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    Reduction of Mn19 Coordination Clusters on a Gold Surface

    Dreiser, Jan, Ako, Ayuk M., Wäckerlin, Christian, Heidler, Jakoba, Anson, Christopher E., Powell, Annie K., Piamonteze, Cinthia, Nolting, Frithjof, Rusponi, Stefano, Brune, Harald
    École Polytechnique Fédérale de Lausanne (EPFL)
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    Title: Reduction of Mn19 Coordination Clusters on a Gold Surface
    Author: Dreiser, Jan; Ako, Ayuk M.; Wäckerlin, Christian; Heidler, Jakoba; Anson, Christopher E.; Powell, Annie K.; Piamonteze, Cinthia; Nolting, Frithjof; Rusponi, Stefano; Brune, Harald
    Publisher: Amer Chemical Soc (Washington)
    Date: 2015
    Subject: Chemistry;
    Description: The magnetic properties of a Mn-19 coordination cluster equipped with methylmercapto substituents on the organic ligands, [(Mn12Mn7II)-Mn-III(mu(4)-O)(8)(mu(3)-Cl)(7.7)(mu(3)-OMe)(0.3)(HLSMe)(12)(MeOH)(6)]Cl-2 center dot 27MeCN (Mn-19(SMe)) (H3LSMe = 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 MnII 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 2-3 monolayers shows the presence of Mn-III, suggesting that a decoupling layer could stabilize the Mn-19 core on a metallic surface.
    Identifier: 10.1021/jp510240b (DOI)