Two zirconium-pyrogallic porphyrin MOFs, ZrPPF-n (n = 1, 2), featuring infinite ZrIV-pyrogallate (= 1,2,3-trioxobenzene) coordination chains linked via porphyrin macrocycles by eclipsed arrangement, have been successfully constructed through a top-down process (viz. from simulation to preparation). They are the first examples of Zr-MOFs (even if MOFs) based on phenolic porphyrins. Despite of its nanoscale crystal size, ZrPPF-1, as a representative, not only exhibits acid resistance (pH = 1, HCl) but also remains intact in saturated NaOH aqueous solution (ca. 20M) as long as 1 week immersed, ranking among the widest of pH tolerance for all MOFs. Endowed with spatial alignment of protic sites (like partially-protonated hydroxyls with the enhancement of acidity provided by coordination to ZrIV), the newly-synthesized ZrPPF-n reveal ultrahigh proton 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).

Design of (metallo)porphyrin-based coordination frameworks for electrochemical studies

253rd National Meeting (2017)

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