The first syntheses of functionalized silaadamantanes via site-selective reactions are described. Mechanistic inquiry into the isomerization of silaadamantane revealed new approaches for installing halides at the 2-position of the cluster. Meanwhile, isomerization via Lewis acid catalysts with non-nucleophilic counteranions provided access to sila-adamantane on the gram-scale, enabling us to discover strategies for substituting its 1-, 3-, 5-, and 7-positions with identical or distinct functional groups. Optical absorbance and density functional theory studies show that σ-withdrawing substituents at the 1-position strongly perturb optical absorbance in sila-adamantane, whereas substituents at the exocyclic and 2-position are optically inert. As silicon diamondoids are atomically precise models for silicon nanocrystals, our findings suggest that passivation at tertiary surface sites carries an outsized impact on the optical properties of surface-functionalized Si nanocrystals.

Molybdenum complexes devoid of a strongly coordinating pendant arm result in enhanced catalytic activity.

This article reviews the scope of inorganic cluster compounds measured in single-molecule junctions. The article explores how the structure and bonding of inorganic clusters give rise to specific quantum transport phenomena in molecular junctions.