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Updated: Dec 12, 2025
Synthesis of Single-Crystalline Core-Shell Metal-Organic Frameworks
Published on: February 10, 2023
Single-Crystal-to-Single-Crystal Installation of Ln4 (OH)4 Cubanes in an Anionic Metallosupramolecular Framework
Nobuto Yoshinari1, Natthaya Meundaeng1,2, Hiroyasu Tabe3
1Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka, 560-0043, Japan.
Abstract:
Postsynthetic installation of lanthanide cubanes into a metallosupramolecular framework via a single-crystal-to-single-crystal (SCSC) transformation is presented. Soaking single crystals of K6 [Rh4 Zn4 O(l-cys)12 ] (K6 [1]; l-H2 cys=l-cysteine) in a water/ethanol solution containing Ln(OAc)3 (Ln3+ =lanthanide ion) results in the exchange of K+ by Ln3+ with retention of the single crystallinity, producing Ln2 [1] (2Ln ) and Ln0.33 [Ln4 (OH)4 (OAc)3 (H2 O)7 ][1] (3Ln ) for early and late lanthanides, respectively. While the Ln3+ ions in 2Ln exist as disordered aqua species, those in 3Ln form ordered hydroxide-bridged cubane clusters that connect [1]6- anions in a 3D metal-organic framework through coordination bonds with carboxylate groups. This study shows the utility of an anionic metallosupramolecular framework with carboxylate groups for the creation of a series of metal cubanes that have great potential for various applications, such as magnetic materials and heterogeneous catalysts.
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