南开大学师唯团队近日实现了具有磁各向异性的空气稳定手性Dy^III配合物的强可切换磁光效应。相关论文于2025年6月3日发表在《美国化学会杂志》上。

在分子水平上组装手性和磁性单元是实现强磁光（MO）效应的关键，特别是对于具有特定4f电子构型的镧系配合物。然而，f-f转换通常受到选择规则的限制，这使得观察MO反应极具挑战性。

研究组报道了两种高度空气稳定的手性Dy^III配合物1-R和1-S的合成，以及一对定制的螯合手性配体。除了在宽温度范围内的磁化动力学外，1-R和1-S的磁圆二色性（MCD）在可见-近红外区域显示了Dy^III中心f-f跃迁的显著MO响应，1-R与1-S的CD光谱首次实验观察到了与Dy^III在450nm处的f-f跃迁相对应的室温CD峰。 

重要的是，从700到1100nm的CD信号的方向可以通过外部磁场可逆地切换。机理研究表明，Dy^III中心的强磁各向异性是诱导显著室温MO效应的关键。这项工作不仅为构建空气稳定的磁性和手性配合物提供了一种简便的方法，而且还深入了解了磁各向异性对室温下宽光谱范围内强MO效应的影响。

附：英文原文

Title: Strong and Switchable Magneto-Optical Effect in Air-Stable Chiral DyIII Complexes with Magnetic Anisotropy

Author: Yuewei Wu, Ze-Yu Ruan, Chengcheng Zhang, Jia-Nan Chen, Xin-Yi Wang, Zhonghang Chen, Xiaoshuang Gou, Wenlong Lan, Xiang-Jian Kong, Jun-Liang Liu, Peng Cheng, Wei Shi

Issue&Volume: June 3, 2025

Abstract: Assembling chiral and magnetic units at a molecular level is a key to achieving a strong magneto-optical (MO) effect, especially for lanthanide complexes with a specific 4f electronic configuration. However, the f–f transitions are generally restricted by selection rules, making the observation of the MO response extremely challenging. Herein, we reported the synthesis of two highly air-stable chiral DyIII complexes 1-R and 1-S, with a pair of tailored chelating chiral ligands. Besides magnetization dynamics in a wide temperature range, the magnetic circular dichroism (MCD) of 1-R and 1-S shows remarkable MO responses of f–f transitions of DyIII centers in the vis–NIR region, and CD spectra of 1-R and 1-S provide the first experimental observation of room-temperature CD peaks corresponding to the f–f transition of DyIII at 450 nm. Importantly, the direction of CD signals from 700 to 1100 nm can be reversibly switched by external magnetic fields. Mechanism study reveals that the strong magnetic anisotropy of the DyIII center is a key to inducing the remarkable room-temperature MO effect. This work not only provides a facile way to construct air-stable magnetic and chiral complexes but also gains insights into the influence of magnetic anisotropy on the strong MO effect in a wide spectrum range at room temperature.

DOI: 10.1021/jacs.5c04297

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.5c04297