FullThrOTTLE-TrIR: Time-Resolved IR Spectroscopy of Electrochemically Generated Species Using a Full Throughput Optically Transparent Thin-Layer Electrochemical Cell.

An optically transparent thin-layer electrochemical cell with stopped-flow sample transport has been developed for optical-pump infrared-probe transient absorption spectroscopy of prereduced or preoxidized molecules. Time-resolved IR-spectra of Re(bpy)(CO)X (X = Cl, Br) complexes in different oxidation states are presented as a proof-of-principle application for this combined electrochemical and spectroscopic tool. The excited-state lifetimes and IR-spectroscopic signatures of various oxidation states of the molecule, including follow-up reaction intermediates, are disentangled by kinetic sorting, using lifetime density analysis. The method can be applied to assign and differentiate molecular intermediates in photo- and electrochemical reactions, adding new analytic coordinates to classical FTIR- and UV-vis-spectroelectrochemistry.