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  The Ligand Field of the Azido Ligand: Insights into Bonding Parameters and Magnetic Anisotropy in a Co(II)–Azido Complex

Schweinfurth, D., Sommer, M. G., Atanasov, M., Demeshko, S., Hohloch, S., Meyer, F., et al. (2015). The Ligand Field of the Azido Ligand: Insights into Bonding Parameters and Magnetic Anisotropy in a Co(II)–Azido Complex. Journal of the American Chemical Society, 137(5), 1993-2005. doi:10.1021/ja512232f.

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 Urheber:
Schweinfurth, David1, Autor
Sommer, Michael G.1, Autor
Atanasov, Mihail2, 3, Autor           
Demeshko, Serhiy4, Autor
Hohloch, Stephan1, Autor
Meyer, Franc4, Autor
Neese, Frank2, Autor           
Sarkar, Biprajit1, Autor
Affiliations:
1Institut für Chemie und Biochemie, Freie Universität Berlin, Fabeckstraße 34-36, D-14195 Berlin, Germany, ou_persistent22              
2Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society, ou_3023886              
3Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, 1113 Sofia, Bulgaria, ou_persistent22              
4Institut für Anorganische Chemie, Georg-August-Universität Göttingen, Tammannstraße 4, D-37077 Göttingen, Germany, ou_persistent22              

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 Zusammenfassung: The azido ligand is one of the most investigated ligands in magnetochemistry. Despite its importance, not much is known about the ligand field of the azido ligand and its influence on magnetic anisotropy. Here we present the electronic structure of a novel five-coordinate Co(II)–azido complex (1), which has been characterized experimentally (magnetically and by electronic d–d absorption spectroscopy) and theoretically (by means of multireference electronic structure methods). Static and dynamic magnetic data on 1 have been collected, and the latter demonstrate slow relaxation of the magnetization in an applied external magnetic field of H = 3000 Oe. The zero-field splitting parameters deduced from static susceptibility and magnetizations (D = −10.7 cm–1, E/D = 0.22) are in excellent agreement with the value of D inferred from an Arrhenius plot of the magnetic relaxation time versus the temperature. Application of the so-called N-electron valence second-order perturbation theory (NEVPT2) resulted in excellent agreement between experimental and computed energies of low-lying d–d transitions. Calculations were performed on 1 and a related four-coordinate Co(II)–azido complex lacking a fifth axial ligand (2). On the basis of these results and contrary to previous suggestions, the N3 ligand is shown to behave as a strong σ and π donor. Magnetostructural correlations show a strong increase in the negative D with increasing Lewis basicity (shortening of the Co–N bond distances) of the axial ligand on the N3 site. The effect on the change in sign of D in going from four-coordinate Co(II) (positive D) to five-coordinate Co(II) (negative D) is discussed in the light of the bonding scheme derived from ligand field analysis of the ab initio results.

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Sprache(n): eng - English
 Datum: 2014-11-302015-01-282015-02-11
 Publikationsstatus: Erschienen
 Seiten: 13
 Ort, Verlag, Ausgabe: -
 Inhaltsverzeichnis: -
 Art der Begutachtung: Expertenbegutachtung
 Identifikatoren: DOI: 10.1021/ja512232f
 Art des Abschluß: -

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Titel: Journal of the American Chemical Society
  Andere : JACS
  Kurztitel : J. Am. Chem. Soc.
Genre der Quelle: Zeitschrift
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Ort, Verlag, Ausgabe: Washington, DC : American Chemical Society
Seiten: - Band / Heft: 137 (5) Artikelnummer: - Start- / Endseite: 1993 - 2005 Identifikator: ISSN: 0002-7863
CoNE: https://pure.mpg.de/cone/journals/resource/954925376870