Electronic Structure of [NiS4]^- Investigated by Single-Crystal EPR and Density Functional Theory
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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]•½H_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 gy-axis of [Ni(dddt)_2]^- is approximately on or perpendicular to the [NiS_4]^- plane while the gy-axis of [Ni(dmit)_2]^- is on the plane, though DFT study of the complexes of this study and previously reported [NiS4]^- complexes indicate that the gy-axis is on the [NiS4]^- plane.
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]•½H_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 gy-axis of [Ni(dddt)_2]^- is approximately on or perpendicular to the [NiS_4]^- plane while the gy-axis of [Ni(dmit)_2]^- is on the plane, though DFT study of the complexes of this study and previously reported [NiS4]^- complexes indicate that the gy-axis is on the [NiS4]^- plane.
참고문헌 (21)
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