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Single-Crystal-to-Single-Crystal Installation of Ln4(OH)4 Cubanes in an Anionic Metallosupramolecular Framework
Author(s)
Yoshinari, Nobuto
Meundaeng, Natthaya
Tabe, Hiroyasu
Yamada, Yusuke
Yamashita, Satoshi
Nakazawa, Yasuhiro
Konno, Takumi
Date Issued
October 5, 2020
Type
Article
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[Rh4Zn4O(l-cys)12] (K6[1]; l-H2cys=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(H2O)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.
Citation
Angewandte Chemie International Edition, 59(41), 18048-18053, 2020