K at 0 GPa. Following this approach, based on the diamond anvil cell, K_{4}N_{6} composed of 100\% aromatic hexazine [N_{6}]^{4-} anion is synthesized at 45 GPa after laser-heating and identified by synchrotron X-ray diffraction and Raman spectroscopy. Our results bring us closer to achieving aromatic N6 rings at ambient condition.

11 pages, 4 figures