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Abstract <p>A new dimeric vanadate tungstate with lithium countercations Li<sub>10</sub>[Co<sub>4</sub>(H<sub>2</sub>O)<sub>2</sub>(VW<sub>9</sub>O<sub>34</sub>)<sub>2</sub>]·34H<sub>2</sub>O (<b>1</b>) has been synthesized and characterized by IR, electronic absorption, and <sup>51</sup>V NMR spectroscopy. The composition and structure of <b>1</b> were determined by ESI mass spectrometry. The isotopic distribution contains a maximum peak at <i>m</i>/<i>z</i> = 1198.401, corresponding to the [Co<sub>4</sub>(H<sub>2</sub>O)<sub>2</sub>(VW<sub>9</sub>O<sub>34</sub>)<sub>2</sub> Li<sub>3</sub>H<sub>3</sub>]<sup>4−</sup> ion, which forms a sandwich structure. The study of the temperature dependence of the magnetic susceptibility product (χ<sub>m</sub><i>T</i>) and the inverse magnetic susceptibility (<InlineEquation ID="IEq1"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="10733_2025_8800_Article_IEq1.gif" Format="GIF" Height="20" Rendition="HTML" Resolution="72" Type="Linedraw" Width="28" /> </InlineMediaObject> <EquationSource Format="TEX">\(\chi _{{\text{m}}}^{{ - 1}}\)</EquationSource> <!--HighEn2570046Dzhabieva-m1--> </InlineEquation>) showed the predominance of ferromagnetic interactions Co(II)···Co(II) compared to a similar dimer with a P heteroatom in the polyoxometalate matrix Li<sub>10</sub>[Co<sub>4</sub>(H<sub>2</sub>O)<sub>2</sub>(РW<sub>9</sub>O<sub>34</sub>)<sub>2</sub>]·24H<sub>2</sub>O (<b>2</b>). The reaction of photochemical oxidation of water under visible light irradiation in the presence of electron scavenger Na<sub>2</sub>S<sub>2</sub>O<sub>8</sub>, photosensitizer bpy<sub>3</sub>RuCl<sub>2</sub>, and catalyst was studied. The efficiency of the catalytic system under optimal reaction conditions (pH 8, [<b>1</b>] = 5 μmol/L), the catalyst turnover number TON = 405, and the quantum yield of photogenerated oxygen (Ф = 0.71) are higher than those of similar catalyst <b>2</b> (TON = 330, Ф = 0.46).</p>

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Nanoscale Tetranuclear Cobalt Cluster: Structure, Magnetic and Catalytic Properties, and Reactions of Water Oxidation in Artificial Photosynthesis

  • 期刊论文

  • 发表日期：

    2025年11月19日

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  • Z. M. Dzhabieva,
  • V. Yu. Il’yashchenko,
  • G. V. Shilov,
  • A. I. Dmitriev,
  • M. V. Zhidkov,
  • T. A. Savinykh,
  • N. N. Denisov,
  • M. S. Dmitrieva,
  • T. S. Dzhabiev

摘要

Abstract

A new dimeric vanadate tungstate with lithium countercations Li10[Co4(H2O)2(VW9O34)2]·34H2O (1) has been synthesized and characterized by IR, electronic absorption, and 51V NMR spectroscopy. The composition and structure of 1 were determined by ESI mass spectrometry. The isotopic distribution contains a maximum peak at m/z = 1198.401, corresponding to the [Co4(H2O)2(VW9O34)2 Li3H3]4− ion, which forms a sandwich structure. The study of the temperature dependence of the magnetic susceptibility product (χmT) and the inverse magnetic susceptibility ( \(\chi _{{\text{m}}}^{{ - 1}}\) ) showed the predominance of ferromagnetic interactions Co(II)···Co(II) compared to a similar dimer with a P heteroatom in the polyoxometalate matrix Li10[Co4(H2O)2(РW9O34)2]·24H2O (2). The reaction of photochemical oxidation of water under visible light irradiation in the presence of electron scavenger Na2S2O8, photosensitizer bpy3RuCl2, and catalyst was studied. The efficiency of the catalytic system under optimal reaction conditions (pH 8, [1] = 5 μmol/L), the catalyst turnover number TON = 405, and the quantum yield of photogenerated oxygen (Ф = 0.71) are higher than those of similar catalyst 2 (TON = 330, Ф = 0.46).