Formation of Nanoscale [Ge₄O₁₆Al₄₈(OH)₁₀₈(H₂O)₂₄]²⁰ from Condensation of ϵ‐GeAl₁₂⁸ Keggin Polycations**.

Shohel, Mohammad; Bjorklund, Jennifer L.; Smith, Jack A.; Kravchuk, Dmytro V.; Mason, Sara E.; Forbes, Tori Z.

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‐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 ϵ‐isomer is the key for the formation of Ge4Al48 because it activates deprotonation at key surface sites that control the self‐condensation process.

PROTON transfer reactions; LIGHT scattering; ISOMERS; X-ray diffraction; CONDENSATION; OLIGOMERIZATION

Angewandte Chemie, 2021, Vol 133, Issue 16, p8837

0044-8249

Academic Journal

10.1002/ange.202017321