Formation Of Nanoscale [Ge4o16al48(Oh)(108)(H2o)(24)](20+) From Condensation Of Epsilon-Geal128+ 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 (delta), but herein we report the isolation of largest Keggin-type cluster that occurs through self-condensation of four epsilon-isomers epsilon-GeAl128+ to form [Ge4O16Al48(OH)(108)(H2O)(24)](20+) cluster (Ge4Al48). 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 Ge4Al48 in thermally aged solutions. DFT calculations reveal that a single atom Ge substitution in tetrahedral site of epsilon-isomer is the key for the formation of Ge4Al48 because it activates deprotonation at key surface sites that control the self-condensation process.