Experimental and Theoretical Insights on Gas Trapping of Noble Gases in MFU‐4‐Type Metal–Organic Frameworks

Isostructural metal–organic frameworks (MOFs), namely MFU‐4 and MFU‐4‐Br, in which the pore apertures are defined by anionic side ligands (Cl$^{−}$ and Br$^{−}$, respectively), were synthesized and loaded with noble gases. By selecting the type of side ligand, one can fine‐tune the pore aperture size, allowing for precise regulation of the entry and release of gas guests. In this study, we conducted experiments to examine gas loading and release using krypton and xenon as model gases, and we complemented our findings with computational modeling. Remarkably, the loaded gas guests remained trapped inside the pores even after being exposed to air under ambient conditions for extended periods, in some cases for up to several weeks. Therefore, we focused on determining the energy barrier preventing gas release using both theoretical and experimental methods. The results were compared in relation to the types of hosts and guests, providing valuable insights into the gas trapping process in MOFs, as well as programmed gas release in air under ambient conditions. Furthermore, the crystal structure of MFU‐4‐Br was elucidated using the three‐dimensional electron diffraction (3DED) technique, and the bulk purity of the sample was subsequently verified through Rietveld refinement.