RESUMEN
At low temperatures, the magnetization of the molecular ferric wheel NaFe6 exhibits a step at a critical field B(c) due to a field-induced level crossing. By means of high-field torque magnetometry we observed a hysteretic behavior at the level crossing with a characteristic butterfly shape which is analyzed in terms of a dissipative two-level model. Several unusual features were found. The nonzero bias field of the level crossing suggests the possibility of cooling by adiabatic magnetization.
RESUMEN
A simple template-mediated route, starting from triethalolamine 1, sodium hydride or caesium carbonate, and iron(III) chloride led to the six- and eight-membered iron coronates [Na c [Fe6[N(CH2CH2O)3]6]]+ (2) and [Cs c (Fe8[N(CH2CH2O)3]8]]+ (3). In the reaction of N-methyldiethanolamine 4 (H2L1) or N-(2,5-dimethylbenzyl)iminodiethanol 6 (H2L2) with calcium hydride followed by addition of a solution of iron(III) chloride, the neutral unoccupied coronands [Fe6Cl6(L1)6] (5) and [Fe6Cl6(L2)6] (7) were formed. Subsequent exchange of the chloride ions of 7 by bromide or thiocyanate ions afforded the ferric wheels [Fe6Br6(L2)6] (8) or [Fe6(NCS)6(L2)6] (9), respectively. Titration experiments of solutions of dianion (L1)2- with iron(III) chloride in THF revealed interesting mechanistic details about the self-assembling process leading to 5. At an iron/ligand ratio of 1:1.5 star-shaped tetranuclear [Fe[Fe(L1)2]3] (11) was isolated. However, at an iron/ligand ratio of 1:2, complex 11 was transformed into the ferric wheel 5. It was shown, that the interconversion of 5 and 11 is reversible. Based on the mechanistic studies, a procedure was developed which works for both the synthesis of homonuclear 11 and the star-shaped heteronuclear clusters [Cr[Fe(L1)2]3] (12) and [Al[Fe(L1)2]3] (13). The structures of all new compounds were determined unequivocally by single-crystal X-ray analyses.
RESUMEN
Reaction of divalent hexacoordinate metal ions with either tetradentate N-(2-piridylmethyl)iminodiethanol (3; H2L4) or tridentate N-(2-chlorobenzyl)iminodiethanol (5; H2L5) resulted in the formation of two completely different products. Starting from nickel(II) acetate and tetradentate 3, linear trinuclear complex [[Ni(HL4)]2-Ni(OAc)2(HCO2)2] (4) was formed. However, when tridentate 5 was allowed to react with cobalt(II) acetate, the novel octadecametallic square box [Na2-(Co4(HL5)3(OAc)5]4(HCO2)2] (6) was isolated. Chiral 6 has D2-molecule symmetry and crystalizes with both enantiomers in the unit cell. The structures of all new compounds were determined unequivocally by single-crystal X-ray analyses.
RESUMEN
The magnetic anisotropy of the cyclic octanuclear Fe(III) cluster [Cs subsetFe(8)[N(CH(2)CH(2)O)(3)](8)]Cl was investigated. Based on a spin Hamiltonian formalism and the consequent use of all symmetries, the magnetic anisotropy could be calculated exactly to first order, i.e., in the strong exchange limit. Experimentally, the magnetic anisotropy was investigated by magnetic susceptibility and high-field torque magnetometry of single crystals. The field and angle dependence of the torque at 1.7 K could be accurately reproduced by the calculations with one single parameter set, providing accurate results for the coupling constant and single-ion zero-field-splitting. These magnetic parameters are compared to those of several related hexanuclear ferric wheels and are discussed with respect to magneto-structural correlations for both coupling constant and single-ion anisotropy.
