Exchange interactions in tropylium bis(1,2-dicyanoethylene dithiolato) nickelate (III)

Manoharan, P. T. ; Noordik, J. H. ; de Boer, E. ; Keijzers, C. P. (1981) Exchange interactions in tropylium bis(1,2-dicyanoethylene dithiolato) nickelate (III) Journal of Chemical Physics, 74 (3). p. 1980. ISSN 0021-9606

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The compound tropylium bis[1,2‐dicyanoethylenedithiolato] nickelate (III), i.e., (C7H7)+ [Ni(mnt)2], has been prepared and its crystal structure determined; the space group is P21/c, Z=2, the unit cell axes are a=6.364, b=7.458, c=17.991 Å, and β=91.22 °. The Ni(mnt)2− and C7H7+ ions form segregated stacks in the direction of the b axis. This is in contrast with the structure of the analogous thiete complex (C7H7)+ [NiS2C2 (CF3)2], in which crystals alternating stacks of cations and anions are present. The susceptibility appears to be dominated by a strong one‐dimensional, isotropic, antiferromagnetic exchange coupling (J0=−4.4 cm−1). However, the angular dependence of the EPR linewidth at room temperature has to be explained with an additional anisotropic exchange interaction of 0.26 cm−1. Furthermore, Q‐band EPR measurements in the ab plane reveal a very small interstack exchange interaction (0.015 cm−1 at room temperature) which increases by a factor of 4 upon lowering the temperature to 8 K and which might be responsible for a possible long range order at low temperature.

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