Coordination Polymerization of 5,5′-Dinitro-2H,2H′-3,3′-bi-1,2,4-triazole Leads to a Dense Explosive with High Thermal Stability
Coordination Polymerization of 5,5′-Dinitro-2H,2H′-3,3′-bi-1,2,4-triazole Leads to a Dense Explosive with High Thermal Stability
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DOI：
10.1021/acs.inorgchem.6b02383
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发表时间：
2017-01-02
影响因子：
4.6
通讯作者：
Matzger, Adam J.
中科院分区：
文献类型：
--
作者：
Seth, Saona;Matzger, Adam J.
基于富氮配体的高能配位聚合物是一类新兴的炸药。然而，高能CP的能量性质的调控及其结构-功能关系的建立仍处于起步阶段。本文介绍了配位聚合技术在调节二次炸药5，5‘-二硝基-2H，2H’-3，3‘-二-1，2，4-三氮唑(DNBT)的密度和热稳定性等关键能量性质应用方面的应用。Ni-DNBT是一种密度低于DNBT的离散八面体配合物。与Ni-DNBT中的八面体金属配位结构类似，Cu-DNBT中也含有八面体金属配位，但由于反应过程中铜-Ⅱ部分还原为铜-Ⅰ离子及其独特的几何构型，使得八面体的铜-Ⅱ配合物通过四面体的铜-Ⅰ离子连接起来，使合成的材料成为高密度的一维聚合物。事实上，在所有基于DNBT的能级中，Cu-DNBT具有最高的密度。此外，Cu-DNBT的热稳定性优于Ni-DNBT和DNBT。Cu-DNBT是两种基于DNBT的含能材料之一，也是为数不多的在300℃以上温度下稳定的含能材料之一。
High-energy coordination polymers (CPs) based on nitrogen-rich ligands are an emerging class of explosives. However, modulation of the energetic properties of high-energy CPs and the establishment of their structure-function relationship remain in their infancy. In the present study, the utility of coordination polymerization as a technique to modulate the application of critical energetic properties, such as density and thermal stability, of a secondary explosive, 5,5 '-dinitro-2H,2H '-3,3 '-bi-1,2,4-triazole (DNBT), is presented. Ni-DNBT is a discrete octahedral complex with density lower than that of DNBT. Cu-DNBT also contains octahedral metal coordination, similar to that in Ni-DNBT, as the building unit; however, the partial reduction of Cu-II to Cu-I ions during the reaction and their unique geometrical preferences lead to linking of the octahedral Cu-II complexes by tetrahedral Cu-I ions and render the resultant material a one-dimensional polymer with high density. In fact, Cu-DNBT has the highest density among all of the DNBT-based energetics. Furthermore, Cu-DNBT exhibits thermal stability superior to that of both Ni-DNBT and DNBT. Cu-DNBT is one of the two DNBT-based energetic materials and one of the few energetics that are stable at temperatures higher than 300 degrees C.