UMR CNRS 6521, Chimie, Electrochimie Moléculaires, Chimie Analytique, Université de Bretagne Occidentale , BP 809, 29285 Brest Cedex, France.
Inorg Chem. 2014 Jan 6;53(1):97-104. doi: 10.1021/ic401721x. Epub 2013 Dec 23.
New Fe(II) coordination polymeric neutral chains of formula [Fe(aqin)2(μ2-M(CN)4)] (M = Ni(II) (1) and Pt(II) (2)) (aqin = Quinolin-8-amine) have been synthesized and characterized by infrared spectroscopy, X-ray diffraction, and magnetic measurements. The crystal structure determinations of 1-2 reveal in both cases a one-dimensional structure in which the planar M(CN)4 (M = Ni(II) (1) and Pt(II) (2)) anion acts as a μ2-bridging ligand, and the two aqin molecules as chelating coligands. Examination of the intermolecular contacts in the two compounds reveals that the main contacts are ascribed to hydrogen bonding interactions involving the amine groups of the aqin chelating ligands and the nitrogen atoms of the two non bridging CN groups of the M(CN)4 (M = Ni(II) (1) and Pt(II) (2)) anion. The average values of the six Fe-N distances observed respectively at room temperature (293 K) and low temperature (120 K), that is, 2.142(3) and 2.035(2) Å for 1, and 2.178(3) and 1.990(2) Å for 2, and the thermal variation of the cell parameters (performed on 2) are indicative of the presence of an abrupt HS-LS spin crossover (SCO) transition in both compounds. The thermal dependence of the product of the molar magnetic susceptibility times the temperature (χmT), in cooling and warming modes, confirms the SCO behavior at about 145 and 133 K in 1 and 2, respectively, and reveals the presence of a small thermal hysteresis of about 2 K for each compound.
已经合成并通过红外光谱、X 射线衍射和磁性测量对[Fe(aqin)2(μ2-M(CN)4)](M = Ni(II)(1)和 Pt(II)(2))(aqin = 喹啉-8-胺)的新型 Fe(II)配位聚合物中性链进行了表征。1-2 的晶体结构测定表明,在这两种情况下,都存在一维结构,其中平面M(CN)4(M = Ni(II)(1)和 Pt(II)(2))阴离子作为 μ2-桥联配体,两个 aqin 分子作为螯合共配体。检查两种化合物的分子间接触表明,主要接触归因于氢键相互作用,涉及螯合配体 aqin 的胺基和 M(CN)4(M = Ni(II)(1)和 Pt(II)(2))阴离子的两个非桥接 CN 基团的氮原子。在室温(293 K)和低温(120 K)下分别观察到的六个 Fe-N 距离的平均值,即 1 中为 2.142(3)和 2.035(2)Å,2 中为 2.178(3)和 1.990(2)Å,以及晶格参数的热变化(在 2 上进行)表明在两种化合物中存在突然的高自旋-低自旋自旋交叉(SCO)转变。在冷却和升温模式下,摩尔磁化率与温度之积(χmT)的热依赖性证实了 1 和 2 分别在约 145 和 133 K 处的 SCO 行为,并揭示了每种化合物约 2 K 的小热滞后。