Hexalacunary [α-H2P2W12O48]12− Wells-Dawson Anion: X-ray Crystal Structural Evidence and Oligomerization to WO(OH2)4+-Bridged Dimer and Trimers

Sugiarto

Sadakane Masahiro

Chemistry A European Journal

We report the first single-crystal X-ray structural evidence of the potassium salt of the hexalacunary [α-H2P2W12O48]12− (abbreviated as {P2W12}) anion after its discovery by Contant and Ciabrini in 1977. In addition, we observed oligomerization of {P2W12} into a {WO(OH2)}4+-bridged Pacman-shaped [{WO(OH2)}(α-HP2W12O48)2]22− ({P4W25}) dimer and a cyclic [{WO(OH2)}3(P2W12O48)3]30− ({P6W39}) trimer. The three phosphotungstate anions were synthesized through recrystallization of (NH4)12[α-H2P2W12O48] from slightly alkaline (HOCH2)3CNH2/KCl, CH3NH3Cl/KCl, and CH3NH3Cl/NH4Cl solutions. The structure of {P2W12} is derived from [α-P2W18O62]6− that has six tungsten atoms one from each polar group and four from the belt–removed, and the center of the lacunary site is capped by a potassium cation. Structures of {P4W25} and {P6W39} are constructed by connecting two and three {P2W12} units with {WO(OH2)}4+, respectively. The isolation of a pure {P6W39} phosphotungstate framework without coordination with transition metal cations is unprecedented. Powder X-ray diffraction confirmed the bulk purity of these compounds, indicating that selective crystallization was achieved through the selection of countercations and pH.

lacunary Dawson

phosphotungstate

polyoxometalate

X-ray crystallography

eng

Wiley

This is the peer reviewed version of the following article: Sugiarto, M. Sadakane, Chem. Eur. J. 2023, 29, e202301051., which has been published in final form at https://doi.org/10.1002/chem.202301051. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions. This article may not be enhanced, enriched or otherwise transformed into a derivative work, without express permission from Wiley or by statutory rights under applicable legislation. Copyright notices must not be removed, obscured or modified. The article must be linked to Wiley’s version of record on Wiley Online Library and any embedding, framing or otherwise making available the article or pages thereof by third parties from platforms, services and websites other than Wiley Online Library must be prohibited.

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[DOI] https://doi.org/10.1002/chem.202301051 isVersionOf

日本学術振興会

Japan Society for the Promotion of Science

[Crossref Funder] https://doi.org/10.13039/501100001691

超セラミックスの次元・形態制御

Controls of Structural dimensionality and Crystal morphology of Supra-ceramics

22H05144