Geometrical Isomer of Open-Dawson Polyoxometalate

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  • Open-Dawson型ポリオキソメタレートの構造異性体
  • 2017年度神奈川大学総合理学研究所共同研究助成論文 Open-Dawson型ポリオキソメタレートの構造異性体
  • 2017ネンド カナガワ ダイガク ソウ ゴウリガク ケンキュウジョ キョウドウ ケンキュウ ジョセイ ロンブン Open-Dawsonガタ ポリオキソメタレート ノ コウゾウ イセイタイ

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Abstract

By the reaction of β-Keggin-type polyoxometalate (POM), [A-β-SiW9O34]10- with Fe3+ at pH 3, the β, β-isomer of open-Dawson POM containing the tetra-iron(III) cluster [{Fe4(OH2) (OH)5}(β, β-Si2W18O66)]9- (β, β-Fe4-open) was successfully synthesized as potassium salt and the molecular structure was determined. It was unequivocally characterized by complete elemental analysis, thermogravimetric and differential thermal analysis (TG/DTA), FTIR and UV-vis absorption spectroscopy, cyclic voltammetry, and X-ray crystallography. X-ray crystallography revealed that the {Fe4(H2O)(OH)5}7+ cluster ion was embedded in the open pocket moiety of the β, β-type open-Dawson POM [β, β-Si2W18O66]16- formed by the fusion of two tri-lacunary β -Keggin POMs, [A-β-SiW9O34]10-, via two W-O-W bonds. The β, β-open-Dawson POM corresponds to an opened structure of the usual γ-Dawson POM. β, β-Fe4-open is the first example of the geometrical isomer of the previously reported α, α-open-Dawson POM containing the tetra-iron(III) cluster [{Fe4(OH)6}(α, α-Si2W18O66)]10- (α, α-Fe4-open).

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