Based on DFT calculations (ωB97XD/def2-SVP/SVPfit), the ability and mechanism of noble gas encapsulation by series of cryptophanes were investigated. The focus was set to study the influence of different functionalization groups placed at the “gates” of cryptophanes cavity entrance by which the energy criteria were chosen as a main indicator for selective encapsulation of noble gases. Chosen functionalization groups were CH₃, OCH₃, OH, NH₂, and Cl, and the encapsulation process of these cryptophanes was compared to a cryptophane without any functionalization group on its outer rim. Those groups were selected based on their different chemical properties and based on their size which will subsequently put additional steric restrictions on the cavity entrance. Chosen functionalization groups, beside their steric influence on the energy barrier magnitude, influence also the gating process through its chemical nature by which they can put an additional stabilization on noble gases encapsulation transition states enhancing the encapsulation process. Objective of this study was clearly to get better insights on the influence of those functional groups on the whole encapsulation process of noble gases. Large-size noble gases (Xe and Rn) from all noble gases are best accommodated in the cavities of selected cryptophanes, on the other hand these noble gases require to pass the highest energy barrier through the gating process. From the series of investigated cryptophanes, the cryptophane with the OCH₃ functionalization group has been identified as the one with the best capabilities to host investigated noble gases, but on the other side this cryptophane puts the highest energy criteria required for the previous gating process.

中文翻译：

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隐翅对惰性气体的完全封装过程的研究


基于 DFT 计算 （ωB97XD/def2-SVP/SVPfit），研究了一系列隐匿素包封惰性气体的能力和机制。重点设定为研究放置在隐晶素腔入口“门”的不同官能团的影响，通过这些基团选择能量标准作为惰性气体选择性封装的主要指标。选择的功能化基团是 CH₃、OCH₃、OH、NH₂ 和 Cl，并将这些隐烷的包埋过程与外缘上没有任何官能化基团的隐烷进行比较。这些组是根据它们不同的化学性质和大小来选择的，这将对腔入口施加额外的空间限制。选定的官能团化基团，除了对能垒大小的空间影响外，还通过其化学性质影响门控过程，通过化学性质，它们可以对惰性气体封装过渡态进行额外的稳定化，从而增强封装过程。本研究的目的显然是更好地了解这些官能团对惰性气体整个包埋过程的影响。来自所有惰性气体的大尺寸惰性气体（Xe 和 Rn）最好容纳在选定的隐质的空腔中，另一方面，这些惰性气体需要通过门控过程通过最高的能垒。 从一系列研究的隐烷中，具有 OCH₃ 官能团化基团的隐烷已被确定为具有承载所研究的惰性气体的最佳能力的隐烷，但另一方面，这种隐烷具有先前门控过程所需的最高能量标准。