Controllable Structural Modulation: Assembling Variable Dimension Energetic Metal-Organic Frameworks via Free Protons.

Herein, we provide an efficient strategy for constructing three-dimensional (3D) energetic coordination polymers (ECPs), namely, metal-organic frameworks (EMOFs), avoiding solvent coordination without changing the organic ligands or metal nodes. Three ECPs with the same ligand and metal center, namely, two-dimensional (2D) layer ECP [Pb(HOBTT)(H 2 O) 2 ] n ( 1 ), 3D solvent-free EMOFs [Pb(HOBTT)] n ( 2 ), and dense [Pb 3 (OBTT) 2 ] n ( 3 ) (H 3 OBTT = 4,5-bis(1-hydroxytetrazol-5-yl)-2 H -1,2,3-triazole), were rationally designed and synthesized via free protons. As expected, the theoretical density of 3 (4.080 g·cm -3 ) is greater than those of 2 (3.299 g·cm -3 ) and 1 (3.055 g·cm -3 ). Thermal stabilities indicate that their decomposition temperature exceeds 300 °C. Theoretical calculations show that the detonation performance of 3 is better than that of 1 and 2 . The detonation performance of 1 - 3 was further proven by laser irradiation.