Photoinduced modulation of the oxidation state of dibenzothiophene S-oxide molecules on an insulating substrate

Abstract

Abstract On-surface chemistry aims to overcome the limitations of conventional in-solution synthesis by taking advantage of the confinement in two dimensions to master highly ordered covalent structures with tailored properties. So far, most of the reported work is conducted on metal substrates and relies on unconventional mechanisms, thereby precluding a direct transposition of well-established organic reactions from solutions to surfaces. In addition, the intrinsic properties and reactivity of metal substrates often limit the activation methods available to trigger on-surface reactions, and photoinduced processes are especially difficult to handle due to quenching of the adsorbed precursor molecules. Herein, the photoinduced deoxygenation of dibenzothiophene S -oxide (DBTO) derivatives is transposed from solutions to insulating alkali halide surfaces in ultra-high vacuum. By combining in-solution and on-surface investigations by means of scanning tunneling microscopy, non-contact atomic force microscopy, as well as bias spectroscopy measurements, we provide evidence of the successful on-surface deoxygenation of individual DBTO derivatives under UV irradiation. The photoinduced deoxygenation is conducted at low temperature (<25 K) on a NaCl thin film formed on a Au(111) substrate to yield the reduced dibenzothiophene (DBT) product with excellent chemoselectivity. This work thus opens the way to in-situ photocontrolled charge state manipulation in purely organic compounds.