Modeling of Spin Crossover in Iron(II) Complexes with N4S2 Coordination
Modeling of Spin Crossover in Iron(II) Complexes with N4S2 Coordination
复制标题
N4S2 配位铁 (II) 配合物中自旋交叉的建模
DOI：
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发表时间：
2019
影响因子：
3.7
通讯作者：
O. Reu
中科院分区：
文献类型：
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作者：
S. Klokishner;O. Reu
典型的Fe II自旋交叉（SCO）配合物表现出{N6}配位，其提供比{N4 S2}配体集合更强的配体场。近年来，以氮-硫混合配体为配体，铁（II）为配体的中性单核配合物[Fe（bpte）（NCE）2]（其中E = S，Se，或BH 3）的合成、晶体结构、磁性和光谱学研究都得到了报道。先验，目前尚不清楚什么是SCO在这些配合物，其中包含在最近的周围的Fe II离子四个氮配体，创造一个晶体场的中间强度，和两个硫配体，给一个弱得多的领域的起源。本文着眼于如何在密度泛函理论计算的基础上，可以给出的解释SCO现象的铁（II）配合物与混合的氮-硫配位环境。结果表明，在化合物[Fe（bpte）（NCE）2]（E = S，BH 3）中，铁（II）态参与的自旋交叉的经典方案是不稳定的。
Typical FeII spin crossover (SCO) complexes exhibit {N6} coordination, which offers a stronger ligand field than the {N4S2} ligand set. Recently, the synthesis, crystal structures, and magnetic and spectroscopic studies on the family of neutral mononuclear complexes, [Fe(bpte)(NCE)2] (where E = S, Se, or BH3) with mixed nitrogen–sulfur ligand surrounding of the iron(II) ions have been reported. A priori, it is not clear what is the origin of SCO in these complexes, which contain in the nearest surrounding of the FeII ion four nitrogen ligands, creating a crystal field of intermediate strength, and two sulfur ligands, giving a much weaker field. The present paper looks at how on the basis of density functional theory calculations an explanation can be given of the SCO phenomenon in the iron(II) complexes with mixed nitrogen–sulfur coordination environment. It is demonstrated that in compounds [Fe(bpte)(NCE)2] (E = S, BH3), the classical scenario of spin crossover with the participation of iron(II) states w...