Research Article


2011, 4(4): 376–384


Formation of Extended Covalently Bonded Ni Porphyrin Networks on the Au(111) Surface

Sergey A. Krasnikov1, 2 (), Catherine M. Doyle1, Natalia N. Sergeeva3, Alexei B. Preobrajenski4, Nikolay A. Vinogradov4, Yulia N. Sergeeva3, Alexei A. Zakharov4, Mathias O. Senge3, and Attilio A. Cafolla1

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1 School of Physical Sciences, Dublin City University, Glasnevin, Dublin 9, Ireland
2 Centre for Research on Adaptive Nanostructures and Nanodevices (CRANN), School of Physics, Trinity College Dublin, Dublin 2, Ireland
3 SFI Tetrapyrrole Laboratory, School of Chemistry, Trinity College Dublin, Dublin 2, Ireland
4 MAX-Lab, Lund University, Box 118, 22100 Lund, Sweden

Keywords: Porphyrins, covalently bonded networks, scanning tunnelling microscopy, X-ray photoemission spectroscopy, near-edge X-ray absorption fine structure, Au(111)
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  • Abstract
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The growth and ordering of {5,10,15,20-tetrakis(4-bromophenyl)porphyrinato}nickel(II) (NiTBrPP) molecules on the Au(111) surface have been investigated using scanning tunnelling microscopy, X-ray absorption, core-level photoemission, and microbeam low-energy electron diffraction. When deposited onto the substrate at room temperature, the NiTBrPP forms a well-ordered close-packed molecular layer in which the molecules have a flat orientation with the porphyrin macrocycle plane lying parallel to the substrate. Annealing of the NiTBrPP layer on the Au(111) surface at 525 K leads to dissociation of bromine from the porphyrin followed by the formation of covalent bonds between the phenyl substituents of the porphyrin. This results in the formation of continuous covalently bonded porphyrin networks, which are stable up to 800 K and can be recovered after exposure to ambient conditions. By controlling the experimental conditions, a robust, extended porphyrin network can be prepared on the Au(111) surface that has many potential applications such as protective coatings, in sensing or as a host structure for molecules and clusters.
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Formation of Extended Covalently Bonded Ni Porphyrin Networks on the Au(111) Surface. Nano Res. 2011, 4(4): 376–384

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