engleski

Single Crystal Growth, Structural Characterization and Magnetic Properties Study of an Antiferromagnetic Trinuclear Iron(III) Acetate Complex with Uncoordinated Hexamine

Structural characterization of novel Fe(III) basic acetate with 1, 3, 5, 7- tetraazaadamantane (hexamine – HEX), [Fe3(μ3-O) (OAc)6(H2O)3)](NO3) (HEX)2(H2O)5] (1), revealed a molecular structure typical for Fe(III) basic carboxylates, with a triangular array formed by three iron atoms being equilateral and with an uncoordinated hexamine molecule and nitrate anion present in the crystal structure. Despite the hexamine molecule being uncoordinated, it plays a crucial role in the formation of a supramolecular network. The magnetic properties of the compound were characterized by magnetic susceptibility, Mössbauer and EPR spectroscopy. These studies indicate the presence of high- spin iron ions in +3 oxidation state with non- Curie-like behaviour. A small room temperature value of the effective magnetic moment and a decrease of the product χ⋅T with decreasing temperature both speak in favour of antiferromagnetic interactions between the three individual Fe(III) ions of complex 1 with a total ground state spin of St = 1/2 per trinuclear cluster. EPR spectroscopy confirmed the formation of a St = 1/2 ground state, but also suggested the presence of weak intermolecular exchange interactions between two (or more) clusters of neighbouring molecules. The temperature-dependent Mössbauer spectra show a slowing-down of the fast spin- lattice relaxation rates of the paramagnetic Fe(III) ion below about 60 K, however, yet no static spin regime is reached down to 3.6 K.

acetate ; antiferromagnetic ; complex ; hexamine

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