Does it click? : interfacial click reactions and H–bonded arrays as studied by ambient mass spectrometry and X–ray photoelectron spectroscopy

This thesis narrates an approach towards amalgamation of synthetic organic and material chemistry. It explores the frontiers of covalent surface modification and subsequent chemical functionalization from an organic chemist’s perspective. Solid surfaces are diverse in their characteristics - this diversity also applies to the need for diverse modification and functionalization methodologies. Generally speaking, surface modification usually involves either deposition of physisorbed overlayers, or formation of covalent bonds between the exposed surficial groups and a reagent in either solution or gas phase to form strongly bound mono- or polymeric layers. For optimal results a successful interfacial reaction has to fulfill the stringent criterion of excellent yields and no side–products with fast kinetics. The development of reaction methodologies and tailoring of known organic reactions to suit such stringent demands of an interfacial “click” transformation are the challenges we have tried to tackle in the research reported in this thesis. To this end, we focus on several reactions that are orthogonally reactive, fast, form stable products and yielding little to no byproducts.