Trinuclear Triplesalophen Building Blocks with Terminal Cyanides and Implications for the Spin-Polarization Mechanism for Low-Spin Fe-III and Cr-III Ions

Oldengott J, von Richthofen C-G, Walleck S, Stammler A, Bögge H, Glaser T (2018)
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY (46): 4987-4996.

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Zeitschriftenaufsatz | Veröffentlicht | Englisch
Abstract / Bemerkung
In order to further optimize our triplesalen-based single-molecule magnets, we have synthesized the triplesalophen ligand H(6)baron(Me), where the completely sp(2)-hybridized ligand backbone should enable almost planar complexes. Here, we report the new complexes [(baron(Me)){(FeCl)-Cl-III}(3)], [(baron(Me)){Fe-III(CN)(2)}(3)](3-), and [(baron(Me)){Cr-III(CN)(2)}(3)](3-). As intended the local anisotropy axes, defined by the cyanide ligands, deviate only by ten degrees from the molecular C-3-axis. The exchange coupling in [(baron(Me)){Fe-III(CN)(2)}(3)](3-) is ferromagnetic with J = 2.2 cm(-1) but antiferromagnetic in [(baron(Me)){Cr-III(CN)(2)}(3)](3-) with J = -1.76 cm(-1). The ferromagnetic coupling in the Fe-III low-spin complex is rationalized by a good pi overlap of the d(yz) magnetic orbital with the O(p(z)) orbitals of the central phloroglucinol unit. The three unpaired electrons of the Cr-III ions in [(baron(Me)){Cr-III(CN)(2)}(3)](3-) provide competing spin-delocalization and spin-polarization pathways, which explains the overall antiferromagnetic coupling. These two complexes are the first l.s. Fe-III and Cr-III complexes of triplesalen-like ligands and emphasize the strong impact of the specific electronic configuration on the spin-polarization mechanism via the central phloroglucinol. The potential of [(baron(Me)){Fe-III(CN)(2)}(3)](3-) and [(baron(Me)){Cr-III(CN)(2)}(3)](3-) as molecular building blocks for nonanuclear complexes by coordination to the six cyanides is discussed.
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EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
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46
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4987-4996
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Oldengott J, von Richthofen C-G, Walleck S, Stammler A, Bögge H, Glaser T. Trinuclear Triplesalophen Building Blocks with Terminal Cyanides and Implications for the Spin-Polarization Mechanism for Low-Spin Fe-III and Cr-III Ions. EUROPEAN JOURNAL OF INORGANIC CHEMISTRY. 2018;(46):4987-4996.
Oldengott, J., von Richthofen, C. - G., Walleck, S., Stammler, A., Bögge, H., & Glaser, T. (2018). Trinuclear Triplesalophen Building Blocks with Terminal Cyanides and Implications for the Spin-Polarization Mechanism for Low-Spin Fe-III and Cr-III Ions. EUROPEAN JOURNAL OF INORGANIC CHEMISTRY(46), 4987-4996. doi:10.1002/ejic.201801042
Oldengott, J., von Richthofen, C. - G., Walleck, S., Stammler, A., Bögge, H., and Glaser, T. (2018). Trinuclear Triplesalophen Building Blocks with Terminal Cyanides and Implications for the Spin-Polarization Mechanism for Low-Spin Fe-III and Cr-III Ions. EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 4987-4996.
Oldengott, J., et al., 2018. Trinuclear Triplesalophen Building Blocks with Terminal Cyanides and Implications for the Spin-Polarization Mechanism for Low-Spin Fe-III and Cr-III Ions. EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, (46), p 4987-4996.
J. Oldengott, et al., “Trinuclear Triplesalophen Building Blocks with Terminal Cyanides and Implications for the Spin-Polarization Mechanism for Low-Spin Fe-III and Cr-III Ions”, EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2018, pp. 4987-4996.
Oldengott, J., von Richthofen, C.-G., Walleck, S., Stammler, A., Bögge, H., Glaser, T.: Trinuclear Triplesalophen Building Blocks with Terminal Cyanides and Implications for the Spin-Polarization Mechanism for Low-Spin Fe-III and Cr-III Ions. EUROPEAN JOURNAL OF INORGANIC CHEMISTRY. 4987-4996 (2018).
Oldengott, Jan, von Richthofen, Carl-Georg, Walleck, Stephan, Stammler, Anja, Bögge, Hartmut, and Glaser, Thorsten. “Trinuclear Triplesalophen Building Blocks with Terminal Cyanides and Implications for the Spin-Polarization Mechanism for Low-Spin Fe-III and Cr-III Ions”. EUROPEAN JOURNAL OF INORGANIC CHEMISTRY 46 (2018): 4987-4996.