Self‐Assembly of Nanosize Coordination Cages on Si(100) Surfaces

Bottom‐up fabrication of 3D organic nanostructures on Si(100) surfaces has been achieved by a two‐step procedure. Tetradentate cavitand 1was grafted on the Si surface together with 1‐octene (Oct) as a spatial spectator by photochemical hydrosilylation. Ligand exchange between grafted cavitand 1and self‐assembled homocage 2, derived from cavitand 5bearing a fluorescence marker, led to the formation of coordination cages on Si(100). Formation, quantification, and distribution of the nanoscale molecular containers on a silicon surface was assessed by using three complementary analytical techniques (AFM, XPS, and fluorescence) and validated by control experiments on cavitand‐free silicon surfaces. Interestingly, the fluorescence of pyrene at ≈4 nm above the Si(100) surface can be clearly observed.