How aromatic system size affects the sensitivities of highly energetic molecules?

Veljković, Ivana; Radovanović, Jelena I.; Veljković, Dušan Ž.

doi:10.1039/d1ra06482g

Cited by 6 publications

(4 citation statements)

References 33 publications

(34 reference statements)

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“…The weakest Mayer bond order of C-NO 2 bond for compound DMPT-1 (BN = 0.794) is shorter than that of DMPT-2 (BN = 0.797), showing that the bond strength of C-NO 2 bonds in DMPT-1 is stronger than that of DMPT-2 , which could explain in part the difference in thermal stability. Generally, aromaticity is considered an important parameter for the determination of molecular stability [ 30 , 31 ]. Therefore, the aromaticity of each heterocycle atmosphere could also be quantitatively described through the multicenter bond orders analysis using Multiwfn3.5 [ 32 ].…”

Section: Resultsmentioning

confidence: 99%

N-Functionalization of 5-Aminotetrazoles: Balancing Energetic Performance and Molecular Stability by Introducing ADNP

Xiong

Chang

Cai

et al. 2022

IJMS

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5-aminotetrazole is one of the most marked high-nitrogen tetrazole compounds. However, the structural modification of 5-aminotetrazole with nitro groups often leads to dramatically decreased molecular stability, while the N-bridging functionalization does not efficiently improve the density and performance. In this paper, we report on a straightforward approach for improving the density of 5-aminotetrazole by introducing 4-amino-3,5-dinitropyrazole. The following experimental and calculated properties show that nitropyrazole functionalization competes well with energetic performance and mechanic sensitivity. All compounds were thoroughly characterized using IR and NMR spectroscopy, elemental analysis, and differential scanning calorimetry (DSC). Two energetic compounds (DMPT-1 and DMPT-2) were further confirmed by implementing single-crystal X-ray diffraction studies. Compound DMPT-1 featured a high crystal density of 1.806 g cm−3, excellent detonation velocity (vD = 8610 m s−1), detonation pressure (P = 30.2 GPa), and impact sensitivity of 30 J.

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Section: Resultsmentioning

confidence: 99%

N-Functionalization of 5-Aminotetrazoles: Balancing Energetic Performance and Molecular Stability by Introducing ADNP

Xiong

Chang

Cai

et al. 2022

IJMS

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“…Hydrogen‐bonding interactions can influence the electron density of an HEDM and may play a role in the sensitivity of the molecule. [ 38 ] In the azo molecules, these interactions pull the electron density away from the azo nitrogens to strengthen the CN azo bond. Azole‐based HEDMs tend toward planarity in the absence of sterics to maximize these hydrogen bonds.…”

Section: Resultsmentioning

confidence: 99%

“…[30] Initiation of explosive decomposition could be attributed to a trigger bond within the explosophore, defined as the bond that breaks to initiate detonation. [6,31,32] Several computational methods have been used to analyze sensitivities of new HEDMs, including atoms in molecules (AIM), [33,34] bond dissociation energies (BDEs), [35][36][37][38] distributed multipole analysis, [39,40] unimolecular decomposition activation barriers, [41,42] estimation of impact sensitivities, [30,32,40,43,44] and Mulliken population analysis. [45][46][47] Our group and others have applied Wiberg bond index (WBI), [48] a measure of the bond's electron density, to identify trigger linkages in HEDMs.…”

Section: Introductionmentioning

confidence: 99%

Trigger bond analysis of azo‐based energetic materials

Zengel

Garcia

Goodrich

et al. 2022

J of Physical Organic Chem

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Azo‐based energetic materials may initiate explosive decomposition by extruding molecular nitrogen to produce radical fragments. Density functional theory and Wiberg bond index analysis were used to determine trends in bond strength for a series of aromatic azo compounds. Interactions between ortho ring hydrogens and an azo nitrogen lone pair favor a planar molecule with a strengthened azo linkage. Steric groups substituted ortho to the azo linkage cause the molecule to twist, which disrupts delocalization of the π density and weakens the CNazo bond. The results of this study are generally consistent with the low sensitivity of various aromatic azo‐based energetic materials. Discrepancies between calculated bond strengths and the experimental impact sensitivities could be attributed to packing forces that affect molecular planarity in the solid state.

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“…Fused ring energetic compounds are important skeletons for the future design of novel energetic compounds due to their conjugated planar structures that can effectively increase the density and molecular stability of the compounds with good thermal stability and low Molecules 2024, 29, 353 2 of 12 sensitivity [4]. The appearance of fused rings and the increase in the number of rings affect the value of the electrostatic potential in the central region of the surface of the explosive molecule, which is related to the sensitivity of the energetic materials [5]. They improve the safety of the synthesis, transfer, and storage of energetic materials.…”

Section: Introductionmentioning

confidence: 99%

High-Density Energetic Materials with Low Mechanical Sensitivity and Twinning Derived from Nitroimidazole Fused Ring

Liu,

Lv,

Zhang

et al. 2024

Molecules

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The innovative synthesis of 3,8-dibromo-2,9-dinitro-5,6-dihydrodiimidazo [1,2-a:2′,1′-c]pyrazine and 3,9-dibromo-2,10-dinitro-6,7-dihydro-5H-diimidazo [1,2-a:2′,1′-c][1,4]diazepine is described in this study. The tricyclic fused molecular structures are formed by the respective amalgamation of piperazine and homopiperazine with the imidazole ring containing nitro. Compound 1 and 2 possess excellent high-density physical properties (ρ1 = 2.49 g/cm3, ρ2 = 2.35 g/cm3) due to the presence of a fused ring structure and Br atom. In addition to their high density, they have high decomposition temperatures (Td > 290 °C) which means that they have excellent thermal stability and can be used as potential heat-resistant explosives. Low mechanical sensitivities (IS > 40 J, FS > 360 N) are observed. The twinning structure of 2 was resolved by X-ray diffraction. Non-covalent interaction analysis, Hirshfeld surfaces, 2D fingerprint plot, and Electrostatic potential analysis were used to understand the intramolecular interactions in relation to physicochemical properties. The unique structures of this type of compound provide new potential for the evolution of energetic materials.

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How aromatic system size affects the sensitivities of highly energetic molecules?

Abstract: DFT calculations showed that with the increase of the aromatic system size, values of positive electrostatic potential above the central areas of energetic molecules decrease, leading to the decrease in the sensitivities towards detonation.

Cited by 6 publications

References 33 publications

N-Functionalization of 5-Aminotetrazoles: Balancing Energetic Performance and Molecular Stability by Introducing ADNP

N-Functionalization of 5-Aminotetrazoles: Balancing Energetic Performance and Molecular Stability by Introducing ADNP

Trigger bond analysis of azo‐based energetic materials

High-Density Energetic Materials with Low Mechanical Sensitivity and Twinning Derived from Nitroimidazole Fused Ring

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