Regulating hydrogen transfer for diverse energetics

Hydrogen Transfer (HT) serves as a pivotal strategy for regulating the structure and properties of high-energy-density materials (HEDMs). However, conventional HT is confined to the parent skeleton ring of hydrogen-donor groups due to spatial constraints and energy barriers. In this work, we report a transannular HT phenomenon in nitramino energetics (ANTT), where hydrogen in nitroamino intriguingly migrate to the most distal site. Remarkably, tetrazole functionalization on ANTT further enables a secondary transannular HT with a record-breaking transfer distance of 8.058 Å—the longest HT ever documented to date. Combining with traditional intermolecular HT, we demonstrate totally four distinct HT modes, which endow the resulting compounds with divergent physicochemical properties and versatile applications: (1) High explosive: ANTT with transannular HT; (2) Initiator: ANTT-Tz with secondary transannular HT; (3) Insensitive explosive: ANTT-NH4/N2H5 with nonmetallic-ionic HT; (4) Pyrotechnic agents: ANTT-Li/Na/Sr with hydrogen elimination. Single-crystal X-ray and quantum calculations reveal that specific HT modes alter molecular charge distribution and H-bonding interactions, directly influencing the resulting material properties. This work advances HT chemistry and provides atom-level insights for tailoring organic functional materials.