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)] (RBzPyR' = derivatives of benzylpyridinium) to elucidate magnetostructural correlations and the nature of the weak intermolecul...

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Published in:Journal of the American Chemical Society Vol. 127; no. 41; pp. 14330 - 14339
Main Authors: Zhaoping Ni, Ren, Xiaoming, Jing Ma, Jingh Xie, Chunlin Ni, Zhida Chen, Meng, Qingjin
Format: Article
Published: American Chemical Society 10/19/2005
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Online Access:View this record in EBSCOhost
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      dt: 10/19/2005
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        10.1021/ja050631z
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        atl: Theoretical Studies on the Magnetic Switching Controlled by Stacking Patterns of Bis(maleonitriledithiolato) Nickelate(III) Dimers.
      aug:
        au:
          Zhaoping Ni
          Ren, Xiaoming
          Jing Ma
          Jingh Xie
          Chunlin Ni
          Zhida Chen
          Meng, Qingjin
        affil:
          Coordination Chemistry Institute, State Key Laboratory of Coordination Chemistry.
          Institute of Theoretical and Computational Chemistry, Key Laboratory of Mesoscopic Chemistry of MOE, Nanjing University, Nanjing, 210093.
          P. R. China, and State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, P. R. China.
      su:
        Dimers
        Density functionals
        Oligomers
        Temperature
        Benzopyrene
        Chemical bonds
      sug:
        subj:
          Dimers
          Density functionals
          Oligomers
          Temperature
          Benzopyrene
          Chemical bonds
      ab: Magnetic switchable maleonitriledithiolate (mnt) complexes were studied by density functional theory. The calculations were performed for anion dimers of [RBzPyR'][Ni(mnt)] (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)] at low temperature. The weak antiferromagnetic and ferromagnetic interactions were also reproduced for [1 -benzyl-4-aminopyridinium][Ni(mnt)] and [1 -(4'-fluorobenzyl)pyridinium](Ni(mnt)] 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 magnetic bistability. Further investigations with varying interlayer distance d, the extent of slippage (slipping distance r and deviation angle α), and rotational angle θ suggested that the extent of slippage played an important role in magnetic interactions. Therefore, the abrupt modulation of the extent of slippage in the [Ni(mnt)] complexes by external perturbations provided new possibilities for the design of molecular magnetic switching devices.
      pubtype: Academic Journal
      doctype: Article
      src: R
    language: English
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