Many commercial HEMs suffer from a combination of harsh nitration conditions in synthesis (RDX, HMX, TNT, CL-20), significant toxicity (RDX, Pb(N3)2, AP), or deleterious environmental impacts in storage and use. In light of these factors, nitrogen-rich explosives have garnered significant attention as replacements for canonical primary and secondary explosives. However, a lack of reported structure-property relationships for nitrogen-rich functionalities such as organic azides and nitrogen-containing heterocycles hampers the rational design of new heterocyclic explosives and structural tuning of existing HEMs.