title: Magneto-Structural Analysis of Iron(III) Keggin Polyoxometalates.
abstract: A computational study and magnetic susceptibility measurements of three homonuclear Fe(III) Keggin structures are herein presented: the [FeO4@Fe12F24(μ-OCH3)12]5-anion (1), the [Bi6{FeO4@Fe12O12(OH)12}(μ-O2CCCl3)12]+cation (2) and its polymorph [Bi6{FeO4@Fe12O12(OH)10(H2O)2}(μ-O2CCF3)10]3+(3). These results are contrasted with the exchange interactions present in the previously characterized [Fe6(OH)3Ge2W18O68(OH)6]11-and [H12As4Fe8W30O120(H2O)2]4-anions. The computational analysis shows that the most significant antiferromagnetic spin coupling takes place at the junction between each of the {Fe3O6(OH)3}/{Fe3F6(OCH3)3} framework motifs, a possibility that had been previously discarded in the literature on the basis of the Fe-Fe distances. For all the examined iron(III) Keggin structures, it is found that the magnitude of the magnetic couplings within each structural subunit follows the same trend.
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology , Av. Països Catalans 16, Tarragona 43007, Spain.|Centro de Química e Bioquímica, Faculdade de Ciências, Universidade de Lisboa , Campo Grande, 1749-016 Lisboa, Portugal.|Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa , Avenida Rovisco Pais, 1049-001 Lisboa, Portugal.
authors.forename: Nuno A G
authors.initials: NA
authors.lastname: Bandeira
authors.affiliation: Department of Chemistry, Oregon State University , Corvallis, Oregon 97331, United States.
authors.forename: Omid
authors.initials: O
authors.lastname: Sadeghi
authors.affiliation: Chemistry Department Texas A&M University , P.O. Box 30012, College Station, Texas 77842-3012, United States.
authors.forename: Toby J
authors.initials: TJ
authors.lastname: Woods
authors.affiliation: Chemistry Department Texas A&M University , P.O. Box 30012, College Station, Texas 77842-3012, United States.
authors.forename: Yuan-Zhu
authors.initials: YZ
authors.lastname: Zhang
authors.affiliation: Fakultät für Physik, Universität Bielefeld , Postfach 100131, D-33501 Bielefeld, Germany.
authors.forename: Jürgen
authors.initials: J
authors.lastname: Schnack
authors.affiliation: Chemistry Department Texas A&M University , P.O. Box 30012, College Station, Texas 77842-3012, United States.
authors.forename: Kim
authors.identifier: http://orcid.org/0000-0001-5728-7805
authors.initials: K
authors.lastname: Dunbar
authors.affiliation: Department of Chemistry, Oregon State University , Corvallis, Oregon 97331, United States.
authors.forename: May
authors.identifier: http://orcid.org/0000-0002-1787-0518
authors.initials: M
authors.lastname: Nyman
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology , Av. Països Catalans 16, Tarragona 43007, Spain.|Chemistry Department Texas A&M University , P.O. Box 30012, College Station, Texas 77842-3012, United States.|Departament de Química-Física i Inorgànica, Universitat Rovira i Virgili , Carrer Marcel·lí Domingo, Tarragona 43007, Spain.
authors.forename: Carles
authors.initials: C
authors.lastname: Bo