Zhai Lianjie, Bi Fuqiang, Zhang Junlin, Zhang Jiarong, Li Xiangzhi, Wang Bozhou, Chen Sanping
State Key Laboratory of Fluorine & Nitrogen Chemicals, Xi'an Modern Chemistry Research Institute, Xi'an 710065, China.
College of Chemistry and Materials Science, Northwest University, Xi'an 710127, China.
ACS Omega. 2020 May 4;5(19):11115-11122. doi: 10.1021/acsomega.0c01048. eCollection 2020 May 19.
The design and preparation of new nitrogen-rich heterocyclic compounds are of considerable significance for the development of high-performing energetic materials. By combining nitrogen-rich tetrazole and oxygen-rich furoxan, a linear C-C bonded pentaheterocyclic energetic compound, 3,4-bis(3-tetrazolylfuroxan-4-yl) furoxan (BTTFO), was synthesized using a facile and straightforward method. Comprehensive X-ray analysis reveals the key role of hydrogen bonds, π-π interactions, and short contacts in the formation of dense packing of BTTFO and explains why a long chain-shaped molecule has a high density. This multicyclic structure incorporating three furoxan and two tetrazole moieties results in an exceptionally high heat of formation (1290.8 kJ mol) and favorable calculated detonation performances ( , 8621 m s, , 31.5 GPa). The interesting structure and fascinating properties demonstrated the feasibility of a linear multicyclic approach as a high-energy-density skeleton. Additionally, the thermodynamic parameters, electrostatic potential (ESP), and frontier molecular orbitals were also studied to get a better understanding of structure-property correlations.
新型富氮杂环化合物的设计与制备对于高性能含能材料的发展具有相当重要的意义。通过将富氮四唑和富氧呋咱相结合，采用简便直接的方法合成了一种线性C-C键合的五元杂环含能化合物3,4-双(3-四唑基呋咱-4-基)呋咱(BTTFO)。全面的X射线分析揭示了氢键、π-π相互作用和短程接触在BTTFO紧密堆积形成中的关键作用，并解释了为什么一个长链状分子具有高密度。这种包含三个呋咱和两个四唑部分的多环结构导致了异常高的生成热(1290.8 kJ/mol)和良好的计算爆轰性能(爆速8621 m/s，爆压31.5 GPa)。有趣的结构和迷人的性质证明了线性多环方法作为高能量密度骨架的可行性。此外，还研究了热力学参数、静电势(ESP)和前线分子轨道，以更好地理解结构-性能关系。
