Synthesis of a high-energy-density material through rapid replacement of crystal water of hydrates

Abstract

<h2>Summary</h2> An energetic cocrystal TNBI-TANPDO (TNBI, 4,4′,5,5′-tetranitro-2,2′-bi-1H-imidazole; TANPDO, 2,4,6-triamino-5-nitropyrimidine-1,3-dioxide) was rapidly self-assembled in aqueous solution from the precursors of TNBI dihydrate and TANPDO monohydrate. Benefiting from the formation of a novel strong hydrogen bond synthon between TNBI and TANPDO by replacing crystal H₂O molecules in its precursors, TNBI-TANPDO exhibits nearly all of the desirable properties required by energetic materials, including higher density (1.89 g cm⁻³ at room temperature), higher thermostability (275°C), and lower solubility (21 mg in 100 mL) in water relative to the two precursors. Additionally, TNBI-TANPDO is insensitive to mechanical stimuli, although exhibiting an excellent detonation performance (D_v = 8,648 m s⁻¹, P = 33.17 GPa). These desirable properties make TNBI-TANPDO an extremely promising insensitive high explosive. This work provides a new insight into eliminating crystal H₂O of hydration, and a new family of energetic cocrystals with excellent properties can be prepared based on this work.