Cirulli Martina, Salvadori Enrico, Zhang Zhi-Hui, Dommett Michael, Tuna Floriana, Bamberger Heiko, Lewis James E M, Kaur Amanpreet, Tizzard Graham J, van Slageren Joris, Crespo-Otero Rachel, Goldup Stephen M, Roessler Maxie M
School of Biological and Chemical Sciences, Queen Mary University of London, Mile End Road, London, E1 4NS, UK.
Department of Chemistry, University of Torino, Via Giuria 7, 10125, Torino, Italy.
Angew Chem Int Ed Engl. 2021 Jul 12;60(29):16051-16058. doi: 10.1002/anie.202103596. Epub 2021 Jun 14.
Mechanically chelating ligands have untapped potential for the engineering of metal ion properties. Here we demonstrate this principle in the context of Co -based single-ion magnets. Using multi-frequency EPR, susceptibility and magnetization measurements we found that these complexes show some of the highest zero field splittings reported for five-coordinate Co complexes to date. The predictable coordination behaviour of the interlocked ligands allowed the magnetic properties of their Co complexes to be evaluated computationally a priori and our combined experimental and theoretical approach enabled us to rationalize the observed trends. The predictable magnetic behaviour of the rotaxane Co complexes demonstrates that interlocked ligands offer a new strategy to design metal complexes with interesting functionality.
机械螯合配体在金属离子性质工程方面具有尚未开发的潜力。在此，我们在钴基单离子磁体的背景下证明了这一原理。通过多频电子顺磁共振、磁化率和磁化测量，我们发现这些配合物表现出了迄今为止报道的五配位钴配合物中一些最高的零场分裂。互锁配体可预测的配位行为使得其钴配合物的磁性能够通过先验计算进行评估，并且我们结合实验和理论的方法使我们能够合理解释观察到的趋势。轮烷钴配合物可预测的磁性行为表明，互锁配体为设计具有有趣功能的金属配合物提供了一种新策略。
