Reduction of Mn19 Coordination Clusters on a Gold Surface

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• 作者：Jan Dreiser ; Ayuk M. Ako ; Christian W盲ckerlin ; Jakoba Heidler ; Christopher E. Anson ; Annie K. Powell ; Cinthia Piamonteze ; Frithjof Nolting ; Stefano Rusponi ; Harald Brune
• 刊名：Journal of Physical Chemistry C
• 出版年：2015
• 出版时间：February 19, 2015
• 年：2015
• 卷：119
• 期：7
• 页码：3550-3555
• 全文大小：281K
• ISSN：1932-7455

文摘

The magnetic properties of a Mn₁₉ coordination cluster equipped with methylmercapto substituents on the organic ligands, [Mn^III₁₂Mn^II₇(渭₄-O)₈(渭₃-Cl)_7.7(渭₃-OMe)_0.3(HL^SMe)₁₂(MeOH)₆]Cl₂路27MeCN (Mn₁₉(SMe)) (H₃L^SMe = 2,6-bis(hydroxymethyl)-4-mercaptomethylphenol) deposited on Au(111) surfaces from solution, have been investigated by X-ray absorption spectroscopy and X-ray magnetic circular dichroism. The data reveal that in the submonolayer regime the molecules contain only divalent Mn^II in contrast to the presence of Mn^II and Mn^III ions in the powder sample. Brillouin function fits to the field-dependent magnetization suggest that the total spin ground state in the submonolayer is much lower than S_TOT = 83/2 of the pristine molecules. These findings suggest that significant changes of the electronic structure, molecular geometry, and intramolecular exchange coupling take place upon surface deposition. A sample with coverage of 2鈥? monolayers shows the presence of Mn^III, suggesting that a decoupling layer could stabilize the Mn₁₉ core on a metallic surface.