Immobilization of molecules onto electrodes has been focused on anchoring molecules that participate in redox reactions as discussed above. Heterogenization of a molecular catalyst onto an electric-addressable surface helps reduce the kinetic barrier of electron transfer within the double layer. However, as mentioned in the above examples, the molecularly modified electrode is not limited to serving as the catalytically active species. In Section 4.2, we discussed the interfacial electrostatic interaction induced by an electric field and inductive and through-space effects caused by ligand substitution. However, the electronic properties of an attached molecule could be tuned, in principle, by the applied electric field instead of chemical modifications of the molecular structure. A recent study on electron-inductive effects took advantage of molecularly modified electrodes as functional groups in cross-coupling and amidation reactions to replace traditional electron-donating and withdrawing substituents on the substrates. The electronic properties of the molecules being immobilized on the gold electrode could be tuned by applying different voltages: applying a negative potential imitated electron-donating groups, whereas a positive potential imitated electronwithdrawing groups. By doing so, a continuous and in situ tuning of the electronic property was performed on the substrate (Figure ). For example, in a Pd-catalyzed Suzuki-Miyaura cross-coupling reaction, the reaction rate was slowest at +0.3 V and increased upon applying a negative potential. The highest activity was reached at -0.15 V, as monitored by SERS (Figure ). This observation agreed with the trend observed when an electron-donating substitution was performed on the arylbromide substrate. Alternating the electronic property of the substrate throughout the catalytic cycle could be very challenging but may enhance the activity dramatically for the steps that require opposite electron-inductive effects. For example, the amidation reaction (Figure ) could be accelerated when 1) the nucleophilicity of the oxygen in the carboxylic acid was enhanced and 2) the electrophilicity of the carbonyl carbon in O-acylurea was enhanced. Applying a negative voltage first, then inverting to a positive voltage should facilitate the reaction. Applying -0.7 V and then switching to +0.4 V did increase the intensity of the peak of the desired product in SERS. This study showcases the possibility of utilizing electrodes as functional groups of the immobilized molecules by switching the voltage between positive and negative values to mimic electron-withdrawing and donating effects. The electron-inductive effect could be well extended to the immobilized catalyst in different catalytic systems to satisfy various electronic demands on the catalyst. This study also opens up the field of electrosynthesis in redox and non-redox reactions: in addition to directly supplying and withdrawing electrons, the electrostatic effect provided by the electrode could also be considered or employed as a tool. Reprinted with permission from AAAS.