Robust Porphyrin-Spaced Zirconium Pyrogallate Frameworks with High Proton Conduction

An isoreticular family of zirconium polyphenolate networks (ZrPP- n, n = 1 and 2), bridged by porphyrinic macrocycles in an eclipsed arrangement, have excellent stability toward water, especially strong basic media of saturated NaOH aqueous solution. Endowed with spatial alignment of protic sites, viz., partially protonated phenols of acidity enhanced by coordination to Zr⁴⁺, along with guest dimethylamine cations, the newly synthesized ZrPP- n reveal exceptional conductivity (8.0 × 10^-3 and 4.2 × 10^-3 S cm^-1, for n = 1 and 2, respectively, pelleted sample, under 98% relative humidity at 25 °C).