International audienceSTM Observation of Open- and Closed-Ring Forms of Functionalized Diarylethene Molecules Self-Assembled on a Au(111) Surface Abstract HTMLFull Text HTML PDFHi-Res PDF[3988 KB] PDFPDF w/ Links[782 KB] Supporting Info Figures Your current credentials do not allow retrieval of the full text. Purchase the full-text Cart PDF/HTML, figures/images, references and tables, (where available) PDF Sergii V. Snegir†‡||, Alexandr A. Marchenko§, Pei Yu, Francois Maurel#, Oleksiy L. Kapitanchuk, Sandra Mazerat, Marc Lepeltier, Anne Léaustic, and Emmanuelle Lacaze*†|| Institut des NanoSciences de Paris (INSP), CNRS, 4 place Jussieu, 75251 Paris, France Institut des NanoSciences de Paris (INSP), UPMC Université Paris 6, 4 place Jussieu, 75251 Paris, France ‡Chuiko Institute of Surface Chemistry, §Institute of Physics, and Bogolyubov Institute for Theoretical Physics, National Academy of Sciences of Ukraine, Kyiv, Ukraine Institut de Chimie Moléculaire et des Matériaux d'Orsay, UMR 8182, Université Paris Sud 11, 91405 Orsay, France Univ Paris Diderot, Sorbonne Paris Cité, ITODYS, UMR CNRS 7086, 15 rue J-A de Baïf, 75205 Paris Cedex 13, France J. Phys. Chem. Lett., 2011, 2 (19), pp 2433-2436 DOI: 10.1021/jz200875c Publication Date (Web): August 24, 2011 Copyright © 2011 American Chemical Society E-mail: Emmanuelle.lacaze@insp.jussieu.fr. CASSection: Surface Chemistry and Colloids Abstract Abstract Image Ordered self-assembled monolayers (SAMs) of thiolated diarylethene photochromic molecules have been built on a Au(111) surface and characterized by mean of scanning tunneling microscopy (STM) for the first time. It has been revealed that molecules deposited from UV-illuminated (closed-ring isomer) and initial solutions (open-ring isomer) both occupy 4 × 2√3 adsorption sites on Au(111) and present a conformation where conjugated parts are parallel to the surface, forming "umbrella-like" structure. On the basis of the distances measured from STM images with intramolecular resolution and on quantum chemical DFT calculations of electronic structure for single molecules, an identical model of molecular packing with a 4 × 4√3 unit cell is proposed for both isomers. The variation of internal orbitals between open- and closed-ring isomers leads to significant change of STM contrast, allowing direct identification of each diarylethene isomer using STM images

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The light-induced and STM-tip-induced switching of photochromic thiol functionalized terphenylthiazole-based diarylethene self-assembly on Au(111) has been investigated in ambient conditions. For such a purpose, we took advantage of the formation of highly ordered domains of opened-ring (1o) or closed-ring (1c) diarylethene isomers. We evidenced a STM-tip-induced switching for the 1o isomer characterized by a tip bias threshold of 1000 mV above which switching of all molecules of the ordered 1o domains occurs into the 1c isomer. In contrast, switching from 1c form into 1o form is not observed at the same tunnelling conditions within a domain formed by ordered 1c molecules. We compared tip-induced switching of ordered 1o domains and switching of single 1o isomers embedded in 1c domains. This led to the demonstration that the process of switching of the 1o isomer is determined by geometry of the molecules but also that the stability of the switched 1c isomer depends on the nature of the surrounding isomers. We also compare tip-induced switching and switching under the action of external UV light irradiation of ordered 1o domains. In contrast with STM tip-induced switching, the UV light induces switching of 1o domains into their stable 1c form, in agreement with a collective switching under irradiation, which cannot occur under the action of STM tip.

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