Ligand-to-metal ratio controlled assembly of tetra- and hexanuclear clusters towards single-molecule magnets.

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.