Plasmon-mediated On-Surface Synthesis

ended

Photochemistry on solid surfaces is a promising candidate for overcoming the current limitations of on-surface synthesis (OSS), including the constraints of metallic substrates, poor spatiotemporal control, and demand for high temperatures. However, this nascent approach has evidenced to date relatively modest efficiencies compared to thermally induced reactions. Concomitantly, the field of plasmon-mediated chemical reactions (PMCRs) has experienced pronounced growth. PMCRs rely on the ability of plasmonic nanostructures to harness the advantages of milder visible light and efficiently transforming it into chemical energy. The rapid progress in PMCRs can be attributed to the development of novel methodologies for engineering the nano-optical properties of the localized surface plasmon resonance (LSPR). In this context, achieving precise atomic-level control over how reactants interact with plasmonic catalytic substrates holds the potential to drastically increase the chemoselectivity, efficacy and sustainability of reactions. The scientific objective of this proposal is to combine my expertise on scanning probe microscopy (SPM) and plasmonic nanocavities with the large experience of the host in OSS, targeting to direct PMCRs on surfaces at the atomic scale. Specifically, this proposal seeks to investigate three model photodimerization reactions, exploring the conditions under which the SPM-controlled optical hotspot -used for tip-enhanced Raman spectromicroscopy- can be transformed into a chemical hotspot with improved selectivity and efficiency. Furthermore, the goal is to elucidate the mechanisms governing tip-induced PMCRs, with the ultimate aim of controlling the fabrication of low-dimensional extended polymers with molecular precision using visible light. The synergistic integration of these innovative methodologies will decisively contribute to the successful realization of the project, remarkably enhancing my career trajectory and personal development.