Theoretical Studies on the Magnetic Switching Controlled by Stacking Patterns of Bis(maleonitriledithiolato) Nickelate(III) Dimers

Magnetic switchable maleonitriledithiolate (mnt) complexes were studied by density functional theory. The calculations were performed for anion dimers of [RBzPyR‘][Ni(mnt)2] (RBzPyR‘ = derivatives of benzylpyridinium) to elucidate magnetostructural correlations and the nature of the weak intermolecular chemical bonding. The calculated results showed that the spin delocalization, favored by the eclipsed stacking and the shorter interlayer distance, was responsible for the diamagnetic character of [1-benzyl-4-aminopyridinium][Ni(mnt)2] at low temperature. The weak antiferromagnetic and ferromagnetic interactions were also reproduced for [1-benzyl-4-aminopyridinium][Ni(mnt)2] and [1-(4‘-fluorobenzyl)pyridinium][Ni(mnt)2] at high temperature, respectively. The natural bond orbital analysis suggested that the cooperative effect of the weak intermolecular bondings may be the intrinsic driving force resulting in the switchable property, which is essentially similar to those in organic radicals exhibiting magneti...