Chemical Engineering of Silicon for Supramolecular Recognition

This thesis discusses some strategies to anchor functional molecules on silicon-based substrates in order to introduce onto a solid surface specific functionalities. Two main typologies of silicon-based substrates both of technological interest have been functionalized through synthetic routes based on the hydrosilylation reaction. First typology consists of flat monocrystalline Si(100) which is the surface of election for the development of commercial microelectronic devices, while second substrate typology consists of porous silicon which represents an interesting candidate for novel devices due to its specific properties such as high surface area and luminescence. In particular, the attention is focused on the surface grafting of cavitand-based molecules, synthetic organic compounds with rigid cavities of molecular dimensions, which are interesting and versatile receptors. A key point of this thesis has been the study of the recognition properties of these receptors after surface anchoring. The obtained hybrid materials consisting of cavitand monolayer bonded to silicon surface combined the technological advantages of either Si(100) or porous silicon substratetes with the recognition properties of cavitand, thus allowing various applications ranging from sensing to surface hierarchical nanoassembly.