Weinert Christopher, Ćoćić Dušan, Puchta Ralph, van Eldik Rudi
Fakultät Angewandte Mathematik, Physik und Allgemeinwissenschaften, Technische Hochschule Nuremberg Georg Simon Ohm, Keßlerplatz 12, 90489 Nuremberg, Germany.
Department of Chemistry, Faculty of Science, University of Kragujevac, Radoja Domanovića 12, P.O. Box 60, 34000 Kragujevac, Serbia.
Molecules. 2023 Jul 27;28(15):5676. doi: 10.3390/molecules28155676.
Using DFT-based computational chemistry calculations (ωB97XD/def2-tzvp//ωB97XD/def2-svp/svpfit + ZPE(ωB97XD/def2-svp/svpfit)), binding energies of noble gases encapsulated in a series of dodecahedrane molecules (general formula: XH where X = C, Si, Ge, Sn and Pb, and X where X = N, P, As, Sb and Bi) were calculated to learn about the noble gas selectivity. Based on calculated binding energies, the SnH cage can best accommodate noble gases with a medium size radius (Ar and Kr), while the PbH dodecahedrane cage is best suited for noble gases with the larger radii (Xe and Rn). On the other hand, from the elements of the V main group of the periodic table, the Bi cage has shown the best results to selectively encapsulate Ar and Kr, with the amounts of energy being released being -5.24 kcal/mol and -6.13 kcal/mol, respectively. By monitoring the geometric changes of all here-reported host cages upon encapsulating the noble gas guest, the host has shown minor to no flexibility, testifying to the high rigidity of the dodecahedrane structure which was further reflected in very high encapsulating energies.
使用基于密度泛函理论（DFT）的计算化学方法（ωB97XD/def2 - tzvp//ωB97XD/def2 - svp/svpfit + ZPE(ωB97XD/def2 - svp/svpfit)），计算了一系列十二面体烷分子（通式：XH，其中X = C、Si、Ge、Sn和Pb，以及X，其中X = N、P、As、Sb和Bi）中封装稀有气体的结合能，以了解稀有气体的选择性。根据计算出的结合能，SnH笼最适合容纳中等半径的稀有气体（Ar和Kr），而PbH十二面体烷笼最适合容纳半径较大的稀有气体（Xe和Rn）。另一方面，从元素周期表第V主族的元素来看，Bi笼在选择性封装Ar和Kr方面表现出最佳结果，释放的能量分别为-5.24 kcal/mol和-6.13 kcal/mol。通过监测所有此处报道的主体笼在封装稀有气体客体时的几何变化，主体显示出很小或没有灵活性，这证明了十二面体烷结构的高刚性，这在非常高的封装能量中进一步得到体现。
