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 (
- Award ID(s):
- 1664379
- NSF-PAR ID:
- 10200960
- Date Published:
- Journal Name:
- Angewandte Chemie International Edition
- Volume:
- 59
- Issue:
- 39
- ISSN:
- 1433-7851
- Page Range / eLocation ID:
- 17286 to 17290
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract 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 theGe4Al48 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 ofGe4Al48 because it activates deprotonation at key surface sites that control the self‐condensation process. -
Abstract 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 theGe4Al48 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 ofGe4Al48 because it activates deprotonation at key surface sites that control the self‐condensation process.