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| Structures, charge and spin density distributions as well as nucleus-independent chemical shifts (NICSs) of [Ni(dmit)2]2-,1-,0 series, along with the dmit2-,1-,0 (dmit = 2-thione-1,3-dithiole-4,5-dithiolate) ligands, are investigated with density functional (B3LYP/6-311+G*) method. Upon oxidation from [Ni(dmit)2]2- to [Ni(dmit)2]0, theoretically deduced bond length change can be well explained by the rule of bonding and antibonding characters and is in good accord with the experimental results. Dmit2- ligand has already been oxidized at the initial coodination to the Ni2+ ion. It is the dmit2- ligand, rather than the central nickel ion, that has been oxidized upon oxidization of the [Ni(dmit)2]2-,1- series. In another word, the concept of oxidation in [Ni(dmit)2]2-,1- should apply to the dmit ligands, more exactly, apply to all sulfur atoms but not to the Ni ion. |
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| Keywords:2-thione-1,3-dithiole-4,5-dithiolate;Ni-dmit complex;electronic structure;density functional theory |
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