Hierarchical chiral framework based on a rigid adamantane tripod on Au(111) |
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Authors: | Katano Satoshi Kim Yousoo Matsubara Hiroaki Kitagawa Toshikazu Kawai Maki |
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Institution: | Surface Chemistry Laboratory, RIKEN, 2-1 Hirosawa, Wako, Saitama 351-0198 Japan. |
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Abstract: | We have investigated the tripod-shaped bromo adamantane trithiol (BATT) molecule on Au(111) using scanning tunneling microscopy (STM) at 4.7 K. Adsorption of BATT leads to formation of highly ordered self-assembled monolayers (SAMs) with three-point contacts on Au(111). The structure of these SAMs has been found to have a two-tiered hierarchical chiral organization. The self-assembly of achiral monomers produces chiral trimers, which then act as the building blocks for chiral hexagonal supermolecules. SAMs begin to form from the racemic mixture of assembled molecules in ribbon-shaped islands, followed by the transformation to enantiomeric domains when SAM layers develop two-dimensionally across hcp domains. Such a chiral phase transition at the two-dimensional domain can arise from a subtle balance between molecule-substrate and intermolecular interactions. Two structural factors, the S atom (stabilization) and the methylene groups (chirality) located just above the S atom, induce the chiral ordering of BATT on Au(111). |
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