The molecularly modified electrode provides ready access to electrons and an electric field. Accurate control over the potential being applied to the electric cell allows precise tuning of the immobilized functionalities on the electrode, emerging as a powerful tool for achieving temporal control in switchable catalysis. The electronic properties of a molecular component that can be tuned traditionally by implementing electron-donating/withdrawing substituents now could be replaced by an incrementally applied potential. In situ alternation of the electronic property (electron sufficient/deficient) on a substrate during a reaction process that could not be accomplished by molecular modification could be circumvented in a hybrid system. Different redox states of a catalytically active metal center in anchored organometallic catalysts can be modulated on demand by applying potentials.