Department of Chemistry, IISER Bhopal, Bhauri, Bhopal bypass road, Bhopal, MP, 462066, India.
Chemistry. 2023 May 22;29(29):e202203664. doi: 10.1002/chem.202203664. Epub 2023 Apr 5.
Tuning the bridging fashion of anilato ligand in dinuclear Dy complexes, reveals a sizable effect on the slow relaxation of magnetization. Combined experimental and theoretical studies divulge that the geometry with high order axial symmetry (pseudo square antiprism) reduces the transverse crystal fields corresponding to QTM (quantum tunneling of magnetization) resulting in a significant increase in energy barrier (U =518 cm ) through the Orbach relaxation process whereas the geometry with lower symmetry (triangular dodecahedron, pseudo D ) enhances the transverse crystal fields that accelerate the ground state QTM process. Notably, the value 518 cm represents the highest energy barrier among anilato ligand based SMMs.
调节双核 Dy 配合物中桥联 fashion 的方式,对磁化弛豫的缓慢过程有显著影响。结合实验和理论研究表明,具有高阶轴向对称(拟平面四方反棱柱)的几何形状会降低对应于量子隧穿的横向晶场(量子隧穿的磁化),从而通过奥巴赫弛豫过程显著增加能垒(U=518cm),而具有较低对称的几何形状(三角十二面体,拟 D)则会增强横向晶场,从而加速基态 QTM 过程。值得注意的是,518cm 是基于 anilato 配体的 SMMs 中最高的能垒值。