The present study illustrates the importance of the oxidation state of iron within the mesoporous iron trimesate [{Fe3O(H2O)2F0.81(OH)0.19}{C6H3(CO2)3}2] denoted MIL-100(Fe) (MIL= Material from Institut Lavoisier) during adsorption of molecules that can interact with the accessible metal sites through π-back donation. Adsorption of CO has been first followed by FTIR spectroscopy to quantify the Lewis acid sites in the dehydrated Fe(III) sample, outgassed at 150 °C, and on the partially reduced Fe(II/III), outgassed at 250 °C. The exposure of MIL-100(Fe) to CO2, propane, propene and propyne has then been studied by FTIR spectroscopy and microcalorimetry. It appears that π-back donating molecules are strongly adsorbed on reduced iron(II) sites despite the weaker Lewis acidity of cus Fe2+ sites compared to that of Fe3+ ones, as shown by pyridine adsorption.
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