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Surfaces 2018, 1(1), 12-28; https://doi.org/10.3390/surfaces1010003

Potential Driven Non-Reactive Phase Transitions of Ordered Porphyrin Molecules on Iodine-Modified Au(100): An Electrochemical Scanning Tunneling Microscopy (EC-STM) Study

1
Department of Chemical Sciences and INSTM Unit, University of Padova, Via F. Marzolo 1, 35131 Padova, Italy
2
Institute of Physical and Theoretical Chemistry, Bonn University, Wegeler-Strasse 12, D-53115 Bonn, Germany
3
Institute of Experimental Physics, Plaza Maxa Borna 9, 50-204 Wroclaw, Poland
*
Authors to whom correspondence should be addressed.
Received: 3 July 2018 / Revised: 22 July 2018 / Accepted: 24 July 2018 / Published: 25 July 2018
(This article belongs to the Special Issue Electrochemical Surface Science: Basics and Applications)
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Abstract

The modelling of long-range ordered nanostructures is still a major issue for the scientific community. In this work, the self-assembly of redox-active tetra(N-methyl-4-pyridyl)-porphyrin cations (H2TMPyP) on an iodine-modified Au(100) electrode surface has been studied by means of Cyclic Voltammetry (CV) and in-situ Electrochemical Scanning Tunneling Microscopy (EC-STM) with submolecular resolution. While the CV measurements enable conclusions about the charge state of the organic species, in particular, the potentio-dynamic in situ STM results provide new insights into the self-assembly phenomena at the solid-liquid interface. In this work, we concentrate on the regime of positive electrode potentials in which the adsorbed molecules are not reduced yet. In this potential regime, the spontaneous adsorption of the H2TMPyP molecules on the anion precovered surface yields the formation of up to five different potential-dependent long-range ordered porphyrin phases. Potentio-dynamic STM measurements, as a function of the applied electrode potential, show that the existing ordered phases are the result of a combination of van der Waals and electrostatic interactions. View Full-Text
Keywords: porphyrins; self-assembly; surface nanostructures; in situ EC-STM; metal-electrolyte interface; potential-dependent structures; combined non-covalent control porphyrins; self-assembly; surface nanostructures; in situ EC-STM; metal-electrolyte interface; potential-dependent structures; combined non-covalent control
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited (CC BY 4.0).
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Kosmala, T.; Blanco, M.; Granozzi, G.; Wandelt, K. Potential Driven Non-Reactive Phase Transitions of Ordered Porphyrin Molecules on Iodine-Modified Au(100): An Electrochemical Scanning Tunneling Microscopy (EC-STM) Study. Surfaces 2018, 1, 12-28.

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