biostudies-literatureUnknown145(32)Badgurjar DAmerican Chemical Society Petroleum Research FundCharge-transfer events central to energy conversion and storage and molecular sensing occur at electrified interfaces. Synthetic control over the interface is traditionally accessed through electrode-specific covalent tethering of molecules. Covalent linkages inherently limit the scope and the potential stability window of molecularly tunable electrodes. Here, we report a synthetic strategy that is agnostic to the electrode's surface chemistry to molecularly define electrified interfaces. We append ferrocene redox reporters to amphiphiles, utilizing non-covalent electrostatic and van der Waals interactions to prepare a self-assembled layer stable over a 2.9 V range. The layer's voltammetric response and <i>in situ</i> infrared spectra mimic those reported for analogous covalently bound ferrocene. This design is electrode-orthogonal; layer self-assembly is reversible and independent of the underlying electrode material's surface chemistry. We demonstrate that the design can be utilized across a wide range of electrode material classes (transition metal, carbon, carbon composites) and morphologies (nanostructured, planar). Merging atomically precise organic synthesis of amphiphiles with <i>in situ</i> non-covalent self-assembly at polarized electrodes, our work sets the stage for predictive and non-fouling synthetic control over electrified interfaces.Journal of the American Chemical Society17734-17745https://www.ebi.ac.uk/biostudies/studies/S-EPMC10436282biostudies-literatureNon-Covalent Interactions Mimic the Covalent: An Electrode-Orthogonal Self-Assembled Layer.PMC10436282Badgurjar DHuynh MWuttig AMasters BfalseNon-Covalent Interactions Mimic the Covalent: An Electrode-Orthogonal Self-Assembled Layer.Charge-transfer events central to energy conversion and storage and molecular sensing occur at electrified interfaces. Synthetic control over the interface is traditionally accessed through electrode-specific covalent tethering of molecules. Covalent linkages inherently limit the scope and the potential stability window of molecularly tunable electrodes. Here, we report a synthetic strategy that is agnostic to the electrode's surface chemistry to molecularly define electrified interfaces. We append ferrocene redox reporters to amphiphiles, utilizing non-covalent electrostatic and van der Waals interactions to prepare a self-assembled layer stable over a 2.9 V range. The layer's voltammetric response and <i>in situ</i> infrared spectra mimic those reported for analogous covalently bound ferrocene. This design is electrode-orthogonal; layer self-assembly is reversible and independent of the underlying electrode material's surface chemistry. We demonstrate that the design can be utilized across a wide range of electrode material classes (transition metal, carbon, carbon composites) and morphologies (nanostructured, planar). Merging atomically precise organic synthesis of amphiphiles with <i>in situ</i> non-covalent self-assembly at polarized electrodes, our work sets the stage for predictive and non-fouling synthetic control over electrified interfaces.2023-01-01T00:00:00Z2023 Aug2025-04-21T22:10:18.971Z2025-04-05T18:36:54.802ZS-EPMC104362823754895210.1021/jacs.3c04387