title: Tuning the iron redox state inside a microporous porphyrinic metal organic framework.
abstract: Two new 3D porphyrin-based metal organic frameworks were obtained by solvothermally reacting iron(iii) chloride, a free base (5,10,15,20-tetrakis[4-(2,3,4,5-tetrazolyl)phenyl]porphyrin) (H2TTPP) and either pyrazine or 1,4-diazabicyclo[2.2.2]octane (DABCO). Both MOFs displayed a 3-D open framework of the fry topology, where the inorganic building unit is a chain of corner-sharing FeN4O2octahedra and the porphyrinic linker is metallated with iron during the reaction course, with the N-donor base bridging the iron of the porphyrinic cores. Through thorough structural and spectroscopic analyses of the pyrazine containing material the chemical formula [FeIIpzTTP(FeDMF1-xFeOHx)]nwas inferred (x ≥ 0.25). Whereas the already reported carboxylate analogue is built up from a pure iron(iii) inorganic chain, here spectroscopic and structural studies evidenced a mixed valence iron(ii/iii) state, evidencing that, in agreement with the HSAB theory, the substitution of a carboxylate function by a tetrazolate one allows redox tuning. Finally, both materials feature one-dimensional channels of ca. 8 × 12 Å within the structures with permanent microporosity.
authors.affiliation: Univ Lyon, Université Claude Bernard Lyon 1, Laboratoire des Multimatériaux et Interfaces, UMR CNRS 5615, F-69622 Villeurbanne, France. alexandra.fateeva@univ-lyon1.fr.
authors.forename: Brian
authors.initials: B
authors.lastname: Abeykoon
authors.affiliation: Institut des Molécules et Matériaux du Mans, UMR CNRS 6283 Université du Maine - Avenue Olivier Messiaen, 72085 Le Mans, France.
authors.forename: Jean-Marc
authors.initials: JM
authors.lastname: Grenèche
authors.affiliation: Univ Lyon, Université Claude Bernard Lyon 1, Laboratoire des Multimatériaux et Interfaces, UMR CNRS 5615, F-69622 Villeurbanne, France. alexandra.fateeva@univ-lyon1.fr.
authors.forename: Erwann
authors.initials: E
authors.lastname: Jeanneau
authors.affiliation: Swiss-Norwegian Beamline, ESRF BP-220, 38043 Grenoble, France.
authors.forename: Dmitry
authors.initials: D
authors.lastname: Chernyshov
authors.affiliation: Univ Lyon, Université Claude Bernard Lyon 1, Laboratoire des Multimatériaux et Interfaces, UMR CNRS 5615, F-69622 Villeurbanne, France. alexandra.fateeva@univ-lyon1.fr.
authors.forename: Christelle
authors.initials: C
authors.lastname: Goutaudier
authors.affiliation: Institut de Recherches sur la Catalyse et l'Environnement de Lyon, Université Claude Bernard Lyon 1, CNRS UMR 5256, Villeurbanne, France.
authors.forename: Aude
authors.initials: A
authors.lastname: Demessence
authors.affiliation: Institut Lavoisier, UMR CNRS 8180, Université de Versailles Saint-Quentin-en-Yvelines, 45 avenue des Etats-Unis, 78035 Versailles cedex, France and Institut des Matériaux de Nantes, 2 rue de la Houssinière, BP32229, 44322 Nantes cedex 3, France.
authors.forename: Thomas
authors.initials: T
authors.lastname: Devic
authors.affiliation: Univ Lyon, Université Claude Bernard Lyon 1, Laboratoire des Multimatériaux et Interfaces, UMR CNRS 5615, F-69622 Villeurbanne, France. alexandra.fateeva@univ-lyon1.fr.
authors.forename: Alexandra
authors.initials: A
authors.lastname: Fateeva