Skip to main content
SpringerLink
Log in

Self-assembled energetic coordination polymers based on multidentate pentazole cyclo-N5−

多齿五唑N5−的自组装纳米含能配位聚合物

  • Articles
  • Published:
Science China Materials Aims and scope Submit manuscript

Abstract

Coordination to form polymer is emerging as a new technology for modifying or enhancing the properties of the existed energetic substances in energetic materials area. In this work, guanidine cation CN3H6+ (Gu) and 3-amino-1,2,4- triazole C2H4N4 (ATz) were crystallized into NaN5 and two novel energetic coordination polymers (CPs), (NaN5)5[(CH6- N3)N5](N5)3– (1) and (NaN5)2(C2H4N4) (2) were prepared respectively via a self-assembly process. The crystal structure reveals the co-existence of the chelating pentazole anion and organic component in the solid state. In polymer 1, Na+ and N5– were coordinated to form a cage structure in which guanidine cation [C(NH2)3]+ was trapped; for polymer 2, a mixedligand system was observed; N5– and ATz coordinate separately with Na+ and form two independent but interweaved nets. In this way, coordination polymer has been successfully utilized to modify specific properties of energetic materials through crystallization. Benefiting from the coordination and weak interactions, the decomposition temperatures of both polymers increase from 111°C (1D structure [Na(H2O)(N5)] ∙2H2O) to 118.4 and 126.5°C respectively. Moreover, no crystallized H2O was generated in products to afford the anhydrous compounds of pentazole salts with high heats of formation (>800 kJ mol–1). Compared to traditional energetic materials, the advantage in heats of formation is still obvious for the cyclo-N5– based CPs, which highlights cyclo-N5– as a promising energetic precursor for high energy density materials (HEDMs).

摘要

在含能材料领域, 通过协同作用形成聚合物已成为改善或增强现有含能物质性能的一种新技术. 本文将胍阳离子CH3H6+(GU)和氨基-1,2,4-三唑C2H4N4(ATZ)与NaN5一起结晶, 通过自组装过程分别制备了两种新型含能配位聚合物(CPs), (NaN5)5[(CH3H6)N5](N5)3 (1)和(NaN5)2(C2H4N4) (2). 晶体结构表明, 在固体状态下, 螯合的五唑阴离子实现了与其他有机成分共存. 聚合物1, Na+和N5−形成笼状, 并将胍阳离子[C(NH2)3]+围在里面; 而聚合物2是一个混合配体体系, N5−和ATZ与Na+分别形成两个独立但相互交织的网. 这些都说明了通过结晶形成配位聚合物, 来改变含能材料的特定性能是可行的. 受益于配位和弱相互作用, 两种聚合物的热分解温度分别从111°C (一维结构[Na(H2O)(N5)]·2H2O)提高到了118.4和126.5°C. 此外, 他们成功地除去了产物中的结晶水, 成为具有高生成热特点的五唑无水盐(> 800 kJ mol−1). 聚合物1和2比传统能量材料高得多的生成热, 表明N5−作为高能量密度材料(HEDMs)的前驱体, 具有很好的前景.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Christe KO. Polynitrogen chemistry enters the ring. Science, 2017, 355: 351–351

    Article  Google Scholar 

  2. Klapötke TM. Chemistry of High-Energy Materials. Boston: De Gruyter, 2017

    Book  Google Scholar 

  3. Yin P, Shreeve JM. Advances in heterocyclic chemistry. London: Elsevier, 2017, 121: 89–131

    Google Scholar 

  4. Zhang Q, Shreeve J’M. Energetic ionic liquids as explosives and propellant fuels: a new journey of ionic liquid chemistry. Chem Rev, 2014, 114: 10527–10574

    Article  Google Scholar 

  5. Singh RP, Gao H, Meshri DT, Shreeve JM. High Energy Density Materials. Berlin: Springer, 2007, 35–83

    Book  Google Scholar 

  6. Chen SL, Yang ZR, Wang BJ, et al. Molecular perovskite highenergetic materials. Sci China Mater, 2018, doi: 10.1007/s40843-017-9219-9

    Google Scholar 

  7. Gao H, Shreeve J’M. Azole-based energetic salts. Chem Rev, 2011, 111: 7377–7436

    Article  Google Scholar 

  8. Fischer N, Fischer D, Klapötke TM, et al. Pushing the limits of energetic materials—the synthesis and characterization of dihydroxylammonium 5,5’-bistetrazole-1,1’-diolate. J Mater Chem, 2012, 22: 20418–20422

    Article  Google Scholar 

  9. Zhang S, Yang Q, Liu X, et al. High-energy metal–organic frameworks (HE-MOFs): Synthesis, structure and energetic performance. Coord Chem Rev, 2016, 307: 292–312

    Article  Google Scholar 

  10. Li S, Wang Y, Qi C, et al. 3D energetic metal-organic frameworks: synthesis and properties of high energy materials. Angew Chem Int Ed, 2013, 52: 14031–14035

    Article  Google Scholar 

  11. McDonald KA, Seth S, Matzger AJ. Coordination polymers with high energy density: an emerging class of explosives. Cryst Growth Des, 2015, 15: 5963–5972

    Article  Google Scholar 

  12. Zhang J, Shreeve JM. Time for pairing: cocrystals as advanced energetic materials. CrystEngComm, 2016, 18: 6124–6133

    Article  Google Scholar 

  13. Landenberger KB, Bolton O, Matzger AJ. Energetic–energetic cocrystals of diacetone diperoxide (DADP): dramatic and divergent sensitivity modifications via cocrystallization. J Am Chem Soc, 2015, 137: 5074–5079

    Article  Google Scholar 

  14. Haiges R, Boatz JA, Vij A, et al. Polyazide chemistry: preparation and characterization of Te(N3)4 and [P(C6H5)4]2[Te(N3)6] and evidence for [N(CH3)4][Te(N3)5]. Angew Chem Int Ed, 2003, 42: 5847–5851

    Article  Google Scholar 

  15. Fehlhammer WP, Beck W. Azide chemistry—an inorganic perspective, part I metal-azides: overview, general trends and recent developments. Z Anorg Allg Chem, 2013, 639: 1053–1082

    Article  Google Scholar 

  16. Christe KO, Wilson WW, Sheehy JA, et al. N5 +: a novel homoleptic polynitrogen ion as a high energy density material. Angew Chem Int Ed, 1999, 38: 2004–2009

    Article  Google Scholar 

  17. Haiges R, Schneider S, Schroer T, et al. High-energy-density materials: synthesis and characterization of N5 +[P(N3)6]-, N5 +[B(N3)4]-, N5 +[HF2]-·nHF, N5 +[BF4]-, N5 +[PF6]-, and N5 +[SO3F]-. Angew Chem Int Ed, 2004, 43: 4919–4924

    Article  Google Scholar 

  18. Vij A, Pavlovich JG, Wilson WW, et al. Experimental detection of the pentaazacyclopentadienide (pentazolate) anion, cyclo-N5 -. Angew Chem Int Ed, 2002, 41: 3051–3054

    Article  Google Scholar 

  19. Östmark H, Wallin S, Brinck T, et al. Detection of pentazolate anion (cyclo-N5 -) from laser ionization and decomposition of solid p-dimethylaminophenylpentazole. Chem Phys Lett, 2003, 379: 539–546

    Article  Google Scholar 

  20. Steele BA, Oleynik II. Sodium pentazolate: A nitrogen rich high energy density material. Chem Phys Lett, 2016, 643: 21–26

    Article  Google Scholar 

  21. Bazanov B, Geiger U, Carmieli R, et al. Detection of cyclo-N5 -in THF solution. Angew Chem Int Ed, 2016, 55: 13233–13235

    Article  Google Scholar 

  22. Steele BA, Stavrou E, Crowhurst JC, et al. High-pressure synthesis of a pentazolate salt. Chem Mater, 2017, 29: 735–741

    Article  Google Scholar 

  23. Zhang C, Sun C, Hu B, et al. Synthesis and characterization of the pentazolate anioncyclo–N5 -in (N5)6(H3O)3(NH4)4Cl. Science, 2017, 355: 374–376

    Article  Google Scholar 

  24. Xu Y, Wang Q, Shen C, et al. A series of energetic metal pentazolate hydrates. Nature, 2017, 549: 78–81

    Article  Google Scholar 

  25. Zhang C, Yang C, Hu B, et al. A symmetric Co(N5)2(H2O)4·4H2O high-nitrogen compound formed by cobalt(II) cation trapping of a cyclo-N5 -anion. Angew Chem Int Ed, 2017, 56: 4512–4514

    Article  Google Scholar 

  26. Xu Y, Wang P, Lin Q, et al. A carbon-free inorganic–metal complex consisting of an all-nitrogen pentazole anion, a Zn(ii) cation and H2O. Dalton Trans, 2017, 46: 14088–14093

    Article  Google Scholar 

  27. Zhang W, Wang K, Li J, et al. Stabilization of the pentazolate anion in a zeolitic architecture with Na20N60 and Na24N60 nanocages. Angew Chem Int Ed, 2018, 57: 2592–2595

    Article  Google Scholar 

  28. Frisch MJ, Trucks GW, Schlegel HB, et al. Gaussian 09, Revision A.02, Gaussian, Inc, Wallingford CT, 2009

    Google Scholar 

  29. Becke AD. Density-functional thermochemistry. III. The role of exact exchange. J Chem Phys, 1993, 98: 5648–5652

    Google Scholar 

  30. Lee C, Yang W, Parr RG. Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Phys Rev B, 1988, 37: 785–789

    Article  Google Scholar 

  31. Lu T, Chen F. Multiwfn: A multifunctional wavefunction analyzer. J Comput Chem, 2012, 33: 580–592

    Article  Google Scholar 

  32. Johnson ER, Keinan S, Mori-Sanchez P, et al. Revealing noncovalent interactions. J Am Chem Soc, 2010, 132: 6498–6506

    Article  Google Scholar 

  33. SAINT v7.68A Bruker AXS Inc: Madison, WI, 2009

  34. Sheldrick GM. SHELXL-2014/7, University of Göttingen, Germany, 2014

  35. SADABS v2008/1 Bruker AXS Inc.: Madison, WI, 2008

  36. Spek AL. PLATON, An integrated tool for the analysis of the results of a single crystal structure determination. Acta Crystallogr sect A, 1990, 46: C34

    Google Scholar 

  37. Kamlet MJ, Jacobs SJ. Chemistry of detonations. I. A simple method for calculating detonation properties of C–H–N–O explosives. J Chem Phys, 1968, 48: 23–35

    Google Scholar 

  38. Zhang Y, Zhang S, Sun L, et al. A solvent-free dense energetic metal–organic framework (EMOF): to improve stability and energetic performance via in situ microcalorimetry. Chem Commun, 2017, 53: 3034–3037

    Article  Google Scholar 

  39. Xu Y, Liu W, Li D, et al. In situ synthesized 3D metal–organic frameworks (MOFs) constructed from transition metal cations and tetrazole derivatives: a family of insensitive energetic materials. Dalton Trans, 2017, 46: 11046–11052

    Article  Google Scholar 

  40. Wang Y, Zhang J, Su H, et al. A simple method for the prediction of the detonation performances of metal-containing explosives. J Phys Chem A, 2014, 118: 4575–4581

    Article  Google Scholar 

Download references

Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (11702141, 21771108, and U1530101). The authors gratefully acknowledge Dongxue Li (College of Chemical Engineering, Nanjing Tech University) for her tests of the Raman spectra.

Author information

Author notes

  1. These authors contributed equally to this study.

Authors and Affiliations

  1. School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing, 210094, China

    Peng-Cheng Wang  (王鹏程), Yuan-Gang Xu  (许元刚), Qian Wang  (王乾), Yan-Li Shao  (邵艳丽), Qiu-Han Lin  (林秋汉) & Ming Lu  (陆明)

Authors
  1. Peng-Cheng Wang  (王鹏程)
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Yuan-Gang Xu  (许元刚)
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Qian Wang  (王乾)
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Yan-Li Shao  (邵艳丽)
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Qiu-Han Lin  (林秋汉)
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Ming Lu  (陆明)
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Qiu-Han Lin  (林秋汉) or Ming Lu  (陆明).

Additional information

Pengcheng Wang obtained his BSc in 2008 and PhD in 2013 at Nanjing University of Science and Technology (NJUST), and was a postdoc at the National Institute of Advanced Industrial Science and Technology (AIST) from 2013 to 2014. He joined NJUST in 2014. His current research interest is in the synthesis and crystal engineering of energetic materials.

Yuangang Xu was born in 1990. He is a PhD candidate of applied chemistry in NJUST. His research focuses on the synthesis of nitrogen-rich energetic materials.

Qiuhan Lin obtained his BSc in 2008 and PhD in 2013 at Beijing Institute of Technology. He joined NJUST as an associate professor in 2014. His current research interest is in the synthesis and crystal engineering of energetic salts.

Ming Lu obtained his BSc in 1984, MSc in 1989 and PhD in 1999 at NJUST. He then became a professor in 2001. His current research interest focuses on the synthesis and crystal engineering of energetic materials, pharmaceutical intermediates and green chemistry.

Electronic supplementary material

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Wang, PC., Xu, YG., Wang, Q. et al. Self-assembled energetic coordination polymers based on multidentate pentazole cyclo-N5−. Sci. China Mater. 62, 122–129 (2019). https://doi.org/10.1007/s40843-018-9268-0

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s40843-018-9268-0

Keywords

Search

Navigation