| Title | Diarylethene Molecules on a Ag(111) Surface: Stability and Electron-Induced Switching |
| Authors | J. Wirth, N. Hatter, R. Drost, T. R. Umbach, S. Barja, M. Zastrow, K. Rueck-Braun, J. I. Pascual, P. Saalfrank, K. J. Franke |
| Journal | Journal of Physical Chemistry C, |
| Vol. 119, 2015, pg. 4874 |
| Abstract | Diarylethene derivatives are photochromic molecular switches, undergoing a ring-opening/-closing reaction by illumination with light. The symmetry of the closed form is determined by the Woodward-Hoffmann rules according to which the reaction proceeds by conrotatory rotation in that case. Here, we show by a combined approach of scanning tunneling microscopy (STM) and density functional theory (DFT) calculations that the open isomer of 4,4''''''''''''''''-(4,4''''''''''''''''Perfluoro-cyclopent-1-ene-1,2-diyl)-bis(5-methyl-thiophene-4,2-diyl)di-pyridine) (PDTE) retains its open form upon adsorption on a Ag(111) surface. It can be switched into a closed form, which we identify as the disrotatory cyclization product, by controlled manipulation with the STM tip. Evidence of an electric-field dependent switching process is interpreted on the basis of a simple electrostatic model, which suggests that the reaction proceeds via an upright intermediate state. This pathway thus strongly differs from the switching reaction in solution. |
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