Raju Maria Sara, Dhbaibi Kais, Grasser Maxime, Dorcet Vincent, Breslavetz Ivan, Paillot Kévin, Vanthuyne Nicolas, Cador Olivier, Rikken Geert L J A, Le Guennic Boris, Crassous Jeanne, Pointillart Fabrice, Train Cyrille, Atzori Matteo
Laboratoire National des Champs Magnétiques Intenses, Université Grenoble Alpes, INSA Toulouse, Université Toulouse Paul Sabatier, EMFL, CNRS, F-38042 Grenoble, France.
Univ Rennes, CNRS, ISCR (Institut des Sciences Chimiques de Rennes), UMR 6226, F-35000 Rennes, France.
Inorg Chem. 2023 Oct 30;62(43):17583-17587. doi: 10.1021/acs.inorgchem.3c03204. Epub 2023 Oct 19.
Here we report magneto-chiral dichroism (MChD) detected through visible and near-infrared light absorption of a chiral dysprosium(III) coordination polymer. The two enantiomers of [Dy(H6(py))(hfac)] [H6(py) = 2,15-bis(4-pyridyl)ethynylcarbo[6]helicene; hfac = 1,1,1,5,5,5-hexafluoroacetylacetonate], where the chirality is provided by a functionalized helicene ligand, were structurally, spectroscopically, and magnetically investigated. Magnetic measurements reveal a slow relaxation of the magnetization, with differences between enantiopure and racemic systems rationalized on the basis of theoretical calculations. When the enantiopure complexes are irradiated with unpolarized light in a magnetic field, they exhibit multiple MChD signals associated with the f-f electronic transitions of Dy, thus providing the coexistence of MChD-active absorptions and single-molecule-magnet (SMM) behavior. These findings clearly show the potential that rationally designed chiral SMMs have in enabling the optical readout of magnetic memory through MChD.
在此,我们报道了通过手性镝(III)配位聚合物的可见和近红外光吸收检测到的磁手性二向色性(MChD)。对[Dy(H6(py))(hfac)]的两种对映体进行了结构、光谱和磁性研究,其中[H6(py) = 2,15-双(4-吡啶基)乙炔基碳[6]螺旋烯;hfac = 1,1,1,5,5,5-六氟乙酰丙酮],其手性由功能化的螺旋烯配体提供。磁性测量揭示了磁化强度的缓慢弛豫,基于理论计算解释了对映纯体系和外消旋体系之间的差异。当在磁场中用非偏振光照射对映纯配合物时,它们会表现出与Dy的f-f电子跃迁相关的多个MChD信号,从而实现了MChD活性吸收和单分子磁体(SMM)行为的共存。这些发现清楚地表明,合理设计的手性单分子磁体具有通过MChD实现磁记忆光学读出的潜力。