The reaction of [Fe(TMP)(OClO[Formula: see text]], where TMP is the dianion of tetramesitylporphyrin, with a combination of a strong [Formula: see text]-acceptor ligand and a [Formula: see text]-donating imidazole can lead to the preparation of mixed-ligand complexes [Fe(Porph)(4-CNPy)(L)][Formula: see text] where L is imidazole itself or 1-acetylimidazole and 4-cyanopyridine is the strong [Formula: see text] acceptor ligand. The stability of the new mixed-ligand pair is the presumed result of synergic bonding between the two axial ligands. The molecular structure and other characterization of the new mixed axial ligand complex, [Fe(TMP)(4-CNPy)(HIm)]ClO4 is described. The axial ligands have a relative perpendicular arrangement with Fe–N(imidazole) = 1.945 Å and Fe–N(pyridine) = 2.021 Å. The average equatorial Fe–N[Formula: see text] distance is 1.963 Å, which is consistent with the S4-ruffled TMP core. Despite the relative perpendicular arrangement of axial ligands, the EPR spectrum of the complex is a rhombic signal and not a large gmax signal. The EPR g-values are [Formula: see text] 3.05, [Formula: see text] 2.07, and [Formula: see text] 1.22. A quadrupole doublet was seen in the Mössbauer spectrum with an isomer shift of 0.197 mm/s and quadrupole splitting of 1.935 mm/s. Two crystalline forms of [Fe(TMP)(4-CNPy)(HIm)]ClO4 have been characterized; the two forms differ only in the solvent content of the lattice. Crystal data for form A: [Formula: see text] 15.432 (12) Å, [Formula: see text] 20.696 (2) Å, [Formula: see text] 19.970 (5) Å, and [Formula: see text] 99.256 (14)[Formula: see text], monoclinic, space group P21/n, V [Formula: see text] 6295 (2) Å3, Z [Formula: see text] 4, formula FeCl3O4N8C[Formula: see text]H[Formula: see text], 8397 observed data, [Formula: see text] 0.086, [Formula: see text] 0.210, refinement on [Formula: see text]. Crystal data for form B: [Formula: see text]15.267 (3) Å, [Formula: see text]20.377 (6) Å, [Formula: see text] 19.670 (4) Å, and [Formula: see text] 98.14 (1)[Formula: see text], monoclinic, space group P[Formula: see text]/n, V = 6058 (4) Å3, Z = 4, formula C[Formula: see text]H[Formula: see text]Cl[Formula: see text]FeN8O4, 5464 observed data, [Formula: see text] 0.096, [Formula: see text] 0.112, refinement on F.

中文翻译：

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混合轴向配体复合物（4-氰基吡啶）（咪唑）（四苯甲基卟啉）高氯酸铁（iii）的表征。通过协同结合稳定

[Fe(TMP)(OClO[公式：见正文]]的反应，其中 TMP 是四苯甲基卟啉的双阴离子，与强 [公式：见正文]-受体配体和 [公式：见正文]的组合-捐赠咪唑可导致制备混合配体配合物 [Fe(Porph)(4-CNPy)(L)][公式：见正文] 其中 L 是咪唑本身或 1-乙酰咪唑和 4-氰基吡啶是强 [公式: 见正文] 受体配体。新的混合配体对的稳定性是两个轴向配体之间协同键合的假定结果。新的混合轴向配体复合物的分子结构和其他表征，[Fe(TMP)(4 -CNPy)(HIm)]ClO4被描述。轴向配体具有相对垂直排列，Fe-N（咪唑）= 1.945 Å 和 Fe-N（吡啶）= 2.021 Å。平均赤道 Fe-N[公式：见正文] 距离为 1.963 Å，与 S4-褶皱的 TMP 核心。尽管轴向配体相对垂直排列，但复合物的 EPR 光谱是菱形信号，而不是大 g最大限度信号。EPR g 值为 [公式：见正文] 3.05、[公式：见正文] 2.07 和 [公式：见正文] 1.22。在 Mössbauer 光谱中可以看到四极双峰，异构体位移为 0.197 mm/s，四极分裂为 1.935 mm/s。[Fe(TMP)(4-CNPy)(HIm)]ClO的两种晶型4已被表征；这两种形式的区别仅在于晶格的溶剂含量。晶型 A 的晶体数据：[公式：见正文] 15.432 (12) Å，[公式：见正文] 20.696 (2) Å，[公式：见正文] 19.970 (5) Å，和 [公式：见正文] 99.256 (14)【公式：见正文】，单斜，空间群P21/n, V [公式：见正文] 6295 (2) Å3, Z [公式：见正文] 4、公式FeCl3○4ñ8C[公式：见文]H[公式：见文]，8397个观测数据，[公式：见文]0.086，[公式：见文]0.210，[公式：见文]的细化。B型晶体数据：[公式：见正文]15.267 (3) Å，[公式：见正文]20.377 (6) Å，[公式：见正文] 19.670 (4) Å，和[公式：见正文]98.14 (1)[公式：见正文]，单斜，空间群 P[公式：见正文]/n，V = 6058 (4) Å3, Z = 4，公式 C[公式：见正文]H[公式：见正文]Cl[公式：见正文]FeN8○4, 5464 个观测数据，[公式：见正文] 0.096，[公式：见正文] 0.112，对 F 进行细化。