Journal
SCIENCE ADVANCES
Volume 7, Issue 23, Pages -Publisher
AMER ASSOC ADVANCEMENT SCIENCE
DOI: 10.1126/sciadv.abg1790
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Funding
- EPSRC (Cambridge NanoDTC) [EP/L015978/1, EP/L027151/1, EP/S022953/1, EP/P029426/1, EP/R020965/1]
- European Research Council (ERC) under Horizon 2020 Research and Innovation Programme THOR [829067]
- POSEIDON [861950]
- EPSRC Sensor CDT [EP/L015889/1]
- Leverhulme Trust
- Isaac Newton Trust
- Winton Programme for the Physics of Sustainability
- EPSRC [EP/R020965/1, EP/P029426/1, EP/S022953/1, EP/L027151/1] Funding Source: UKRI
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Using a cascaded nano-optics approach, this study tracks the chemical trajectories of single surface-bound molecules, revealing single-molecule deprotonation and binding dynamics under ambient conditions. High-speed field-enhanced spectroscopy allows for monitoring chemical switching of a single carboxylic group between three discrete states, with theoretical calculations identifying reversible proton transfer dynamics and switching between molecule-metal coordination states. These findings open new possibilities for exploring interfacial single-molecule mechanisms and optical manipulation of their reaction pathways.
Understanding single-molecule chemical dynamics of surface ligands is of critical importance to reveal their individual pathways and, hence, roles in catalysis, which ensemble measurements cannot see. Here, we use a cascaded nano-optics approach that provides sufficient enhancement to enable direct tracking of chemical trajectories of single surface-bound molecules via vibrational spectroscopy. Atomic protrusions are laser-induced within plasmonic nanojunctions to concentrate light to atomic length scales, optically isolating individual molecules. By stabilizing these atomic sites, we unveil single-molecule deprotonation and binding dynamics under ambient conditions. High-speed field-enhanced spectroscopy allows us to monitor chemical switching of a single carboxylic group between three discrete states. Combining this with theoretical calculation identifies reversible proton transfer dynamics (yielding effective single-molecule pH) and switching between molecule-metal coordination states, where the exact chemical pathway depends on the intitial protonation state. These findings open new domains to explore interfacial single-molecule mechanisms and optical manipulation of their reaction pathways.
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