A novel family of molecular hybrid materials based on electroactive inorganic species dispersed in conducting organic polymers is reported for use as electrodes for energy storage or conversion. Polyaniline and polypyrrole are effectively doped with electroactive polyoxometalates ([PMo12O40]3-) or ferricyanide ([(FeCN)6]3-) onions as the only doping species. The high charge and size of these anions prevents their deintercalation during reduction in most cases. These hybrids can be synthesised by chemical (bulk powders) and electrochemical (films) methods. For [PMo12O40]3-, nine aniline/pyrrole rings are found for anion in each case and the anion stays in the polymer matrix even after reduction at -0.4V (vs. Ag/AgCl, 2.6 vs. Li). In the case of the polypyrrole-Fe(CN6) hybrid, the pyrrole-ring/Fe(CN)6 ratio was around 10-12, depending on the temperature of synthesis. Temperature also affects the electrical conductivity, with the best values around 60Scm-1 (0°C). Fe(CN)6 stays in the polymer matrix when the hybrid material is reduced in organic media. Hybrids with PMo12 can intercalate up to 5.3 Li+ upon discharge (52Ah/Kg). The hybrid with Fe(CN)6 intercalates 2.7 lithium ions per formula unit (69Ah/Kg). Finally, we note that the incorporation of photoactive anions such as the polyoxometalates in COPs can yield hybrids with interesting photophysical and photocatalytic properties.

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