An unexpected imidazole-induced porphyrinylphosphonate-based MOF-to-HOF structural transformation leading to the enhancement of proton conductivity

Post-synthetic modification of proton-conducting metal-organic frameworks (MOFs) by loading small molecules capable of generating protons into pores is an efficient approach for developing a new type of material with improved ionic conductivity. Herein, the synthesis, characterization and proton conductivity of a novel electroneutral MOF based on palladium(II) -tetrakis(4-(phosphonatophenyl))porphyrinate, IPCE-1Pd, are reported. The exposure of the obtained framework to imidazole by the diffusion vapor method has surprisingly led to its complete crystal-to-crystal MOF-to-HOF transformation, resulting in the formation of a novel hydrogen-bonded organic framework (HOF) IPCE-1Pd_Im, which is the first example of such kind of structural change among all known MOFs. This modification has led to an almost 25-fold increase in the proton conductivity in comparison with the pristine MOF, reaching up to 6.54 × 10 S cm at 85 °C and 95% relative humidity, which is one of the highest values among all known porphyrin-based HOFs.