A multi-method chemometric analysis in spectroelectrochemistry: Case study on molybdenum mono-dithiolene complexes

Spectroelectrochemical (SEC) analyses combine spectroscopic measurements with electrochemical techniques and can provide deep insight into complex multi-component chemical reaction systems. SEC experiments typically produce large amounts of spectroscopic data. Chemometric techniques are required for the data analysis and aim at extracting the underlying pure component information. Here we analyze spectroelectrochemically gained UV-vis data from five molybdenum mono-dithiolene complexes with changing redox states. SEC enables an electrochemical control of the mixture composition which supports the application of chemometric curve resolution techniques. The factor ambiguity problem is addressed by a multi-method approach combining chemometric tools from the evolving factor analysis (EFA) and from the area of feasible solutions (AFS) methodology in combination with factor duality arguments. EFA enables a subsystem analysis. Two subsystems with three species each are identified, which belong to a reductive and to an oxidative region. A joint species is contained in both regions. A complete pure component decomposition becomes possible in a final step. (c) 2021 Elsevier B.V. All rights reserved.

Automated summary

Spectroelectrochemical analyses combine spectroscopic measurements with electrochemical techniques to provide insight into complex chemical reaction systems. Chemometric techniques are used to extract pure component information from the large amount of spectroscopic data generated in SEC experiments.