Spectroelectrochemical Investigation of TPPMn(III/II)‐Driven Liquid | Liquid | Electrode Triple Phase Boundary Anion Transfer into 4‐(3‐Phenylpropyl)‐Pyridine: ClO4−, CO3H−, Cl−, and F−

The triple phase boundary transfer of anions from the aqueous into an organic phase can be driven electrochemically here with the tetraphenylporphyrinato‐Mn(III/II) (or TPPMn) redox system in 4‐(3‐phenylpropyl)‐pyridine) (or PPP). Anions investigated are perchlorate, chloride, fluoride, and bicarbonate. The bicarbonate and fluoride transfer processes are shown to be chemically more complex compared to the perchlorate and chloride cases with UV‐vis‐spectroelectrochemical measurements indicating a combination of HCO₃^?/CO₃^2? transfer processes and association of fluoride with TPPMn(III)⁺, respectively. In situ spectroelectrochemistry is developed for ion‐transfer voltammetry into sub‐microliter organic phase regions on mesoporous ITO conducting film electrodes.