oc9b01096_si_001.pdf (6.88 MB)
Molecular and Crystal Features of Thermostable Energetic Materials: Guidelines for Architecture of “Bridged” Compounds
journal contribution
posted on 2019-12-27, 20:46 authored by Hui Li, Lei Zhang, Natan Petrutik, Kangcai Wang, Qing Ma, Daniel Shem-Tov, Fengqi Zhao, Michael GozinExtensive density functional theory (DFT) calculation
and data
analysis on molecular and crystal level features of 60 reported energetic
materials (EMs) allowed us to define key descriptors that are characteristics
of these compounds’ thermostability. We see these descriptors
as reminiscent of “Lipinski’s rule of 5”, which
revolutionized the design of new orally active pharmaceutical molecules.
The proposed descriptors for thermostable EMs are of a type of molecular
design, location and type of the weakest bond in the energetic molecule,
as well as specific ranges of oxygen balance, crystal packing coefficient,
Hirshfeld surface hydrogen bonding, and crystal lattice energy. On
this basis, we designed three new thermostable EMs containing bridged,
3,5-dinitropyrazole moieties, HL3, HL7,
and HL9, which were synthesized, characterized, and evaluated
in small-scale field detonation experiments. The best overall performing
compound HL7 exhibited an onset decomposition temperature
of 341 °C and has a density of 1.865 g cm–3, and the calculated velocity of detonation and maximum detonation
pressure were 8517 m s–1 and 30.6 GPa, respectively.
Considering HL7’s impressive safety parameters
[impact sensitivity (IS) = 22 J; friction sensitivity (FS) = 352;
and electrostatic discharge sensitivity (ESD) = 1.05 J] and the results
of small-scale field detonation experiments, the proposed guidelines
should further promote the rational design of novel thermostable EMs,
suitable for deep well drilling, space exploration, and other high-value
defense and civil applications.