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基于理查森旋光理论的手性镧系配合物的磁致手性二向色性

Magneto-Chiral Dichroism of Chiral Lanthanide Complexes in the Context of Richardson's Theory of Optical Activity.

作者信息

Cahya Adi Langit, Willis Oliver G, Gabbani Alessio, Rikken Geert L J A, Di Bari Lorenzo, Train Cyrille, Pineider Francesco, Zinna Francesco, Atzori Matteo

机构信息

Laboratoire National des Champs Magnétiques Intenses, CNRS, Univ. Grenoble Alpes, INSA Toulouse, Univ. Toulouse Paul Sabatier, EMFL, F-38042, Grenoble, France.

Dipartimento di Chimica e Chimica Industriale, Università di Pisa, I-56124, Pisa, Italy.

出版信息

Angew Chem Int Ed Engl. 2024 Dec 20;63(52):e202412521. doi: 10.1002/anie.202412521. Epub 2024 Nov 7.

Abstract

Here we report on the Magneto-Chiral Dichroism (MChD) detected through visible and near-infrared light absorption of two enantiomeric pairs of Er and Tm chiral complexes featuring a propeller-like molecular structure. The magnetic properties show typical features of isolated paramagnetic ions associated with I and H ground state terms. MChD spectroscopy shows high g dissymmetry factors of ca. 0.12 T and 0.05 T (T=4.0 K and B=1.0 T) for Er and Tm, respectively, associated with the magnetic-dipole allowed I ← I and H ← H transitions. MChD signals of the two complexes were detected up to room temperature and under magnetic fields up to 5.0 T. For the first time, the MChD results are discussed in the context of the Richardson theory of lanthanide optical activity and provide clear indications on the strongest MChD-active electronic transitions of lanthanide complexes.

摘要

在此,我们报告了通过对两对具有螺旋桨状分子结构的铒(Er)和铥(Tm)手性配合物的可见光和近红外光吸收检测到的磁手性二色性(MChD)。磁性表现出与I和H基态项相关的孤立顺磁性离子的典型特征。MChD光谱显示,对于Er和Tm,g不对称因子分别约为0.12 T和0.05 T(T = 4.0 K,B = 1.0 T),这与磁偶极允许的I ← I和H ← H跃迁相关。在高达室温以及高达5.0 T的磁场下都检测到了这两种配合物的MChD信号。首次在镧系元素光学活性的理查森理论背景下讨论了MChD结果,并为镧系配合物最强的MChD活性电子跃迁提供了明确指示。

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