高能钝感金属配合物的新设计策略:集全四唑高氮配体、少硝基和氧平衡接近于零为一体  

A New Design Strategy for High-energy Insensitive Metal Complexes:A Combination of All-tetrazole High-nitrogen Ligands,Less Nitro and Oxygen Balance Close to Zero

作　　者：刘璇霞 陈维 徐伟 颜高杰 吴琼[1,2,3] 朱卫华 LIU Xuan-xia;CHEN Wei;XU Wei;YAN Gao-jie;WU Qiong;ZHU Wei-hua(School of Materials Science and Engineering,Nanjing Institute of Technology,Nanjing 211167,China;Jiangsu Key Laboratory of Advanced Structural Materials and Applied Technology,Nanjing 211167,China;School of Chemistry and Chemical Engineering,Nanjing University of Science and Technology,Nanjing 210094,China)

机构地区：[1]南京工程学院材料科学与工程学院,江苏南京211167 [2]江苏省先进结构材料与应用技术重点实验室,江苏南京211167 [3]南京理工大学化学与化工学院,江苏南京210094

出　　处：《火炸药学报》2023年第5期449-455,I0013,共8页Chinese Journal of Explosives & Propellants

基　　金：江苏省博士后基金(No.2021K192B);南京工程学院大学生科技创新基金(No.TB202202036,No.TB202202058,No.TB202302041)。

摘　　要：基于4种高氮四唑配体5,5′-联四唑(BTA)、5,5′-偶氮基联四唑(ABTA)、5,5′-肼基联四唑(HBTA)和5-硝基四唑-2N-羟基(NTO)和金属Cu、Ni和Co,构筑了3个系列少硝基且氧平衡接近于零的新型含能金属配合物:M(BTA)(NTO)_(2)、M(ABTA)(NTO)_(2)和M(HBTA)(NTO)_(2);运用密度泛函理论(DFT)等方法预测了其结构与性能,并探究了金属和桥联基团对配合物结构和性能的影响规律。结果表明,Cu元素有利于提高配合物密度和降低配合物感度,Ni元素有利于提升配合物的生成热和能量;桥基-NH-NH-有利于提高配合物密度和降低配合物感度,而桥基-N=N-有利于提高配合物的生成热和能量;所设计的9种配合物的能量都与HMX相当或更优,且感度都明显低于HMX,均具有作为高能钝感化合物候选物的潜力。Three series of new energetic metal complexes,M(BTA)(NTO)_(2),M(ABTA)(NTO)_(2),and M(HBTA)(NTO)_(2),were constructed based on four high-nitrogen ligands 5,5′-tetrazole(BTA),5,5′-azo tetrazole(ABTA),5,5′-hydrazine tetrazole(HBTA),5-nitrotetrazole-2N-hydroxy(NTO)and three metals Cu,Ni and Co.Their structures and properties were predicted theoretically by density functional theory(DFT),and the effects of metal and bridging groups on the structure and properties were also investigated.The results show that Cu can increase the density and reduce the sensitivity of the complexes,while Ni can increase the heat of formation and energy.The bridge group-NH-NH-is good for increasing the density and reducing the sensitivity,while-N N-is beneficial to increase the heat of formation and energy.The energy of all designed complexes is comparative to or better than that of HMX,and the sensitivity is significantly lower than that of HMX,showing that these complexes are potential high energy insensitive compounds.

关 键 词：有机化学 四唑化合物 金属配合物 密度泛函理论 DFT 氧平衡 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] O64[理学—物理化学]