Ab initio simulations of the intercalation of iron(III) porphyrinates in Zn 2 Al-LDH: Structural analysis and evaluation of their basic and acid sites

Density functional theory (DFT) calculations were performed to study the interaction between three dehydrated porphyrinates anions after the intercalation between Zn2Al layered double hydroxide layers, reported experimentally. A good agreement was obtained for the unit cell parameters and an analysis of the simulation approaches was conducted for the first-generation porphyrin metallated with iron(III). Post-processing calculations were also performed in order to evaluate the stabilization of these intercalation compounds and to pinpoint the acid/basic sites. These intercalation compounds are mainly stabilized by charge transfers and, for the case of the iron(III)metallated porphyrins studied in the present work, the acidity of the iron(III) centers analyzed by PDOS was not significantly affected by the porphyrin ring phenyl substitutions.