The synthesis, crystal structure and magnetic properties of the hexametallic Fe(III) cluster Fe(6)(III)O(2)(OH)(2){C(4)N(2)H(2)SMe)(2)C(OH)O}(2) ((t)BuCO(2))(10)] (1) are reported. Compound 1 was prepared by reaction of mixed-valent [Fe(3)O((t)BuCO(2))(6)(py)(3)] with one equivalent of the new ligand di-2-(4-methylthio)pyrimidyl ketone (DTPK) in MeCN solution. Compound 1 consists of a planar array of six Fe( III) ions comprising two [Fe(3)(mu(3)-O)](7+) subunits that are related by an inversion centre and linked at two of their apices, each via one mu-hydroxide and two mu-carboxylate groups. Variable temperature magnetic susceptibility and low temperature magnetization measurements show a well isolated S = 5 electronic spin ground state. Variable temperature W-band EPR measurements on a polycrystalline sample give well resolved spectra and simulations confirm a negative zero-field splitting of D = -0.224 cm (1) but also reveal a very rhombic nature (E/vertical bar D vertical bar = 0.27). Although 1 has a well isolated S = 5 ground state with a negative magnetic anisotropy, it is not a SMM due to this large rhombicity.
Synthesis, structural, magnetic and high frequency EPR studies on a hexametallic Fe(III) complex with a highly rhombic S=5 ground state / Cooper, P.; Tuna, F.; Shanmugam, M.; Sorace, L.; Heath, S. L.; Collison, D.; McInnes, E.J.L.; Winpenny, R.E.P.. - In: INORGANICA CHIMICA ACTA. - ISSN 0020-1693. - STAMPA. - 361:(2008), pp. 3663-3668. [10.1016/j.ica.2008.03.081]
Synthesis, structural, magnetic and high frequency EPR studies on a hexametallic Fe(III) complex with a highly rhombic S=5 ground state
Sorace, L.;
2008
Abstract
The synthesis, crystal structure and magnetic properties of the hexametallic Fe(III) cluster Fe(6)(III)O(2)(OH)(2){C(4)N(2)H(2)SMe)(2)C(OH)O}(2) ((t)BuCO(2))(10)] (1) are reported. Compound 1 was prepared by reaction of mixed-valent [Fe(3)O((t)BuCO(2))(6)(py)(3)] with one equivalent of the new ligand di-2-(4-methylthio)pyrimidyl ketone (DTPK) in MeCN solution. Compound 1 consists of a planar array of six Fe( III) ions comprising two [Fe(3)(mu(3)-O)](7+) subunits that are related by an inversion centre and linked at two of their apices, each via one mu-hydroxide and two mu-carboxylate groups. Variable temperature magnetic susceptibility and low temperature magnetization measurements show a well isolated S = 5 electronic spin ground state. Variable temperature W-band EPR measurements on a polycrystalline sample give well resolved spectra and simulations confirm a negative zero-field splitting of D = -0.224 cm (1) but also reveal a very rhombic nature (E/vertical bar D vertical bar = 0.27). Although 1 has a well isolated S = 5 ground state with a negative magnetic anisotropy, it is not a SMM due to this large rhombicity.File | Dimensione | Formato | |
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