Four-Shell Polyoxometalates Featuring High-Nuclearity Ln sub(26) Clusters: Structural Transformations of Nanoclusters into Frameworks Triggered by Transition-Metal Ions

A series of polyoxometalates (POMs) that incorporate the highest-nuclearity Ln clusters that have been observed in such structures to date (Ln sub(26), Ln=La and Ce) are described, which exhibit giant multishell configurations (LnW sub(6)Ln sub(26)W sub( 100)). Their structures are remarkably differ...

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Bibliographic Details
Published in:Angewandte Chemie 2017-03, Vol.129 (10), p.2708-2713
Main Authors: Li, Zhong, Li, Xin-Xiong, Yang, Tao, Cai, Zhen-Wen, Zheng, Shou-Tian
Format: Article
Language:English
Subjects:
Acetal resins
Clusters
Construction
Copper
Nanostructure
Polyoxometallates
Single crystals
Transformations
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Summary:A series of polyoxometalates (POMs) that incorporate the highest-nuclearity Ln clusters that have been observed in such structures to date (Ln sub(26), Ln=La and Ce) are described, which exhibit giant multishell configurations (LnW sub(6)Ln sub(26)W sub( 100)). Their structures are remarkably different from known giant POMs that feature multiple Ln ions. In particular, the incorporated Ln-O clusters with a nuclearity of 26 are significantly larger than known high-nuclearity ( less than or equal to 10) Ln-O clusters in POM chemistry. Furthermore, they also contain the largest number of La and Ce centers for any POM reported to date and represent a new kind of rare giant POMs with more than 100 Watoms. Interestingly, the La sub(26)-containing POM can undergo a single-crystal to single-crystal structural transformation in the presence of various transition-metal ions, such as Cu super(2+), Co super(2+), and Ni super(2+), from an inorganic molecular nanocluster into an inorganic-organic hybrid extended framework that is built from POM building blocks with even higher-nuclearity La sub(28) clusters bridged by transition-metal complexes.Original Abstract: Vierschalige heterometallische Polyoxowolframate, die Ln sub(26)-Cluster mit hoher Nuklearitaet beinhalten, wurden synthetisiert. Diese konnen 3d-Metallionen einschliesen, waehrend ihre Einkristall-Einkristall-Transformation zu einer neuen Klasse an Polyoxometallaten (POMs) mit ausgedehnten Strukturen fuehrt, die auf Ln sub(28) enthaltenden POMs basieren (TM=Uebergangsmetall).
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.201612046