Synthesis and Characterization of the Heptanuclear [Mn-6(III) co(III)](3+) Triplesalen Complex: Evidence for Exchange Pathways Involving Low-spin Co-III

Krickemeyer E, Höke V, Stammler A, Bögge H, Schnack J, Glaser T (2010)
Zeitschrift für Naturforschung Section B-A Journal of Chemical Sciences 65(3): 295-303.

Zeitschriftenaufsatz | Veröffentlicht | Englisch
 
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Abstract / Bemerkung
The reaction of the tert-butyl-substituted triplesalen ligand H(6)talen(t-Bu2) with Mn-II(OAc)(2)center dot 4H(2)O and K-3[Co-III(CN)(6)] results in the formation of the heptanuclear complex [{(talen(t-Bu2))(Mn-III (MeOH))(3)}(2) {Co-III (CN)(6)}](PF6)(2)(OAc)center dot IIMeOH ([(Mn6CoIII)-Co-III](PF6)(2)(OAc)center dot IIMeOH, 1 center dot IIMeOH), which has been characterized by FT-IR spectroscopy, elemental analysis, ESI-MS, single-crystal X-ray diffraction, and magnetic measurements. The molecular structure of the [(Mn6CoIII)-Co-III](3+) complex is closely related to the already published analogs [(Mn6CrIII)-Cr-III](3+) and [(Mn6FeIII)-Fe-III](3+). Variable-temperature variable-field and mu(eff) vs. T magnetic data have been analyzed in detail by full-matrix diagonalization of the appropriate spin-Hamiltonian consisting of isotropic exchange, zero-field splitting, and Zeeman interaction, taking into account the relative orientation of the D tensors. This allowed a careful inspection of the Mn-III-Mn-III exchange interaction involving a diamagnetic central metal ion. A satisfactory reproduction of the magnetic data required the incorporation not only of an exchange interaction between the Mn-III ions belonging to one triplesalen half unit, but also of an exchange coupling between Will ions belonging to different triplesalen subunits. Satisfactory reproduction of the experimental data has been obtained for the parameter set J(1) = -(0.50 +/- 0.04) cm(-1),J(2) = +(0.05 +/- 0.02) cm(-1), and D= -(2.5 +/- 0.5) cm(-1). A detailed analysis of the J(1) coupling taking into account the molecular structures of the three available heptanuclear complexes [Mn-6(III)](3+) (M = Cr, Fe, Co) indicates that the exchange interaction between the Mn-III ions belonging to the same triplesalen subunit involves not only an exchange pathway through the central phloroglucinol unit but also an exchange pathway through the central metal ion.
Stichworte
Exchange Pathways; Magnetic Properties; Heteronuclear Complexes
Erscheinungsjahr
2010
Zeitschriftentitel
Zeitschrift für Naturforschung Section B-A Journal of Chemical Sciences
Band
65
Ausgabe
3
Seite(n)
295-303
ISSN
0932-0776
eISSN
1865-7117
Page URI
https://pub.uni-bielefeld.de/record/1795475

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Krickemeyer E, Höke V, Stammler A, Bögge H, Schnack J, Glaser T. Synthesis and Characterization of the Heptanuclear [Mn-6(III) co(III)](3+) Triplesalen Complex: Evidence for Exchange Pathways Involving Low-spin Co-III. Zeitschrift für Naturforschung Section B-A Journal of Chemical Sciences. 2010;65(3):295-303.
Krickemeyer, E., Höke, V., Stammler, A., Bögge, H., Schnack, J., & Glaser, T. (2010). Synthesis and Characterization of the Heptanuclear [Mn-6(III) co(III)](3+) Triplesalen Complex: Evidence for Exchange Pathways Involving Low-spin Co-III. Zeitschrift für Naturforschung Section B-A Journal of Chemical Sciences, 65(3), 295-303. https://doi.org/10.1515/znb-2010-0311
Krickemeyer, Erich, Höke, Veronika, Stammler, Anja, Bögge, Hartmut, Schnack, Jürgen, and Glaser, Thorsten. 2010. “Synthesis and Characterization of the Heptanuclear [Mn-6(III) co(III)](3+) Triplesalen Complex: Evidence for Exchange Pathways Involving Low-spin Co-III”. Zeitschrift für Naturforschung Section B-A Journal of Chemical Sciences 65 (3): 295-303.
Krickemeyer, E., Höke, V., Stammler, A., Bögge, H., Schnack, J., and Glaser, T. (2010). Synthesis and Characterization of the Heptanuclear [Mn-6(III) co(III)](3+) Triplesalen Complex: Evidence for Exchange Pathways Involving Low-spin Co-III. Zeitschrift für Naturforschung Section B-A Journal of Chemical Sciences 65, 295-303.
Krickemeyer, E., et al., 2010. Synthesis and Characterization of the Heptanuclear [Mn-6(III) co(III)](3+) Triplesalen Complex: Evidence for Exchange Pathways Involving Low-spin Co-III. Zeitschrift für Naturforschung Section B-A Journal of Chemical Sciences, 65(3), p 295-303.
E. Krickemeyer, et al., “Synthesis and Characterization of the Heptanuclear [Mn-6(III) co(III)](3+) Triplesalen Complex: Evidence for Exchange Pathways Involving Low-spin Co-III”, Zeitschrift für Naturforschung Section B-A Journal of Chemical Sciences, vol. 65, 2010, pp. 295-303.
Krickemeyer, E., Höke, V., Stammler, A., Bögge, H., Schnack, J., Glaser, T.: Synthesis and Characterization of the Heptanuclear [Mn-6(III) co(III)](3+) Triplesalen Complex: Evidence for Exchange Pathways Involving Low-spin Co-III. Zeitschrift für Naturforschung Section B-A Journal of Chemical Sciences. 65, 295-303 (2010).
Krickemeyer, Erich, Höke, Veronika, Stammler, Anja, Bögge, Hartmut, Schnack, Jürgen, and Glaser, Thorsten. “Synthesis and Characterization of the Heptanuclear [Mn-6(III) co(III)](3+) Triplesalen Complex: Evidence for Exchange Pathways Involving Low-spin Co-III”. Zeitschrift für Naturforschung Section B-A Journal of Chemical Sciences 65.3 (2010): 295-303.
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