title: Four-Shell Polyoxometalates Featuring High-Nuclearity Ln26Clusters: Structural Transformations of Nanoclusters into Frameworks Triggered by Transition-Metal Ions.
abstract: A series of polyoxometalates (POMs) that incorporate the highest-nuclearity Ln clusters that have been observed in such structures to date (Ln26, Ln=La and Ce) are described, which exhibit giant multishell configurations (Ln⊂W6⊂Ln26⊂W100). 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 (≤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 W atoms. Interestingly, the La26-containing POM can undergo a single-crystal to single-crystal structural transformation in the presence of various transition-metal ions, such as Cu2+, Co2+, and Ni2+, from an inorganic molecular nanocluster into an inorganic-organic hybrid extended framework that is built from POM building blocks with even higher-nuclearity La28clusters bridged by transition-metal complexes.
authors.affiliation: State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou, Fujian, 350108, China.
authors.forename: Zhong
authors.initials: Z
authors.lastname: Li
authors.affiliation: State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou, Fujian, 350108, China.
authors.forename: Xin-Xiong
authors.initials: XX
authors.lastname: Li
authors.affiliation: State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou, Fujian, 350108, China.
authors.forename: Tao
authors.initials: T
authors.lastname: Yang
authors.affiliation: State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou, Fujian, 350108, China.
authors.forename: Zhen-Wen
authors.initials: ZW
authors.lastname: Cai
authors.affiliation: State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou, Fujian, 350108, China.
authors.forename: Shou-Tian
authors.identifier: 0000-0002-3365-9747
authors.initials: ST
authors.lastname: Zheng
keywords: cluster compounds; lanthanide clusters; polyoxometalates; structure elucidation; transition metals