Ultra-High-Field ⁶⁷Zn and ³³S NMR Studies Coupled with DFT Calculations Reveal the Structure of ZnS Nanoplatelets Prepared by an Organometallic Approach

Herein, we report the successful characterization of sulfur vacancies in ZnS nanoplatelets by in-depth high-field and DNP-enhanced solid-state NMR of S-33 and Zn-67 nuclei and DFT modeling. This twodimensional 1 nm-thick nanomaterial was obtained by reacting a dicyclohexyl zinc complex, ZnCy2, with (TMS)(2)S as the S source under mild conditions (45 degrees C) in dodecylamine. The joint experimental and theoretical studies on these nanoplatelets evidenced that a large fraction of the Zn and S atoms are located near the surface covered by dodecylamine and that the deviation from stoichiometry (agreeing with energy gap and photoluminescence properties of non-stoichiometric material) is due to sulfur vacancies. Additionally, this work reports the first S-33 DNP-NMR spectrum reported in the literature alongside several ultra-high-field S-33 and Zn-67 solid-state NMR spectra.