Journal of the Korean Magnetic Resonance Society (한국자기공명학회논문지)

Korean Magnetic Resonance Society (한국자기공명학회)
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Electronic Structure of [NiS4]- Investigated by Single-Crystal EPR and Density Functional Theory

  • Min, Su-Young (Department of Chemistry, Kyungpook National University) ;
  • Noh, Dong-Youn (Department of Chemistry, Seoul Women's University) ;
  • Choi, Cheol-Ho (Department of Chemistry, Kyungpook National University) ;
  • Lee, Hong-In (Department of Chemistry, Kyungpook National University)
  • Received : 2012.04.28
  • Accepted : 2012.06.08
  • Published : 2012.06.20
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Abstract

To understand the electronic structure of $[NiS_4]^-$ complex ions, two complexes with such $[NiS_4]^-$ core, $FcCH=CHPymCH_3[Ni(dmit)_2]$ (Pym = pyridinium, $dmit^{2-}$ = 2-thioxo-1,3-dithiole-4,5-dithiolate) and $FcCH=CHPymCH_3[Ni(dddt)_2]{\cdot}{\frac{1}{2}}H_2O$ ($dddt^{2-}=5,6-dihydro-1,4-dithiin-2,3-dithiolato$), were synthesized to be characterized by X-ray crystallography, single crystal electron paramagnetic resonance (EPR) and density functional theory (DFT) calculation. Powder EPR spectra show narrow g-anisotropy but the anisotropy is bigger in $[Ni(dmit)_2]^-$ than in $[Ni(dddt)_2]^-$, indicating bigger spin density in Ni(III) d-orbital of $[Ni(dmit)_2]^-$ than in $[Ni(dddt)_2]^-$, which is consistent to DFT results. EPR studies of the crystals of the complexes surprisingly suggest that the $g_y$-axis of $[Ni(dddt)_2]^-$ is approximately on or perpendicular to the $[NiS_4]^-$ plane while the $g_y$-axis of $[Ni(dmit)_2]^-$ is on the plane, though DFT study of the complexes of this study and previously reported $[NiS_4]^-$ complexes indicate that the $g_y$-axis is on the $[NiS_4]^-$ plane.

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