中国化学会第二十三全国金属有机化学学术讨论会

含能材料是国防与民用爆破领域的核心基础。随着现代武器装备对能量密度与安全性要求的不断提升，传统硝胺类化合物（如 RDX、HMX）已难以同时满足高能量与低感度的矛盾需求。近年来，环张力引入被认为是平衡能量与感度的有效策略之一。环丙烷及其稠环体系具有较高的环张力能，可显著提升分子的能量水平，同时其刚性骨架有助于降低机械感度。然而，高张力环的合成难度大、热稳定性可控性差，制约了其在含能材料中的实际应用。本研究围绕高张力环丙烷骨架的构建规律及其在含能分子设计中的应用展开，为新型高能量密度材料提供思路。

含能分子的感度不仅取决于化学能高低，更与分子堆积方式、晶态下氢键及 π-π 相互作用密切相关。晶体工程为调控含能材料的安全性能提供了重要手段。通过引入多硝基氮杂环结构，可以在分子层面同时实现高密度和高氧平衡。但目前对分子结构 — 堆积方式 — 感度三者之间的定量关系仍缺乏系统认识，尤其缺乏从单晶结构出发建立的感度预测模型。本研究通过溶剂挥发法培养了一系列多硝基氮杂环化合物的单晶，利用 X 射线衍射解析其晶体结构，并结合撞击感度和摩擦感度测试，建立了结构描述符与感度之间的关联模型。

Over the years, low-valent main-group compounds have emerged as powerful alternatives to their transition metal counterparts in inert bond activation and catalysis, owing to their abundance, lower cost, and sustainability. Among these, pnictinidenes (R-Pn(I); Pn = P, As, Sb, Bi), as the carbene analogues, have received particular attention due to their versatile electronic structures and unique reactivity. Depending on the nature of R and the coordination sphere, pnictinidenes may have either a singlet or a triplet ground state. Analogous to carbene-metal complexes, pnictinidene-complexes can be classified as Schrock-type where both the metal and the pnictinidene fragments are in a triplet electronic state, and Fischer-type where both components adopt a singlet electronic state. Lewis base-stabilized pnictinidenes, usually in a singlet ground state, have garnered significant attention for their potential in small-molecule activation and redox catalysis. Modulating substituents on pnictinidenes undoubtedly have a profound effect on their reactivity and provides valuable opportunities for developing more robust pnictinidene-based catalysts with broader reaction scope. Currently, the most extensively reported pnictinidenes feature aryl or electron-withdrawing groups. In contrast, the simple alkyl-substituted pnictinidenes bearing strong electron-donating groups remain exceedingly rare, and are typically stabilized as Schrock-type metal complex. This scarcity stems notably from their inherent instability, which likely originates from the electronic repulsion arising from the coordination of strong electron-donating groups to the electron rich low-valent Pn(I) center.