Hybrid redox polyethers: Electrochemical investigations in molecular melts of metalloporphyrins and metal bipyridine complexes.

摘要

Chapter 1 describes a brief history of solid state voltammetry as studied in the laboratory of Professor Royce Murray. Earlier work involved two types of solid state materials: redox polymers and polymer electrolytes. More recent efforts have been focussed on hybrid redox polyethers, which combine some of the properties of both polymer electrolytes and redox polymers.; Chapter 2 explores techniques for assessing charge transport dynamics in a cobalt bipyridine complex polyether hybrid. Electrochemical time-of-flight measurements are based on the generation of a concentration pulse at a generator electrode. The concentration pulse then diffuses across a small gap to an adjacent collector electrode and is detected. The diffusion coefficient is related to the flight time between the two electrodes. Results obtained from time-of-flight measurements are compared with chronoamperometry and cyclic voltammetry results.; Chapter 3 investigates the charge transport dynamics of an iron bipyridine complex polyether hybrid. Charge transport for this electroactive material occurs predominantly by an electron hopping mechanism. Diffusion coefficients for the Fe (II/III) reaction are examined as the active iron sites are diluted with corresponding cobalt and nickel complexes. The results are interpreted in the context of percolation theory.; Chapter 4 describes the synthesis, characterization, and neat phase electrochemistry of polyether hybrids of metalloporphyrins. Information on electron self-exchange dynamics is obtained from electrochemical measurements of the charge transport rates as a function of specific redox couple, temperature, and supporting electrolyte concentration. Ligation of the porphyrin by CO and pyridine is explored by voltammetry.; Chapter 5 describes the axial ligation reactions of a polyether-iron-porphyrin hybrid. Voltammetry is used to examine the potential shifts induced for the Fe (III/II) reaction by ligation with pyridine. Volatile ligands are added to a thin film of the porphyrin by passing a bathing gas containing the ligand over the porphyrin film. The dynamics of ligand equilibration with the film are studied by voltammetry.; Chapter 6 introduces a new, selective electrochemical detector for gas chromatography. The detector response is based on the axial ligation reactions of a polyether-iron-porphyrin hybrid. Factors affecting the resulting amperometric signals include: the strength of the specific analyte as an axial ligand; the partition coefficient; the electrode potential; and the temperature.