高氮金属配合物电荷转移效应与激光起爆特性关系研究

High-nitrogen energetic complexes are a class of functional coordination compounds with strong explosive properties, which can be used as the initial energetic materials to apply in the field of a variety of weapons and ammunition; also be used as the energetic catalyst and burning rate adjusting agent in the field of solid propellant, in order to achieve efficient damage and high-energy propulsion of the weapon system. The project intends to carry out the research of the molecular design, controllable preparation, structural characterization, and explosive properties for the high-nitrogen energetic complexes, as well as the mechanism of laser acting on them based on molecular engineering and coordination chemistry principle. So, the high-nitrogen tetrazine compounds will been chosen as ligands, and Fe2+, Co2+, Cu2+, etc. will been used as center ions. The coordination ions have been obtained by reacting tetrazine compounds with the center ions. Then, the title complexes would be formed by the electrostatic attraction with the outside perchlorate ion. Firstly, time-dependent density functional theory (TD-DFT) was used to investigate charge transfer effects and the photo absorption properties, furthermore, the relationship between the molecular structure and the charge transfer effects will be revealed. Then, the molecule will be designed and the laser initiation characteristics will be predicted for the novel laser sensitive high-nitrogen energetic complexes, furthermore, the relationship model between charge transfer effect and laser initiation characteristics will be obtained. Lastly, the low threshold near infrared laser initiation complexes with the better combination property will be chosen, and the preparation, structural characterization and laser sensitivity will be investigated. This proposal has very important theoretical significance to clarify the complexes bonding rules and explosive decomposition mechanism; in addition, it will provide the theoretical guidance and application value to develop the novel energetic complexes.

高氮含能配合物是一类具有强烈爆炸性的功能配合物，具有高能、钝感等特点，既可作初始能源用于武器弹药，也可作燃烧催化剂用于固体推进剂，以实现武器系统的高效毁伤和高能推进。基于分子工程学和配位化学原理，开展高氮配合物的分子设计、构筑表征、感度测试及其与激光作用机理研究。选择高氮嗪类化合物为配体，Fe、Co、Cu等为中心离子，通过配位反应生成配离子，再与高氯酸根通过静电作用生成配合物。首先，采用TD-DFT方法研究高氮配合物的电荷转移效应和光吸收性质，揭示其分子结构与电荷转移效应的关系。其次，开展新型激光敏感高氮配合物的分子设计和激光起爆特性研究，获得其电荷转移效应与激光起爆特性的关系模型。最终，优选出性能优异的低阈值近红外激光起爆配合物，研究其制备、表征与激光感度，掌握其感度调制技术。选题对阐明高氮配合物的荷移效应和激光起爆机理具有重要的理论意义，对探索新型高氮含能配合物应用具有重要的实用价值。

高氮含能配合物是一类具有强烈爆炸性的功能配合物，具有高能、钝感等特点，既可作初始能源用于武器弹药，也可作燃烧催化剂用于固体推进剂，以实现武器系统的高效毁伤和高能推进。.本项目按照项目申请书和计划书的要求，重点完成了如下研究工作：开展了激光敏感多氮含能配合物吸收光谱、电子跃迁供体受体、电子跃迁模式理论研究，从理论上研究了高氮含有配合物的核移光谱性质及光起爆特性；合成得到了系列吡唑四嗪类化合物及其含能配合物，进行系统的结构表征表征，测试了配合物的光谱吸收特性、激光起爆感度；开展了氨基三唑、硝基氨基胍等系列高氮含能配体研究，并制备了其系列含能配合物，研究了其分子结构、感度性能。共优选出了8种高氮含能配体，制备得到了25种高氮含能配物，其中获得晶体结构的有7种，从中优选出了4种高氮含能配合物，重点研究了其机械感度、激光感度和起爆性能。我们将在现有研究成果的基础上，进一步筛选出的机械感度适中、具有特征激光感度的目标配合物，并探索其在激光点火和激光起爆领域中的应用。.在项目执行过程中，积极组织、参加国内、国际学术会议、学术交流活动，与国外同行充分开展合作与交流。研究过程中发表论文26篇，其中SCI收录22篇，EI收录1篇；授权专利2项，申请专利3项。项目研究过程中，培养出站博士后1人，毕业博士生、硕士生各3人，在读博士生3人、硕士生2人。