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Updated: May 29, 2025

Synthesis of a Water-soluble Metal–Organic Complex Array
Published on: October 8, 2016
Anion-Guided Hierarchical Assembly of Heterometallic Clusters
Weiming Huang1, Qingsong Yang1, Wanmin Chen1
1Department of Chemistry and Key University Laboratory of Rare Earth Chemistry of Guangdong, Southern University of Science and Technology, Shenzhen 518055, China.
Abstract:
Anions are important as templates for the construction of many structurally sophisticated and functional supramolecular architectures. Deciphering the specific role of such templates remains a great challenge due to the unique characteristics of anions. Herein, three heterometallic Ce-Ni clusters, namely, [Ce24Ni36L36(μ-OAc)6(OH)52(Cl)8]Cl6·110H2O (CeNi, OAc = acetate ion, L = N-methyliminodiacetate), [Ce17Ni27L27(μ-CO)6(OH)15(Cl)16(H2O)19](ClO4)2Cl6·45H2O (CeNi), and [Ce21Ni30L30(μ-CO)2(μ-OAc)(OH)32(Cl)15(H2O)14](ClO4)4Cl7·55H2O (CeNi), were obtained and structurally characterized; the formation of these cage-like clusters was assisted, respectively, by acetate, oxalate, and a combination of the two as templates. Structural analyses generate key information on the anion-directed hierarchical assembly, starting from a primary building block of {CeNi3} to two anion-specific secondary building blocks (SBUs)─the tetragonal {Ce4Ni8(OAc)} and the pentagonal {Ce5Ni9(CO)}. Further assembly steps are guided by these curved SBUs, affording a truncated octahedral CeNi and a lantern-like CeNi, with acetate and oxalate being the sole template, respectively. The combined use of acetate and oxalate produced CeNi, a cluster with an unprecedented structure viewable as a hybrid of a truncated octahedron and a dodecahedron.
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