Photomodification of benzyl germanane with group 6 metal carbonyls

[Display omitted] •Post-modification of 2D material (benzyl germanane).•Photochemical modification of 2D material.•Surface modification with transition metal carbonyl.•In-depth characterization.•The modification allows next utilization as catalysts or further modification. Successful postmodification of germanene-based materials opens new applications in the chemistry of monoelemental two-dimensional materials. Here, we demonstrate the successful synthesis of germanane bearing benzyl group and its coordination with carbonyl metal complexes from the group 6. The photochemical reaction was used for in situ formation of reactive intermediates based on chromium, molybdenum and tungsten carbonyls and led to the attachment of the metal-carbonyl group to the benzyl group on the germanane surface. Successful functionalization was proven by various spectroscopic methods including FTIR, Raman and x-ray photoelectron spectroscopy as well as TG-MS measurements showing the evolution of carbon monoxide at elevated temperature. The homogeneous distribution of metals and morphology was also approved by microscopy method SEM/EDS and AFM. This work shows new possibilities in the chemistry of two-dimensional monoelemental materials like germanane giving the opportunity to homogenously distribute metal atoms over the sheet surface by coordination to the benzyl group.