Voltammetry of electroactive liquid redox systems: anion insertion and chemical reactions in microdroplets of para-tetrakis (6-methoxyhexyl) phenylenediamine, para- and meta-tetrahexylphenylenediamine

The effect of the structure of the organic precursor molecule on the electr oinsertion of anions and on the formation of materials in the ionic liquid state is compared for three compounds, para-N, N, N', N'-tetrahexylphenylen ediamine (p-THPD), meta-N, N, NI, N'-tetrahexylphenylene diamine (m-THPD), and para-N, N, N', N'-tetrakis(6-methoxyhexyl)phenylenediamine (p-TMHPD), b y characterising their condensed phase voltammetric properties in aqueous m edia. The electrochemically driven anion insertion in p-THPD and p-TMHPD in the presence of ClO4-, F-, Cl-, Br-, I-, and SO42- is shown to be extremel y sensitive to structure. The introduction of the methoxy end groups in p-T MHPD causes(1) a considerable shift to more negative electroinsertion poten tials, (2) a less stable response which upon continuous cycling decreases, and (3) considerably lower anion selectivity. For the insertion of sulfate, only p-TMHPD yields an electrochemical response which is shown to be consi stent with insertion of the dianion SO42-. The electrochemical oxidation of a deposit of m-THPD is accompanied by anion insertion and a chemical react ion step in an EC-type electrochemical process. The product of the chemical step is electrochemically active and results in a new reversible electroin sertion process. Starting materials and products of the microdroplet reacti ons are characterised by Maldi-TOF mass spectrometry and a reaction mechani sm based on condensed phase polymerisation is proposed.