Laboratoire de Chimie Supramoléculaire, ISIS , Université de Strasbourg , 8 Allée Gaspard Monge , 67000 Strasbourg , France.
CNRS, CRPP, UMR 5031 , F-33600 Pessac , France.
J Am Chem Soc. 2018 Jul 5;140(26):8218-8227. doi: 10.1021/jacs.8b03735. Epub 2018 Jun 21.
The iron(II) [2×2] grid complex Fe-8H has been synthesized and characterized. It undergoes spin-crossover (SCO) upon deprotonation of the hydrazine-based terpyridine-like ligand. The deprotonation patterns have been determined by X-ray crystallography and H NMR spectroscopy and discussed in relation to the spin state of the iron(II) centers, which influences greatly the p K of the ligand. The synthesis of the magnetically silent zinc(II) analogue is also reported, and its (de)protonation behavior has been characterized to serve as a reference for the study of the Fe grid complexes. DFT computations have also been performed in order to investigate how the successive deprotonation of the bridging ligands affects the SCO behavior within the grid.
铁(II) [2×2] 网格配合物 Fe-8H 已被合成并进行了表征。它在基于肼的三联吡啶样配体去质子化时经历自旋交叉 (SCO)。通过 X 射线晶体学和 H NMR 光谱确定了去质子化模式，并与铁(II)中心的自旋态相关联进行了讨论，这对配体的 p K 影响很大。还报道了磁性锌(II)类似物的合成，并对其 (去)质子化行为进行了表征，以作为研究 Fe 网格配合物的参考。还进行了 DFT 计算，以研究桥联配体的连续去质子化如何影响网格内的 SCO 行为。
