Reduction-Triggered Self-Assembly of Nanoscale Molybdenum Oxide Molecular Clusters

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• 作者：Panchao Yin ; Bin Wu ; Tao Li ; Peter V. Bonnesen ; Kunlun Hong ; Soenke Seifert ; Lionel Porcar ; Changwoo Do ; Jong Kahk Keum
• 刊名：Journal of the American Chemical Society
• 出版年：2016
• 出版时间：August 24, 2016
• 年：2016
• 卷：138
• 期：33
• 页码：10623-10629
• 全文大小：458K
• 年卷期：0
• ISSN：1520-5126

文摘

Understanding the formation mechanism of giant molecular clusters is essential for rational design and synthesis of cluster-based nanomaterials with required morphologies and functionalities. Here, typical synthetic reactions of a 2.9 nm spherical molybdenum oxide cluster, {Mo₁₃₂} (formula: [Mo^VI₇₂Mo^V₆₀O₃₇₂(CH₃COO)₃₀(H₂O)₇₂]^42–), with systematically varied reaction parameters have been fully explored to determine the morphologies and concentration of products, reduction of metal centers, and chemical environments of the organic ligands. The growth of these clusters shows a typical sigmoid curve, suggesting a general multistep self-assembly mechanism for the formation of giant molecular clusters. The reaction starts with a lag phase period when partial Mo^VI centers of molybdate precursors are reduced to form {Mo^V₂(acetate)} structures under the coordination effect of the acetate groups. Once the concentration of {Mo^V₂(acetate)} reaches a critical value, it triggers the co-assembly of Mo^V and Mo^VI species into the giant clusters.