Switching from antiferromagnetic to ferromagnetic coupling in heptanuclear [(M6Mc)-M-t](n+) complexes by going from an achiral to a chiral triplesalen ligand

Mukherjee C, Höke V, Stammler A, Bögge H, Schnack J, Glaser T (2014)
Dalton Transactions 43(25): 9690-9703.

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Abstract
The chiral triplesalen ligand H(6)chand(RR) has been used to synthesize the chiral heptanuclear complexes [{(chand(RR))Mn-3(III)}(2){Fe-II(CN)(6)}](ClO4)(2) ((RR)[(Mn6FeII)-Fe-III](ClO4)(2)) and [{(chand(RR))Fe-3(III)}(2){Fe-II(CN)(6)}](ClO4)(2) (RR[(Fe6FeII)-Fe-III](ClO4)(2)), which have been characterized by single-crystal X-ray diffraction, mass spectrometry, elemental analysis, FT-IR, Mossbauer, and UV-vis spectroscopies, electrochemistry, as well as DC and AC magnetic susceptibility measurements. The half-wave potential of the Fe-III/Fe-II couple in (RR)[(Mn6FeII)-Fe-III](2+) and (RR)[(Fe6FeII)-Fe-III](2+) is E-1/2 = +0.21 and +0.75 V vs. Fc(+)/Fc, respectively, which (i) corresponds to a strong stabilization of the reduced Fe-II species compared to the redox couple of free [Fe-II/(III)(CN)(6)](4-/3-) and (ii) indicates a significant difference of the electronic coupling with the {(chand(RR))M-t}(3+) units (M-t = Mn-III, Fe-III). Analysis of the DC magnetic data (mu(eff) vs. T, VTVH) of both complexes by a full-matrix diagonalization of the spin-Hamiltonian including isotropic exchange, zero-field splitting with full consideration of the relative orientation of the D tensors and Zeeman interactions reveals ferromagnetic interactions of J(Mn-Mn) = +0.17 +/- 0.02 cm(-1) with DMn = -3.4 +/- 0.3 cm(-1) for (RR)[(Mn6FeII)-Fe-III](2+) and J(Fe-Fe) = +0.235 +/- 0.005 cm(-1) with D-Fe = 0 for (RR)[(Fe6FeII)-Fe-III](2+). The comparison of the molecular structures of (RR)[(Mn6FeII)-Fe-III](2+) and (RR)[(Fe6FeII)-Fe-III](2+) with those of the heptanuclear complexes [(M6Mc)-M-t](n+) using the achiral triplesalen ligand (talen(t-Bu2))(6-) reveals significant differences in the ligand folding, smaller C-C bond distances in the central phloroglucinol ring and larger HOMA values. This indicates more aromatic character and less heteroradialene contribution in (RR)[(Mn6FeII)-Fe-III](2+) and (RR)[(Fe6FeII)-Fe-III](2+), which explains the switching from antiferromagnetic coupling in [(M6Mc)-M-t](n+) to ferromagnetic coupling in (RR)[(M6Mc)-M-t](n+) by a stronger contribution of the spin-polarization mechanism. This establishes a magnetostructural correlation between the structural parameters describing the aromaticity of the central phloroglucinol unit and the observed exchange couplings J(Mn-Mn).
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Mukherjee C, Höke V, Stammler A, Bögge H, Schnack J, Glaser T. Switching from antiferromagnetic to ferromagnetic coupling in heptanuclear [(M6Mc)-M-t](n+) complexes by going from an achiral to a chiral triplesalen ligand. Dalton Transactions. 2014;43(25):9690-9703.
Mukherjee, C., Höke, V., Stammler, A., Bögge, H., Schnack, J., & Glaser, T. (2014). Switching from antiferromagnetic to ferromagnetic coupling in heptanuclear [(M6Mc)-M-t](n+) complexes by going from an achiral to a chiral triplesalen ligand. Dalton Transactions, 43(25), 9690-9703.
Mukherjee, C., Höke, V., Stammler, A., Bögge, H., Schnack, J., and Glaser, T. (2014). Switching from antiferromagnetic to ferromagnetic coupling in heptanuclear [(M6Mc)-M-t](n+) complexes by going from an achiral to a chiral triplesalen ligand. Dalton Transactions 43, 9690-9703.
Mukherjee, C., et al., 2014. Switching from antiferromagnetic to ferromagnetic coupling in heptanuclear [(M6Mc)-M-t](n+) complexes by going from an achiral to a chiral triplesalen ligand. Dalton Transactions, 43(25), p 9690-9703.
C. Mukherjee, et al., “Switching from antiferromagnetic to ferromagnetic coupling in heptanuclear [(M6Mc)-M-t](n+) complexes by going from an achiral to a chiral triplesalen ligand”, Dalton Transactions, vol. 43, 2014, pp. 9690-9703.
Mukherjee, C., Höke, V., Stammler, A., Bögge, H., Schnack, J., Glaser, T.: Switching from antiferromagnetic to ferromagnetic coupling in heptanuclear [(M6Mc)-M-t](n+) complexes by going from an achiral to a chiral triplesalen ligand. Dalton Transactions. 43, 9690-9703 (2014).
Mukherjee, Chandan, Höke, Veronika, Stammler, Anja, Bögge, Hartmut, Schnack, Jürgen, and Glaser, Thorsten. “Switching from antiferromagnetic to ferromagnetic coupling in heptanuclear [(M6Mc)-M-t](n+) complexes by going from an achiral to a chiral triplesalen ligand”. Dalton Transactions 43.25 (2014): 9690-9703.
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