Abstract
Development of thermally stable, insensitive materials with attractive physiochemical properties continues to be heavily pursued in the field of energetic materials. High-energy-density compounds assembled by the combination of polynitro, nitroamino or azo groups and nitrogen-rich frameworks are often thermally unstable and sensitive to impact and friction. This conflicting nature of energy and stability strongly encourages designers of molecules to study existing structures at the molecular level in order to develop new methodologies for construction of potential energetic materials. In this work, a robust strategy which takes advantage of π-philic molecular recognition between planar energetic anions and cations is pursued. Our work not only generates insights for the design and synthesis of new energetic sandwich salts with good thermal stability and low sensitivity but also inspires the enrichment of a variety of new excellent performing high-energy materials.