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.