极端条件下DAAF、DAAzF的结构稳定性与化学分解研究

3,3′-diamino-4,4′-azoxyfurazan (DAAF) and 3,3′-diamino-4,4′-azofurazan (DAAzF) are two important furoxan derivatives energetic materials. The different charge distributions of azoxy and azo groups in their structures can directly affect the intra- and inter- molecular interactions and the electron transport mechanism of the whole molecule. These secondary bonds interactions and the electron transport mechanism have a great impact on the structural stability and chemical decomposition of DAAF and DAAzF under extreme conditions. In this project, diamond anvil cells technology, together with Raman spectra, infrared spectra, absorption spectra, fluorescence spectra and electrical resistivity measurements were used to investigated the microscopic structure changes, electronic structure evolution and chemical decomposition reaction mechanism of DAAF and DAAzF under high temperature and high pressure. This project made the inter- and intra- molecular interactions and electron transfer mechanism of DAAF and DAAzF under extreme conditions clearly. The nature of the relationship between their structure characteristics and the sensitivity was revealed. It laied the foundation for designing and synthesising new types of furoxan derivatives energitc compounds with high energy and low sensitivity.

3,3′-二氨基-4,4′-氧化偶氮呋咱 (DAAF)和3,3′-二氨基-4,4′-偶氮呋咱(DAAzF)具有良好的爆轰性能，是两种潜在的高能钝感炸药。它们的结构中氧化偶氮基和偶氮基的不同引入不仅会影响分子内及分子间氢键相互作用，还会直接影响分子内的电子转移机制，这些次级键相互作用及电子转移对极端条件下DAAF、DAAzF的结构稳定性及化学分解反应有着极为重要的影响。本项目采用金刚石对顶砧高压加载技术，结合拉曼、红外、荧光、吸收等原位光谱以及高压电学技术，开展极端条件下DAAF和DAAzF的微观结构、电子结构演化及化学分解反应的实验研究，明晰DAAF、DAAzF在温压耦合条件下分子间相互作用、电子迁移的变化规律，揭示它们的结构特征与感度之间的本质关系，为新型高能低感含能呋咱化合物的设计和合成奠定基础。

3,3′-二氨基-4,4′-氧化偶氮呋咱 (DAAF)和3,3′-二氨基-4,4′-偶氮呋咱(DAAzF)具有良好的爆轰性能，是两种潜在的高能钝感炸药。它们的结构中氧化偶氮基和偶氮基的不同引入不仅会影响分子内及分子间氢键相互作用，还会直接影响分子内的电子转移机制，这些次级键相互作用及电子转移对极端条件下DAAF、DAAzF的结构稳定性及化学分解反应有着极为重要的影响。本项目系统研究了含能呋咱化合物DAAF、DAAzF的微观结构、电子结构及化学反应规律在温度和压力加载条件下的响应。明确了氧化偶氮基和偶氮基的不同引入对DAAF、DAAzF发光性质影响机制；利用压力来有效调控材料的微观结构和光学性质，揭示了高压下次级键相互作用对呋咱化合物DAAF、DAAzF的光学性质、微观结构、电子结构的影响规律。获得了在热力刺激作用下分子内及分子间相互作用变化规律对其热力学响应的影响机制，从实验上明确了DAAF在高温高压下氢转移的分解机制。采用高压电学及吸收光谱手段，初步探索了含能呋咱化合物在高压及低温高压下电子结构的改变。本项目研究为极端条件下具有π堆叠结构和平行逐层分子排列的高能钝感含能材料的光电性质研究及其感度的本质研究，提供了重要参考。