title: Synthesis and Magnetic Characterization of Fe(III)-Based 9-Metallacrown-3 Complexes Which Exhibit Magnetorefrigerant Properties.
abstract: The structural characterization and magnetic properties of three related 9-metallacrown-3 (9-MC-3) structures are reported. Each of these iron complexes is shown to exhibit significant magnetic refrigerant properties. FeIII(acetate)3[9-MCFeIIIN(shi)-3](MeOH)3·MeOH·7H2O (1-OAc) and FeIII(benzoate)3[9-MCFeIIIN(shi)-3](MeOH)3·MeOH·4H2O (1-OBz) are structurally analogous tetranuclear iron(III) clusters which exhibit drastically different magnetic properties, due to differences in intermolecular and intramolecular π interactions which affect superexchange. 1-OAc displays a magnetocaloric effect with a maximum entropy change of -ΔSm= 15.4 J kg-1K-1at T = 3 K and an applied field change of μoΔH = 7 T, whereas 1-OBz exhibits a maximum -ΔSm= 7.4 J kg-1K-1at T = 7 K and μoΔH = 7 T and displays an inverse magnetocaloric effect at lower temperatures and field changes. 1-OAc has -ΔSmvalues comparable to those of other Fe-based MCE materials and displays a significant MCE at lower applied fields, with -ΔSm= 11.2 J kg-1K-1at 3 K and μoΔH = 3 T. The tetranuclear core of 1 may be linked with isophthalate to form an octanuclear FeIII2(isophthalate)3[9-MCFeIIIN(shi)-3]2dimer (2) that crystallizes in a honeycomb packing arrangement and exhibits solvation-dependent magnetic properties. The MCE for this molecule ranges from -ΔSm= 9.9 J kg-1K-1at T = 5 K and μoΔH = 7 T, when the pores of the material are highly occupied with solvent, to -ΔSm= 5.4 J kg-1K-1, when the system is fully desolvated.
authors.affiliation: Department of Chemistry, University of Michigan , Ann Arbor, Michigan 48109-1055, United States.
authors.forename: Chun Y
authors.initials: CY
authors.lastname: Chow
authors.affiliation: Institut de Chemie Moléculaire et des Matériaux d'Orsay, CNRS, Université de Paris Sud 11 , 91405 Orsay Cedex, France.
authors.forename: Régis
authors.initials: R
authors.lastname: Guillot
authors.affiliation: Institut de Chemie Moléculaire et des Matériaux d'Orsay, CNRS, Université de Paris Sud 11 , 91405 Orsay Cedex, France.
authors.forename: Eric
authors.initials: E
authors.lastname: Rivière
authors.affiliation: Department of Chemistry, University of Michigan , Ann Arbor, Michigan 48109-1055, United States.
authors.forename: Jeff W
authors.initials: JW
authors.lastname: Kampf
authors.affiliation: Institut de Chemie Moléculaire et des Matériaux d'Orsay, CNRS, Université de Paris Sud 11 , 91405 Orsay Cedex, France.
authors.forename: Talal
authors.initials: T
authors.lastname: Mallah
authors.affiliation: Department of Chemistry, University of Michigan , Ann Arbor, Michigan 48109-1055, United States.
authors.forename: Vincent L
authors.initials: VL
authors.lastname: Pecoraro