在一系列双核 Fe(ii)三螺旋配合物中表现出多样的自旋交叉行为。
Varied spin crossover behaviour in a family of dinuclear Fe(ii) triple helicate complexes.
机构信息
School of Physical and Chemical Sciences, University of Canterbury, Private Bag 4800, Christchurch, 8140, New Zealand.
出版信息
Dalton Trans. 2018 Jun 19;47(24):7965-7974. doi: 10.1039/c8dt01567h.
Dinuclear triple-helicate complexes of the formula Fe2L34·solv (solv = CH3CN, CHCl3, H2O) have been synthesised and structurally characterised. The bis-bidentate ligands, L, present either strong-field 2-pyridylimine (1) or weaker-field 2-imidazolylimine (2) and 4-imidazolylimine (3) coordination spheres about Fe(ii) centres in an octahedral geometry. Whereas 1 is pervasively diamagnetic, spin crossover (SCO) behaviour is observed in 2 and 3 and has been studied using variable-temperature structural, UV-visible spectroscopic, magnetic and photo-magnetic techniques. Variable-temperature (1.8-400 K) magnetic-susceptibility measurements reveal the T1/2 values of 2 and 3 to be strongly dependent upon the solvent and degree of solvation. Photomagnetic studies at 10 K under white-light irradiation revealed an inefficient photo-induced SCO in 2, but full switching in 3.
已经合成并结构表征了Fe2L34·溶剂（溶剂=CH3CN、CHCl3、H2O）的双核三联螺旋配合物。双齿配体 L 呈现出强场 2-吡啶亚胺（1）或较弱场 2-咪唑基亚胺（2）和 4-咪唑基亚胺（3）配位球体，以八面体几何形状围绕 Fe(ii)中心。尽管 1 是普遍抗磁性的，但在 2 和 3 中观察到自旋交叉（SCO）行为，并使用变温结构、紫外可见光谱、磁性和光磁技术进行了研究。变温（1.8-400 K）磁化率测量表明 2 和 3 的 T1/2 值强烈依赖于溶剂和溶剂化程度。在 10 K 下进行的白光照射光磁研究表明，2 中存在低效的光诱导 SCO，但 3 中完全切换。
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