Probing surface structure on two-dimensional metal-organic layers to understand suppressed interlayer packing

Two-dimensional metal-organic layers (MOLs) from alternatively connected benzene-tribenzoate ligands and Zr₆(µ₃-O)₄(µ₃-OH)₄ or Hf₆(µ₃-O)₄(µ₃-OH)₄ secondary building units can be prepared in gram scale via solvothermal synthesis. However, the reason why the monolayers did not pack to form thick crystals is unknown. Here we investigated the surface structure of the MOLs by a combination of sum-frequency generation spectroscopy, nanoscale infrared microscopy, atomic force microscopy, aberration- corrected transmission electron microscopy, and compositional analysis. We found a partial coverage of the monolayer surface by dangling tricarboxylate ligands, which prevent packing of the monolayers. This finding illustrates low-density surface modification as a strategy to prepare new two-dimensional materials with a high percentage of exposed surface.