Electrofluorochromic molecules share the unique property that their fluorescence changes as a function of their oxidation state. This makes them interesting from a fundamental perspective as molecular dyads are designed and synthesized to tune the interplay of electrochemical and luminescent properties of molecules. Electrofluorochromic systems also find applications in sensing because a fluorescent signal can be detected with high sensitivity. Moreover, in the recent years the interest in redox-switchable fluorescent polymers has strongly increased due to their applicability in display devices. Here, we review electrofluorochromic molecules and polymers; we emphasize their structures and functional principles and point to specific applications.

In nanofluidic electrochemical sensors based on redox cycling, zeptomole quantities of analyte molecules can be detected as redox-active molecules travel diffusively between two electrodes separated by a nanoscale gap. These sensors are employed to study the properties of multiferrocenylic compounds in nonpolar media, 2,3,4-triferrocenylthiophene and 2,5-diferrocenylthiophene, which display well-resolved electrochemically reversible one-electron transfer processes. Using stochastic analysis, we are able to determine, as a function of the oxidation states of a specific redox couple, the effective diffusion coefficient as well as the faradaic current generated per molecule, all in a straightforward experiment requiring only a mesoscopic amount of molecules in a femtoliter compartment. It was found that diffusive transport is reduced for higher oxidation states and that analytes yield very high currents per molecule of 15 fA.

Classical methods to study single enzyme molecules have provided valuable information about the distribution of conformational heterogeneities, reaction mechanisms, and transients in enzymatic reactions when individual molecules instead of an averaging ensemble are studied. Here, we highlight major advances in all-electrical single enzyme studies with a focus on recent micro- and nanofluidic tools, which offer new ways of handling and studying small numbers of molecules or even single enzyme molecules. We particularly emphasize nanofluidic devices, which enable the integration of electrochemical transduction and detection.