具有方形金字塔 N4X 配位的中间自旋 (S = 3/2) 铁(III) 配合物的轴向扰动:固态结构和电子特性

Sebastian Egner, Oluseun Akintola, Winfried Plass, Phil Liebing, Nils Schlörer, Gerald Hörner, Birgit Weber
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引用次数: 0

摘要

众所周知,平面定向、强场[N4]配体与弱轴向场成分的结合可使五配位铁(III)配合物稳定在其他不常见的自旋态。在这项研究中,耶格尔型[N4]大环配体[Fe(L)X](X:Cl、Br、I、NCS)的一系列轴向扰动铁(III)络合物给出了中自旋基态,并具有轴向引导的高自旋态(S = 3/2;5/2)。根据单晶 X 射线衍射获得的固态结构,讨论了从 SQUID 磁力测定法、固体中的 57Fe 莫斯鲍尔光谱以及(冷冻)溶液中的 1H NMR 和 EPR 光谱推断出的电子基态的性质。建立了一个基于 DFT 的协议,以量化轴向场效应,并通过纳入相关 [N4] 系统来预测配体的差分赤道场成分。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Axial Perturbation of Intermediate Spin (S = 3/2) Iron(III) Complexes with Square Pyramidal N4X Coordination: Solid State Structures and Electronic Properties
The combination of planar‐directing, strong‐field [N4] ligands with a weak axial field component is known to stabilize five‐coordinate iron(III) complexes in otherwise uncommon spin states. In this work, a series of axially perturbed iron(III) complexes of an [N4] macrocyclic ligand of the Jäger type, [Fe(L)X] (with X: Cl, Br, I, NCS) gave intermediate‐spin ground states with axially steered admixture of the high‐spin state, S = 3/2; 5/2. The nature of the electronic ground‐state as deduced from SQUID magnetometry, 57Fe Mössbauer spectroscopy in the solid, and 1H NMR and EPR spectroscopies in (frozen) solutions was discussed in the light of the solid‐state structures, which were obtained from single‐crystal X‐ray diffraction. A DFT‐based protocol was established to quantify the axial field effects and, by including relevant [N4] systems, predict the differential equatorial ligand field components.
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