Size matching molecular design utilizing host-guest chemistry is a general, promising strategy for seeking new functional materials. With the growing trend of multidisciplinary investigations, taming the metastable high-energy guest moiety in well-matched frameworks is a new pathway leading to innovative energetic materials. Presented is a selective encapsulation in hydrogen-bonded hydroxylammonium frameworks (HHF) by screening different sized nitrogen-rich azoles. The size-match between a sensitive high-energy guest and an HHF not only gives rise to higher energetic performance by dense packing, but also reinforces the layer-by-layer structure which can stabilize the resulting materials towards external mechanic stimuli. Preliminary assessment based on calculated detonation properties and mechanical sensitivity indicates that HHF competed well with the energetic performance and molecular stability (detonation velocity = 9286 m s⁻¹, impact sensitivity = 50 J). This work highlights the size-matched phenomenon of HHF and may serve as an alternative strategy for exploring next generation advanced energetic materials.

利用主客体化学进行尺寸匹配分子设计是寻找新功能材料的一种通用且有前景的策略。随着多学科研究的发展趋势，在匹配的框架中驯服亚稳态高能客体部分是通向创新含能材料的新途径。提出了通过筛选不同尺寸的富氮唑类来选择性封装在氢键羟铵框架（HHF）中。敏感的高能客体和 HHF 之间的尺寸匹配不仅通过致密堆积产生更高的能量性能，而且还增强了逐层结构，可以稳定所得材料以应对外部机械刺激。基于计算的爆轰特性和机械灵敏度的初步评估表明，HHF 在能量性能和分子稳定性方面表现良好（爆轰速度 = 9286 ms ^-1 ，冲击灵敏度 = 50 J）。这项工作强调了 HHF 的尺寸匹配现象，并可能作为探索下一代先进含能材料的替代策略。