Synthesis of (hemi)carceplex adsorbates for self-assembly on gold

The synthesis of sulfide-functionalized (hemi)carceplexes suitable for self -assembly on gold is described. A noncentrosymmetrical carceplex 9 (guest D MF) was synthesized by the combination of calix[4]arene 4 and resorcin[4]ar ene 3, while a noncentrosymmetrical hemicarceplex 12 (guest NMP) was prepar ed by the combination of two different resorcin[4]-arenes, 3 and 10. These adsorbates form ordered self-assembled monolayers on gold with their quasi C-4v axis perpendicular to the surface. The two positions possible for the incarcerated guest lead to diastereotopic surfaces.