An important goal in the detonation physics and chemistry community is to design explosives with high-performance capabilities, yet sufficiently low impact and shock sensitivities. The traditional ways of developing increasingly energetic explosives have led to an increase in sensitivity. It is, therefore, of practical and theoretical importance to design, from molecular level considerations, polycrystalline explosive systems which clearly exhibit directional sensitivity and initiation properties, and which approach the insensitivity of homogeneous or single-crystal explosives. Theoretical studies indicate that such systems may be constructed from special materials such as high-quality pyrolytic, layered, hexagonal boron nitride (BN) crystals. Intercalation of the crystals with various oxidizing agents can yield an explosive system with the desired properties. Under ordinary laboratory conditions and with modest pressures, the intercalate molecules readily enter the host lattice by exploiting the weak bonding between the layers, resulting in denser, metastable crystals. High energy release is achieved when products containing B2O3 are formed.