Xenon in Rigid Oxide Frameworks: Structure, Bonding and Explosive Properties of Layered Perovskite K₄Xe₃O₁₂

The tendency of high-valence xenon to form consolidated oxide structures is herein supported by the study of K4Xe3O12, the first example of a layered xenon perovskite. Xenon seems to be the only nontransition element that can adopt single-cation oxide perovskite frameworks. At the same time, peculiarities of electronic structure of xenon impose specific features on the bonding within a perovskite structure. Weak supramolecular interactions known as aerogen bonds are the linkers that maintain structural integrity of perovskite slabs in K4Xe3O12. The occurrence of aerogen bonding can provide an insight into the explosive properties of K4Xe3O12: the weakness of supramolecular interactions allows consideration of them as possible trigger bonds responsible for the detonation sensitivity of layered xenon perovskite.本研究通过对K₄Xe₃O₁₂的探究，证实了高氧化态氙易于形成致密氧化物结构的趋势，该化合物是首例层状氙基钙钛矿（layered xenon perovskite）。氙是目前已知唯一可构建单阳离子氧化物钙钛矿骨架的非过渡元素。与此同时，氙的电子结构特性赋予钙钛矿结构内成键以独特特征。被称为气键（aerogen bonds）的弱超分子相互作用，是维系K₄Xe₃O₁₂中钙钛矿片层结构完整性的核心连接纽带。气键的存在可为解析K₄Xe₃O₁₂的爆炸特性提供关键视角：这类超分子相互作用的弱质性，使其可被视作引发层状氙基钙钛矿爆轰感度的潜在引发键。