Two-Leg Molecular Ladders Formed by Hierarchical Self-Assembly of an Organic Radical

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• 作者：Nria Crivillers ; Shuhei Furukawa ; Andrea Minoia ; An Ver Heyen ; Marta Mas-Torrent ; Christian Sporer ; Mathieu Linares ; Alexander Volodin ; Chris Van Haesendonck ; Mark Van der Auweraer ; Roberto Lazzaroni
• 刊名：Journal of the American Chemical Society
• 出版年：2009
• 出版时间：May 6, 2009
• 年：2009
• 卷：131
• 期：17
• 页码：6246-6252
• 全文大小：341K
• 年卷期：v.131,no.17(May 6, 2009)
• ISSN：1520-5126

文摘

The supramolecular organization of a new polychlorotriphenyl (PTM) radical bearing three long alkyl chains has been studied by scanning tunneling microscopy (STM) at the liquid−solid interface. This radical hierarchically self-assembles on graphite forming head-to-head dimers that organize in rows following an interesting spin-containing two-leg molecular ladder topology, in which the alkyl chains determine the space between the radical rows and act as diamagnetic barriers. In addition, these double-rows also self-assemble three-dimensionally, leading to a multilayer organization which is still influenced by the HOPG substrate symmetry. The observed nanostructures are sustained by different intermolecular interactions such as Cl···Cl, Cl···Ph, π−π, van der Waals, and CH···π interactions. Theoretical calculations were used to model the observed assemblies, and the results were in complete agreement with the experimental data. Remarkably, atomic force microscopy (AFM) studies confirmed that this tendency to form double rows composed by the PTM magnetic heads surrounded by the alkyl chains is maintained after the complete evaporation of the solvent. The electrochemical and magnetic properties of these PTM nanostructures were also demonstrated.