title: New iron tetrazolate frameworks: synthesis, temperature effect, thermal behaviour, Mössbauer and magnetic studies.
abstract: The exploration of the FeF3/FeF2-Hamtetraz-HF system in dimethylformamide by solvothermal synthesis evidences two isostructural 3D hybrid fluoroferrates. They are prepared from the same starting mixture at two different synthesis temperatures: 120 °C for [Hdma]·(Fe4(II)Fe(III)F8(H2O)2(amtetraz)4) () and 140 °C for [Hdma]1.5·(Fe4.5(II)Fe0.5(III)F7(H2O)(HCOO)(amtetraz)4) (). Both compounds are characterized by single crystal X-ray diffraction, X-ray thermodiffraction, TGA analysis, Mössbauer spectrometry and SQUID magnetometry. They crystallize in the monoclinic system and are built from two distinct chains connected by aminotetrazolate anions. The first chain ∞(Fe(II)FN4) is common to and and can be found in numerous fluorides. In the second chain ∞(Fe3X12) (X = F, N, O), iron cations adopt both valence states Fe(ii)/Fe(iii). The hydrolysis of DMF implies the formation of a [Hdma](+) cation and a (HCOO)(-) anion. The presence of Fe(3+) in both phases is evidenced by (57)Fe Mössbauer spectrometry. The magnetic properties are studied and two transitions from a paramagnetic regime to a long range ordered state below 30 K and 5 K are identified.
authors.affiliation: IMMM-UMR 6283 CNRS, LUNAM, Faculté des Sciences et Techniques, Université du Maine, Avenue Olivier Messiaen, 72085 Le Mans Cedex 9, France.
authors.forename: Vanessa
authors.initials: V
authors.lastname: Pimenta
authors.forename: Quang Hoang Hanh
authors.initials: QH
authors.lastname: Le
authors.forename: Lucy
authors.initials: L
authors.lastname: Clark
authors.forename: Jérôme
authors.initials: J
authors.lastname: Lhoste
authors.forename: Annie
authors.initials: A
authors.lastname: Hémon-Ribaud
authors.forename: Marc
authors.initials: M
authors.lastname: Leblanc
authors.forename: Jean-Marc
authors.initials: JM
authors.lastname: Grenèche
authors.forename: Gilles
authors.initials: G
authors.lastname: Dujardin
authors.forename: Philip
authors.initials: P
authors.lastname: Lightfoot
authors.forename: Vincent
authors.initials: V
authors.lastname: Maisonneuve