The development of supramolecular materials has opened up unprecedented opportunities for smart, responsive systems. Yet, their practical application in extreme environments—deep space, deep sea, polar regions, high-temperature and high-pressure reservoirs—is fundamentally challenged by the inherent trade-off between structural stability and dynamic adaptability. This review addresses this core issue by presenting a comprehensive framework for understanding and overcoming the stability–dynamism mismatch under harsh condition. We systematically analyze the molecular mechanisms by which severe factors disrupt non-covalent networks. Based on these insights, we outline four universal molecular design strategies that re-establish the balance, and summarize engineering applications across aerospace, marine, energy, and polar exploration. Beyond offering a comprehensive roadmap for rational material design, this review highlights persistent challenges—including multi-field coupling failure mechanisms, industrialization barriers, and the limitations of current systems—and outlines future directions. By bridging fundamental chemistry with extreme environment engineering, this work aims to guide the next generation of supramolecular materials that can reliably serve in the most demanding operational scenarios.

Incorporating comonomers in propylene polymerization plays a critical role in tuning the physical and chemical properties of the resulting polymers. In this study, the impact of three developed comonomers on propylene polymerization over the triethylaluminum-treated TiCl₃ catalyst was investigated in detail by DFT. The results indicate that these comonomers remain highly stable under actual catalytic conditions, with their ions or functional groups showing a low propensity for detachment, which would otherwise poison the catalyst or disrupt the polymerization process. However, the three comonomers on the surface with a strong adsorption capacity may compete with propylene for adsorption, which will affect the polymerization. Among them, Vinyltrimethoxysilane, which exhibits the strongest adsorption ability, tends to form bonds with the ethyl on the catalyst surface, leading to catalyst poisoning and inhibiting the reaction. In contrast, 5-hexenyl methyldichlorosilane demonstrates relatively higher activity due to its balanced properties. The order of reactivity in the polymerization reaction: 5-hexenyl methyldichlorosilane > 5-hexenyldichlorophosphonane > vinyltrimethoxysilane. This work provides fundamental mechanistic insights into how functional comonomers interact with catalytic active sites through adsorption, competitive reactions, and insertion processes. Additional free energy analysis at 333 K confirms that these mechanistic trends remain unchanged under realistic reaction conditions. Rather than directly simulating industrial catalysts, the present study focuses on a model TiCl₃ system to elucidate intrinsic structure-reactivity relationships. These findings contribute to a deeper understanding of comonomer effects in olefin polymerization at the molecular level.