UV–vis–NIR spectroelectrochemistry is a combination of cyclic voltammetry (CV) and absorption spectroscopy in ultraviolet, visible and near infrared regions of the electromagnetic spectrum. Electron transfer reactions at electrodes results in the changes of the electronic structure of the electroactive species. These changes and their influence on the spectroscopic response of the compounds form the background of any spectroelectrochemical method. Thus, coupling cyclic voltammetry measurement with measurement of absorption spectra can give valuable information on the mechanism of the electrochemical reactions, the types of the formed charged species and their electronic structure. The in situ spectroelectrochemical method enables sensitive spectroscopic measurements under electron transfer conditions. Due to the accurate technique, the formation of charged species and evolution of their concentration in dependence on applied potential can be followed. UV–vis–NIR spectroelectrochemistry is the method of choice to study the redox processes in electrochromic materials. These materials can reversible change their color as a result of an electrochemical reaction and are an essential component in all kinds of electrochromic devices (ECDs). For the development and production of tailored ECDs, it is important to understand the mechanisms of the electron transfer reactions in such materials and to identify the species which are responsible for the coloration.
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