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The functionalization of layered materials is one of the current challenges in material science. Exfoliated rhombohedral (gray) arsenic represents a promising layered material for the fabrication of electronic devices and sensors; however, synthetic protocols for tuning its properties or protecting the surface by covalent functionalization are not known. In this communication, we present its covalent functionalization accompanied by the exfoliation of rhombohedral arsenic in the presence of ultraviolet light irradiation and chromium hexacarbonyl. During this modification, the arsenic atoms act as ligands to the chromium metal center. We believe that this study provides a promising approach for the modification of rhombohedral few-layer arsenene and enables its application in various fields, including electronic devices, sensors, and energy devices.

Coordination chemistry of 2D and layered gray arsenic: photochemical functionalization with chromium hexacarbonyl