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The importance of molecular conformation to the properties: a DFT study of the polynitro heterocyclic compounds based on dodecahydrodiimidazo [4,5-b:4′,5′-e]pyrazine structure

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Abstract

Two series of polynitro heterocyclic compounds with three conformations are designed based on the obtained dodecahydrodiimidazo [4,5-b:4′,5′-e]pyrazine “565” structure. First, the conformations including boat, chair, and plane, are optimized at B3PW91/6-311+G(d,p) level and some important properties are calculated. Based on the bond order, bond dissociation enthalpies and molecular energy analysis, it is found that the boat conformation owns lower energy and better bond order than the other two, and thus is most stable. Then, a further study on the electrical potential surfaces (EPS) proves that the stability of boat conformation can be contributed to the better balance between the positive and negative EPS. Next, according to molecular energy gap and density of state, the effect of each group on molecule is investigated: electrons on nitro group, compared with those on the framework, are easier to be activated so as to cause decomposition, thus nitro groups will determine the stability of molecule. Finally, the explosive velocity, pressure, and impact sensitivity of designed compounds are calculated. Results show that their explosive performances are significantly better than current energetic materials, and it is extraordinary enough that some compounds among them also maintain very good sensitivity.

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Acknowledgments

We thank National Natural Science Foundation of China (No: 51374131) for support of this research.

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Authors and Affiliations

  1. School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing, 210094, People’s Republic of China

    Qin Hua Li, Peng Cheng Wang & Ming Lu

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  1. Qin Hua Li
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  2. Peng Cheng Wang
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Correspondence to Ming Lu.

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Li, Q.H., Wang, P.C. & Lu, M. The importance of molecular conformation to the properties: a DFT study of the polynitro heterocyclic compounds based on dodecahydrodiimidazo [4,5-b:4′,5′-e]pyrazine structure. Struct Chem 26, 667–674 (2015). https://doi.org/10.1007/s11224-014-0524-1

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  • DOI: https://doi.org/10.1007/s11224-014-0524-1

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