Structure and Ferromagnetic Interactions in Open-Shell Supramolecular Assemblies Constructed from Radical Cations and Hexacyanometallate Anions
1996
The goal of our work was to design in a controlled manner open-shell supramolecular assemblies with dominant intermolecular ferromagnetic interactions. Along this line, the compounds of formula rad6M(CN)6I3· 2H2O with M = Cr, Fe, and Co have been synthesized; rad+ stands for the 2-(3-N-methylpyridinium)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazo-1-oxyl 3-N-oxide radical cation. The crystal structures have been solved. The three compounds are isomorphous. They crystallize in the trigonal space group P3 (a = 13.178(3) A, c = 10.763(6) A for M = Fe). The structure may be viewed as a two-dimensional honeycomb lattice, with three kinds of hexagons and three kinds of rad- - -rad magnetic interactions. In addition, for M = Cr and Fe, there is a fourth kind of magnetic interaction, occurring between the M(CN)63- anion and the radical core. The magnetic properties of the three compounds have been investigated. They are characteristic of dominant ferromagnetic interactions to which weak antiferromagnetic interactio...
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