School of Chemistry, University College Dublin, Belfield, Dublin 4, Ireland.
Centre for Quantum Materials and Technologies, School of Mathematics and Physics, Queen's University Belfast, Belfast, BT7 1NN, UK.
Chemistry. 2023 Jul 3;29(37):e202300275. doi: 10.1002/chem.202300275. Epub 2023 May 9.
Non-centrosymmetric spin-switchable systems are of interest for their prospective applications as magnetically active non-linear optical materials and in multiferroic devices. Chiral resolution of simple spin-crossover chelate complexes into the Δ and Λ forms offers a facile route to homochiral magnetic switches, which could be easily enantiomerically enriched. Here, we report the spontaneous resolution of a new hysteretic spin-crossover complex, [Mn (sal 323)]SCN ⋅ EtOH (1), into Δ and Λ forms, without the use of chiral reagents, where sal 323 is a Schiff base resulting from condensation of 1,2-bis(3-aminopropylamino)ethane with 2-hydroxybenzaldehyde. The enantiopurity of the Δ and Λ isomers was confirmed by single crystal X-ray diffraction and circular dichroism. Quantum chemistry calculations were used to investigate the electronic structure. The opening of a wide 80 K thermal hysteresis window at high temperature highlights the potential for good magneto-optical function at ambient temperature for materials of this type.
非中心对称自旋开关系统因其有望作为具有磁活性的非线性光学材料和在多铁性器件中的应用而受到关注。简单的自旋交叉螯合物复合物拆分成 Δ 和 Λ 形式的手性拆分提供了一种简便的方法来获得手性磁开关,这可以很容易地对映体富集。在这里,我们报告了一种新的迟滞自旋交叉配合物 [Mn(sal323)]SCN·EtOH(1)在没有使用手性试剂的情况下自发拆分成 Δ 和 Λ 形式,其中 sal323 是由 1,2-双(3-氨丙基氨基)乙烷与 2-羟基苯甲醛缩合得到的席夫碱。通过单晶 X 射线衍射和圆二色性确认了 Δ 和 Λ 异构体的对映纯度。量子化学计算用于研究电子结构。在高温下打开一个宽 80 K 的热滞后窗口突出了此类材料在环境温度下具有良好磁光功能的潜力。