Basal Plane Functionalization of Niobium Disulfide Nanosheets with Cyclopentadienyl Manganese(I) Dicarbonyl

Basal plane-functionalized NbS2 nanosheets were obtained using in situ photolysis to generate the coordinatively unsaturated organometallic fragment cyclopentadienyl manganese(I) dicarbonyl (CpMn(CO)(2)). Under UV irradiation, a labile carbonyl ligand dissociates from the tricarbonyl complex, creating an open coordination site for bonding between the Mn atom and the electron-rich sulfur atoms on the surface of the NbS2 nanosheets. In contrast, no reaction is observed with 2H-MoS2 nanosheets under the same reaction conditions. This difference in reactivity is consistent with the electronic structure calculations, which indicate stronger bonding of the organometallic fragment to electron-poor, metallic NbS2 than to semiconducting, electron-rich MoS2. X-ray photoelectron spectroscopy (XPS), Fourier-transform infrared (FTIR) spectroscopy, and powder X-ray diffraction (PXRD) were used to characterize the bonding between Mn and S atoms on the surface-functionalized nanosheets.

Automated summary

Basal plane-functionalized NbS2 nanosheets were obtained using in situ photolysis to generate the coordinatively unsaturated organometallic fragment, which bonded to electron-rich sulfur atoms on the surface under UV irradiation. The reactivity difference with MoS2 nanosheets was attributed to the stronger bonding with metallic NbS2 than with semiconducting MoS2, as supported by electronic structure calculations and characterization using XPS, FTIR, and PXRD.