Room temperature proton conduction was investigated in ammonium-based formate frameworks [NH4][M(HCOO)3] (M = Mn2+, Co2+) well-known for their ferroelectric and magnetic properties at low temperature. The synthesis was achieved through mechanosynthesis and proton conduction measurements were performed in ambient as well as in humidity and temperature controlled conditions. The proton conduction is activated by reaching the relative humidity (RH) limit of 50 % for both compounds. At 294 K a maximal conductivity of 2.2 ± 0.3 × 10−4 S/cm is observed for [NH4][Mn(HCOO)3] under RH = 70 %. The lack of proton conduction behavior in the isostructural compound Cs [Mn(HCOO)3] corroborates the role played by the NH4+ units as proton vehicle.
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