Journal article
Formation of Nanoscale [Ge4O16Al48(OH)108(H2O)24]20+ from Condensation of ϵ‐GeAl128+ Keggin Polycations
Angewandte Chemie (International ed.), Vol.60(16), pp.8755-8759
04/12/2021
DOI: 10.1002/anie.202017321
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 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.
Self‐condensation of ϵ‐GeAl128+ upon thermal aging is proposed as the mechanism for the formation of tetrameric [Ge4O16Al48(OH)108(H2O)24]20+ (Ge4Al4820+).
Details
- Title: Subtitle
- Formation of Nanoscale [Ge4O16Al48(OH)108(H2O)24]20+ from Condensation of ϵ‐GeAl128+ Keggin Polycations
- Creators
- Mohammad Shohel - University of IowaJennifer L Bjorklund - University of IowaJack A Smith - University of IowaDmytro V Kravchuk - University of IowaSara E Mason - University of IowaTori Z Forbes - University of Iowa
- Resource Type
- Journal article
- Publication Details
- Angewandte Chemie (International ed.), Vol.60(16), pp.8755-8759
- DOI
- 10.1002/anie.202017321
- ISSN
- 1433-7851
- eISSN
- 1521-3773
- Number of pages
- 5
- Grant note
- National Science Foundation (ACI-1548562 though allocation TG-GEO160006)
- Language
- English
- Date published
- 04/12/2021
- Academic Unit
- Civil and Environmental Engineering; Chemistry; Core Research Facilities
- Record Identifier
- 9984216724502771
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