Formation of Nanoscale [Ge 4 O 16 Al 48 (OH) 108 (H 2 O) 24 ] 20+ from Condensation of ϵ-GeAl 12 8+ Keggin Polycations

Keggin-type polyaluminum cations belong to a unique class of compounds with their large positive charge, hydroxo bridges, and divergent isomerization/oligomerization. Previous reports indicated that oligomerization of this species can only occur through one isomer (δ), but herein we report the isolation of largest Keggin-type cluster that occurs through self-condensation of four ϵ-isomers ϵ-GeAl to form [Ge O Al (OH) (H O) ] cluster (Ge Al ). The cluster was crystallized and structurally characterized by single-crystal X-ray diffraction (SCXRD) and the elemental composition was confirmed by ICP-MS and SEM-EDS. Additional dynamic light scattering experiments confirms the presence of the Ge Al in thermally aged solutions. DFT calculations reveal that a single atom Ge substitution in tetrahedral site of ϵ-isomer is the key for the formation of Ge Al because it activates deprotonation at key surface sites that control the self-condensation process.