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Controlling the Reactivity of the [P 8 W 48 O 184 ] 40− Inorganic Ring and Its Assembly into POMZite Inorganic Frameworks with Silver Ions
Author(s) -
Zhan CaiHong,
Zheng Qi,
Long DeLiang,
VilàNadal Laia,
Cronin Leroy
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201911170
Subject(s) - polyoxometalate , ion , cluster (spacecraft) , crystallography , reactivity (psychology) , chemistry , ring (chemistry) , materials science , inorganic chemistry , catalysis , organic chemistry , medicine , alternative medicine , pathology , computer science , programming language
The construction of pure‐inorganic framework materials with well‐defined design rules and building blocks is challenging. In this work, we show how a polyoxometalate cluster with an integrated pore, based on [P 8 W 48 O 184 ] 40− (abbreviated as {P 8 W 48 }), can be self‐assembled into inorganic frameworks using silver ions, which both enable reactions on the cluster as well as link them together. The {P 8 W 48 } was found to be highly reactive with silver ions resulting in the in situ generation of fragments, forming {P 9 W 63 O 235 } and {P 10 W 66 O 251 } in compound ( 1 ) where these two clusters co‐crystallize and are connected into a POMZite framework with 11 Ag + ions as linkers located inside clusters and 10 Ag + linking ions situated between clusters. Decreasing both the concentration of Ag + ions, and the reaction temperature compared to the synthesis of compound ( 1 ), leads to {P 8 W 51 O 196 } in compound 2 where the {P 8 W 48 } clusters are linked to form a new POMZite framework with 9 Ag + ions per formula unit. Further tuning of the reaction conditions yields a cubic porous network compound ( 3 ) where {P 8 W 48 } clusters as cubic sides are joined by 4 Ag + ions to give a cubic array and no Ag + ions were found inside the clusters.