Guest Transition Metals in Host Inorganic Nanocapsules: Single Sites, Discrete Electron Transfer, and Atomic Scale...

Host-guest solution chemistry with a wide range of organic hosts is an important and established research area, while the use of inorganic hosts is a more nascent area of research. In the recent past in a few cases, Keplerate-type molybdenum oxide-based porous, spherical clusters, shorthand notation {Mo₁₃₂}, have been used as hosts for organic guests. Here, we demonstrate the synthetically controlled encapsulation of first-row transition metals (M = Mn, Fe, and Co) within a Keplerate cluster that was lined on the inner core with phosphate anions, {Mo₁₃₂PO₄}. The resulting M²⁺⊂{Mo₁₃₂PO₄} host-guest complexes were characterized by ³¹P NMR and ENDOR spectroscopy that substantiated the encapsulation of the first-row transition metal guest. Magnetic susceptibility measurements showed that the encapsulation of up to 10 equiv showed little magnetic interaction between the encapsulated metals, which indicated that each guest atom occupied a single site. Visualization of the capsules and differentiation of the Mo atoms of the capsule framework and the encapsulated transition metal were possible using spherical and chromatic double aberration-corrected electron microscopy combined with energy-filtered TEM (EFTEM) elemental maps. In addition, use of visible light-induced XPS for chemically resolved electrical measurements (CREM) confirmed the successful encapsulation of M within {Mo₁₃₂PO₄} and furthermore showed photoinduced electron transfer from M to Mo. In the future, such targeted electron transfer between host {Mo₁₃₂} and a transition metal guest could be used as photoinitiated switches using inorganic compounds and for single site photocatalytic reactions in confined space.