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 in situ 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 in
situ non-covalent self-assembly at polarized electrodes,
our work sets the stage for predictive and non-fouling synthetic control
over electrified interfaces.