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Access type: UnknownAuthor: search.filters.author.Nakazawa, Yasuhiro

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    Item type:Publication,
    Single-Crystal-to-Single-Crystal Installation of Ln4(OH)4 Cubanes in an Anionic Metallosupramolecular Framework
    (2020-10-05)
    Yoshinari, Nobuto
    ;
    Meundaeng, Natthaya
    ;
    Tabe, Hiroyasu
    ;
    Yamada, Yusuke
    ;
    Yamashita, Satoshi
    Postsynthetic installation of lanthanide cubanes into a metallosupramolecular framework via a single-crystal-to-single-crystal (SCSC) transformation is presented. Soaking single crystals of K<inf>6</inf>[Rh<inf>4</inf>Zn<inf>4</inf>O(l-cys)<inf>12</inf>] (K<inf>6</inf>[1]; l-H<inf>2</inf>cys=l-cysteine) in a water/ethanol solution containing Ln(OAc)<inf>3</inf> (Ln<sup>3+</sup>=lanthanide ion) results in the exchange of K<sup>+</sup> by Ln<sup>3+</sup> with retention of the single crystallinity, producing Ln<inf>2</inf>[1] (2<inf>Ln</inf>) and Ln<inf>0.33</inf>[Ln<inf>4</inf>(OH)<inf>4</inf>(OAc)<inf>3</inf>(H<inf>2</inf>O)<inf>7</inf>][1] (3<inf>Ln</inf>) for early and late lanthanides, respectively. While the Ln<sup>3+</sup> ions in 2<inf>Ln</inf> exist as disordered aqua species, those in 3<inf>Ln</inf> form ordered hydroxide-bridged cubane clusters that connect [1]<sup>6−</sup> 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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