High Proton Conduction in Three Highly Water-Stable Hydrogen-Bonded Ferrocene-Based Phenyl Carboxylate Frameworks.

To acquire more new crystalline proton conductive materials, three ferrocene-based phenyl carboxylate frameworks (FCFs), [FcCO(o-C6H4COOH)] (FCF 1) (Fc = (η5-C5H5)Fe(η5-C5H4)), [m-FcC6H4COOH] (FCF 2), and [p-FcC6H4COOH] (FCF 3), supported by hydrogen bonds and π···π interactions were prepared. Their structures and phase purities are clarified by single-crystal X-ray diffraction or powder X-ray diffraction (PXRD). In addition, their high thermal and water stability were confirmed by thermogravimetric analyses, PXRD, and scanning electron microscopy determinations. Proton conductivity (σ) of 1-3 was studied under different relative humidities (RHs) and temperatures, and it was found that their σ boosted with the increase of humidity and temperature. Under 100 °C and 98% RH, their optimal σ values are 0.77 × 10-3, 1.94 × 10-4, and 3.46 × 10-3 S·cm-1, respectively. Consequently, their proton conductive mechanisms were proposed by means of activation energy calculation and structural analysis. Note that they are good proton conductive materials and are expected to be used in proton exchange membrane fuel cells.