The chemistry of lead-, azide- and perchlorate-free photosensitive energetic materials suitable for laser-ignition systems is an emerging field of research with a broad range of applications. To develop less toxic materials that would be sufficiently thermostable, safe, and sensitive enough to be ignited by low-power laser, is a formidable challenge. In this work, we designed, prepared, and studied properties of new sulfur-containing energetic molecules (SEMols), based on novel N-(1,3,4-thiadiazol-2-yl)nitramide explosophore. Newly synthesized energetic compounds N-(5-nitro-1,3,4-thiadiazol-2(3H)-ylidene)-nitramide (L1) and N⁵,N^5'-dinitro-[2,2'-bi(1,3,4-thiadiazole)]-5,5'(4H,4'H)-diimine (L4) were found to be more thermostable than their sulfur-free 1,3,4-oxadiazole analogues. In small-scale detonation experiments, L1, L4, and C7 showed better brisance than TNT. Perchlorate-free complex C7 was found to have low-power laser igniting properties, showing an ignition delay time of 11 ms and threshold ignition energy of 12.0 mJ (at 915 nm irradiation). Extensive crystal-level (328-atom super-cell) ab-initio molecular dynamics and TD-DFT calculations were performed to study the laser ignition mechanism of C7. Based on our hypothesis, this photo-thermal ignition is taking place via sequential multi-photon absorption, with energy transfer to vibrational motions in this molecule. We suggest that SEMols, such as C7, can open a new platform for the development of novel energetic materials that have a potential for integration into laser-based safe energetic components in civil, aerospace, and defense applications.

适用于激光点火系统的不含铅、叠氮化物和高氯酸盐的光敏含能材料的化学是一个具有广泛应用的新兴研究领域。开发毒性较小的材料，这些材料具有足够的热稳定性、安全性和灵敏度，足以被低功率激光点燃，这是一项艰巨的挑战。在这项工作中，我们基于新型N -(1,3,4-thiadiazol-2-yl)nitramide 爆炸物设计、制备和研究了新型含硫高能分子 (SEMols) 的性质。新合成的含能化合物N- (5-nitro-1,3,4-thiadiazol-2(3 H )-ylidene)-nitramide ( L1 ) 和N ⁵ , N ^5'-dinitro-[2,2'-bi(1,3,4-thiadiazole)]-5,5'(4 H ,4' H )-diimamine ( L4 ) 比不含硫的 1 ,3,4-恶二唑类似物。在小规模爆炸实验中，L1、L4和C7显示出比 TNT 更好的回弹力。发现不含高氯酸盐的复合物C7具有低功率激光点火特性，其点火延迟时间为 11 ms，阈值点火能量为 12.0 mJ（在 915 nm 照射下）。进行了广泛的晶体级（328 原子超级晶胞）从头算分子动力学和 TD-DFT 计算，以研究C7的激光点火机制. 根据我们的假设，这种光热点火是通过连续的多光子吸收发生的，能量转移到该分子的振动运动中。我们建议 SEMols，如C7，可以为开发新型高能材料开辟一个新平台，这些材料有可能集成到民用、航空航天和国防应用中的基于激光的安全高能组件中。