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Single‐Crystal‐to‐Single‐Crystal Installation of Ln4(OH)4 Cubanes in an Anionic Metallosupramolecular Framework
Authors:Nobuto Yoshinari  Natthaya Meundaeng  Hiroyasu Tabe  Yusuke Yamada  Satoshi Yamashita  Yasuhiro Nakazawa  Takumi Konno
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.
Keywords:cluster compounds  crystal engineering  lanthanides  postsynthetic modification
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