Nanoconfinement Inside Molecular Metal Oxide Clusters: Dynamics and Modified Encapsulation Behavior.

Encapsulation behavior, as well as the presence of internal catalytically active sites, has been spurring the applications of a 3 nm hollow spherical metal oxide cluster {Mo132} as an encapsulation host and a nanoreactor. Due to its well-defined and tunable cluster structures, and nanoscaled internal void space comparable to the volumes of small molecules, this cluster provides a good model to study the dynamics of materials under nanoconfinement. Neutron scattering studies suggest that bulky internal ligands inside the cluster show slower and limited dynamics compared to their counterparts in the bulk state, revealing the rigid nature of the skeleton of the internal ligands. NMR studies indicate that the rigid internal ligands that partially cover the interfacial pore on the molybdenum oxide shells are able to block some large guest molecules from going inside the capsule cluster, which provides a convincing protocol for size-selective encapsulation and separation. [ABSTRACT FROM AUTHOR]