A T-shaped μ3-oxido trinuclear iron cluster with high easy-plane anisotropy:: Structural and magnetic characterization

Publication type:
Journal article
Metadata:
Autoren
  • Pablo Albores
  • Eva Rentschler
Autoren-URL
https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=fis-test-1&SrcAuth=WosAPI&KeyUT=WOS:000259252200014&DestLinkType=FullRecord&DestApp=WOS_CPL
DOI
10.1002/ejic.200800327
Externe Identifier
  • Clarivate Analytics Document Solution ID: 349AW
ISSN
1434-1948
Ausgabe der Veröffentlichung
25
Zeitschrift
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
Schlüsselwörter
  • polynuclear complexes
  • magnetic properties
  • DFT calculations
  • (mu-oxido)iron core
  • easy-plane anisotropy
Paginierung
4004 - 4011
Datum der Veröffentlichung
2008
Status
Published
Titel
A T-shaped μ<sub>3</sub>-oxido trinuclear iron cluster with high easy-plane anisotropy:: Structural and magnetic characterization
Sub types
  • Article

Data source: Web of Science (Lite)

Other metadata sources:
Abstract
<jats:title>Abstract</jats:title><jats:p>The synthesis, crystal structure and magnetochemical characterization of a new μ‐oxido trinuclear iron cluster (oldnomenclature: μ‐oxo trinuclear iron cluster), [Fe<jats:sub>3</jats:sub>(μ<jats:sub>3</jats:sub>‐O)(μ<jats:sub>2</jats:sub>‐CH<jats:sub>3</jats:sub>O)<jats:sub>2</jats:sub>(μ<jats:sub>2</jats:sub>‐CH<jats:sub>3</jats:sub>COO)<jats:sub>2</jats:sub>(phen)<jats:sub>2</jats:sub>Cl<jats:sub>3</jats:sub>], is reported. The reaction of hydrated FeCl<jats:sub>3</jats:sub> with sodium acetate and 1,10‐phenanthroline in a mixture of methanol and acetonitrile afforded crystals suitable for X‐ray crystallographic determination. The new compound crystallizes in the tetragonal <jats:italic>I</jats:italic>4<jats:sub>1</jats:sub>/<jats:italic>a</jats:italic> space group (<jats:italic>a</jats:italic> = <jats:italic>b</jats:italic> = 13.6322 Å, <jats:italic>c</jats:italic> = 37.3538 Å, <jats:italic>Z</jats:italic> = 8, <jats:italic>V</jats:italic> = 6941.7 Å<jats:sup>3</jats:sup>). The core of the complex is an isosceles triangle bridged by a μ<jats:sub>3</jats:sub>‐O ion with a rare T‐shaped geometry. The chloride ions are bound terminally, and the phenanthroline ligands are π‐stacked. Variable‐temperature solid‐state dc magnetization studies were carried out in the 2.0–300 K range. Data were fit with an isotropic Heisenberg spin Hamiltonian, which included an axial anisotropy (zero‐field splitting) term. Two antiferromagnetic exchange parameters for the isosceles triangle arrangement of the iron ion were needed, with values of –11.2 and –47.7 cm<jats:sup>–1</jats:sup>, while a positive <jats:italic>D</jats:italic> value of about 1.5 cm<jats:sup>–1</jats:sup> was obtained. In addition, magnetization (<jats:italic>M</jats:italic>) vs. field (<jats:italic>H</jats:italic>) and temperature (<jats:italic>T</jats:italic>) data established an <jats:italic>S</jats:italic><jats:sub>T</jats:sub> = 5/2 ground‐state spin. We also performed broken‐symmetry DFT calculations, which reproduced the experimental <jats:italic>J</jats:italic> values and the ground‐state spin well. The replacement of one Fe<jats:sup>3+</jats:sup> ion by a Ga<jats:sup>3+</jats:sup> ion allowed for simplification of the three‐centre problem to one treating a dinuclear exchange‐coupled system, and this afforded good computed values. To the best of our knowledge, this is the first time that this specific replacement has been applied within broken‐symmetry DFT calculations. (© Wiley‐VCH Verlag GmbH &amp; Co. KGaA, 69451 Weinheim, Germany, 2008)</jats:p>
Autoren
  • Pablo Alborés
  • Eva Rentschler
DOI
10.1002/ejic.200800327
eISSN
1099-0682
ISSN
1434-1948
Ausgabe der Veröffentlichung
25
Zeitschrift
European Journal of Inorganic Chemistry
Sprache
en
Online publication date
2008
Paginierung
4004 - 4011
Datum der Veröffentlichung
2008
Status
Published
Herausgeber
Wiley
Herausgeber URL
http://dx.doi.org/10.1002/ejic.200800327
Datum der Datenerfassung
2023
Titel
A T‐Shaped μ<sub>3</sub>‐Oxido Trinuclear Iron Cluster with High Easy‐Plane Anisotropy: Structural and Magnetic Characterization
Ausgabe der Zeitschrift
2008

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