Nitronyl Nitroxide Radicals Linked to Exchange-Coupled Metal Dimers - Studies Using X-ray Crystallography, Magnetic Susceptibility Measurements, EPR Spectroscopy, and DFT Calculations

Publikationstyp:
Zeitschriftenaufsatz
Metadaten:
Autoren
  • Martin Jung
  • Ajay Sharma
  • Dariush Hinderberger
  • Sebastian Braun
  • Ulrich Schatzschneider
  • Eva Rentschler
Autoren-URL
https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=fis-test-1&SrcAuth=WosAPI&KeyUT=WOS:000265464100010&DestLinkType=FullRecord&DestApp=WOS_CPL
DOI
10.1002/ejic.200801248
eISSN
1099-0682
Externe Identifier
  • Clarivate Analytics Document Solution ID: 437CQ
ISSN
1434-1948
Ausgabe der Veröffentlichung
11
Zeitschrift
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
Schlüsselwörter
  • Radicals
  • Nitronyl nitroxides
  • Magnetic properties
  • Density functional calculations
Paginierung
1495 - 1502
Datum der Veröffentlichung
2009
Status
Published
Titel
Nitronyl Nitroxide Radicals Linked to Exchange-Coupled Metal Dimers - Studies Using X-ray Crystallography, Magnetic Susceptibility Measurements, EPR Spectroscopy, and DFT Calculations
Sub types
  • Article

Datenquelle: Web of Science (Lite)

Andere Metadatenquellen:
Abstract
<jats:title>Abstract</jats:title><jats:p>To study long‐range magnetic interactions between exchange‐coupled metal centers and a radical moiety coordinated through a peripheral group, three new homodimetallic complexes with Mn<jats:sup>II</jats:sup>, Co<jats:sup>II</jats:sup>, and Zn<jats:sup>II</jats:sup> bridged by a nitronyl nitroxide (NIT) substituted benzoate ligand with the structure [(NIT‐C<jats:sub>6</jats:sub>H<jats:sub>4</jats:sub>‐COO)M<jats:sub>2</jats:sub>(L<jats:sup>R</jats:sup>)](ClO<jats:sub>4</jats:sub>)<jats:sub>2</jats:sub> {M = Mn<jats:sup>II</jats:sup>, Co<jats:sup>II</jats:sup>, and Zn<jats:sup>II</jats:sup>; NIT = nitronyl nitroxide and L<jats:sup>R</jats:sup> = <jats:italic>N</jats:italic>,<jats:italic>N</jats:italic>,<jats:italic>N′</jats:italic>,<jats:italic>N′</jats:italic>‐tetrakis(2‐benzimidazolylalkyl)‐2‐hydroxy‐1,3‐diaminopropane} have been prepared and studied by X‐ray crystallography, magnetic susceptibility measurements, EPR spectroscopy, and density functional theory calculations. For comparison, related complexes with Mn<jats:sup>II</jats:sup> and Co<jats:sup>II</jats:sup> bridged by a diamagnetic nitrobenzoate ligand were investigated by using the same methods. In all complexes, the metal centers have a trigonal‐bipyramidal N<jats:sub>3</jats:sub>O<jats:sub>2</jats:sub> coordination sphere, with the exception of the Mn<jats:sup>II</jats:sup>‐nitrobenzoate, where one of the two manganese centers is in a distorted octahedral environment due to the presence of an additional coordinated acetonitrile molecule. Magnetic susceptibility measurements on powdered samples revealed a dominant antiferromagnetic interaction between the metal ions. For the nitrobenzoate compounds, values of <jats:italic>J</jats:italic><jats:sub>Mn–Mn</jats:sub> = –5.8 cm<jats:sup>–1</jats:sup> and <jats:italic>J</jats:italic><jats:sub>Co–Co</jats:sub> = –12.0 cm<jats:sup>–1</jats:sup> are found. Replacement of the bridging ligand by a NIT‐substituted benzoate group leads to very similar antiferromagnetic metal–metal interactions with <jats:italic>J</jats:italic><jats:sub>Mn–Mn</jats:sub> = –7.2 cm<jats:sup>–1</jats:sup> and <jats:italic>J</jats:italic><jats:sub>Co–Co</jats:sub> = –12.0 cm<jats:sup>–1</jats:sup>. A metal–radical interaction could not be observed. CW‐X‐band EPR measurements at low temperature show the anisotropic NIT signal. This confirms that the radical behaves like an isolated spin center and has no influence on the metal–metal interaction. These experimental data could be confirmed by DFT calculations at the UB3LYP level.(© Wiley‐VCH Verlag GmbH &amp; Co. KGaA, 69451 Weinheim, Germany, 2009)</jats:p>
Autoren
  • Martin Jung
  • Ajay Sharma
  • Dariush Hinderberger
  • Sebastian Braun
  • Ulrich Schatzschneider
  • Eva Rentschler
DOI
10.1002/ejic.200801248
eISSN
1099-0682
ISSN
1434-1948
Ausgabe der Veröffentlichung
11
Zeitschrift
European Journal of Inorganic Chemistry
Sprache
en
Online publication date
2009
Paginierung
1495 - 1502
Datum der Veröffentlichung
2009
Status
Published
Herausgeber
Wiley
Herausgeber URL
http://dx.doi.org/10.1002/ejic.200801248
Datum der Datenerfassung
2023
Titel
Nitronyl Nitroxide Radicals Linked to Exchange‐Coupled Metal Dimers – Studies Using X‐ray Crystallography, Magnetic Susceptibility Measurements, EPR Spectroscopy, and DFT Calculations
Ausgabe der Zeitschrift
2009

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