Spectroelectrochemistry on electroactive self-assembled monolayers: Cyclic voltammetry coupled to spectrophotometry

•Visible and NIR spectroelectrochemistry probes electroactive self-assembled monolayers.•Self-assembled monolayer could be viewed as a highly concentrated solution.•The spectroelectrochemical bench is dedicated to absorption and fluorescence measurements.

We present a spectroelectrochemical bench involving an electrochemical/spectrophotometric coupling dedicated to probe electroactive self-assembled monolayers (SAMs). This bench is validated by the study of the oxidation of a 5,5′-disubstituted-2,2′-bithiophene immobilized on Au substrate, producing a reversible dimerization of the radical cation (i.e. ECDim process) leading to a dimer. A direct comparison between thin layer spectroelectrochemistry in solution and spectroelectrochemistry on SAMs shows that a SAM could be viewed as a highly concentrated solution.

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