Giant porphyrin disks: control of their self-assembly at liquid-solid interfaces through metal-ligand interactions |
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Authors: | Lensen Marga C Elemans Johannes A A W van Dingenen Sandra J T Gerritsen Jan W Speller Sylvia Rowan Alan E Nolte Roeland J M |
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Affiliation: | Institute for Molecules and Materials, Radboud University Nijmegen, Toernooiveld 1, 6525 ED Nijmegen, The Netherlands. |
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Abstract: | The synthesis and self-assembly behaviour of porphyrin dodecamers 1H(2) and Zn-1, which consist of twelve porphyrins that are covalently attached to a central aromatic core, is described. According to STM, 1D and 2D NMR studies, and molecular modelling calculations, the porphyrin dodecamers have a yo-yo-shaped structure. Their large pi surface, in combination with their disk-like shape, allows them to form self-assembled structures, which in the case of Zn-1 can be tuned by adding bidentate ligands. The self-assembly of the molecules at the liquid-solid interface of 1-phenyloctane with highly oriented pyrolytic graphite or Au(111) was imaged by using STM. The porphyrin disks in the self-assembled arrays have an edge-on orientation on the surface. The addition of bidentate axial ligands to the Zn-1 molecules in the arrays allows their intermolecular distance to be precisely controlled. |
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Keywords: | metal–ligand coordination porphyrinoids scanning tunneling microscopy self‐assembly surface chemistry |
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