Manipulation of the Coordination Geometry along the C4 Rotation Axis in a Dinuclear Tb3+ Triple-Decker Complex via a Supramolecular Approach.,Chemistry - A European Journal

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Manipulation of the Coordination Geometry along the C4 Rotation Axis in a Dinuclear Tb3+ Triple-Decker Complex via a Supramolecular Approach.
Chemistry - A European Journal ( IF 3.9 ) Pub Date : 2020-03-25 , DOI: 10.1002/chem.201905400
Keiichi Katoh ₁ , Nobuhiro Yasuda ₂ , Marko Damjanović ₃ , Wolfgang Wernsdorfer _{3,

4,

5} , Brian K Breedlove ₁ , Masahiro Yamashita _{1,

6,

7}

Affiliation

A supramolecular complex (1×C60) was prepared by assembling (C60-Ih)[5,6]fullerene (C60) with the dinuclear Tb3+ triple-decker complex [(TPP)Tb(Pc)Tb(TPP)] (1: Tb3+ = trivalent terbium ion, Pc2- = phthalocyaninato, TPP2- = tetraphenylporphyrinato) with quasi-D4h symmetry to investigate the relationship between the coordination symmetry and single-molecule magnet (SMM) properties. Tb3+-Pc triple-decker complexes (Tb2Pc3) have an important advantage over Tb3+-Pc double-decker complexes (TbPc2) since the magnetic relaxation processes correspond to the Zeeman splitting when there are two 4f spin systems. At 1.8 K, 1 and 1·C60 undergo different magnetic relaxations, and the changes in the ground state affect the spin dynamics. Although 1 and 1·C60 relax via QTM in a zero applied magnetic field (H), H dependencies of the magnetic relaxation times (τ) for H > 1500 Oe are similar. On the other hand, for H < 1500 Oe, the τ values have different behaviors since the off-diagonal terms affect the magnetic relaxation mechanism. From temperature and H dependences of τ, spin-phonon interactions along with direct and Raman mechanisms explain the spin dynamics. We believe that a supramolecular method can be used to control the magnetic anisotropy along the C4 rotation axis and the spin dynamic properties in dinuclear Ln3+-Pc multiple-decker complexes.

中文翻译：

通过超分子方法在双核Tb3 +三层双层复合物中沿C4旋转轴操纵配位几何。

通过将（C60-Ih）[5,6]富勒烯（C60）与双核Tb3 +三层复合物[（TPP）Tb（Pc）Tb（TPP）]组装来制备超分子复合物（1×C60）（1： Tb3 + =三价ter离子，Pc2- =酞菁基，TPP2- =四苯基卟啉（对称），以研究配位对称性与单分子磁体（SMM）性质之间的关系。Tb3 + -Pc双层复合物（Tb2Pc3）比Tb3 + -Pc双层复合物（TbPc2）具有重要优势，因为当存在两个4f自旋系统时，磁弛豫过程对应于塞曼分裂。在1.8 K时，1和1·C60经历不同的磁弛豫，并且基态的变化会影响自旋动力学。尽管1和1·C60在零磁场（H）下通过QTM弛豫，对于H> 1500 Oe，磁弛豫时间（τ）的H依赖性相似。另一方面，对于H <1500 Oe，τ值具有不同的行为，因为非对角项会影响磁弛豫机制。从τ的温度和H依赖关系来看，自旋声子相互作用以及直接和拉曼机理解释了自旋动力学。我们相信，可以使用超分子方法来控制沿C4旋转轴的磁各向异性和双核Ln3 + -Pc多层复合体的自旋动力学性质。自旋声子相互作用以及直接和拉曼机理解释了自旋动力学。我们相信，可以使用超分子方法来控制沿C4旋转轴的磁各向异性和双核Ln3 + -Pc多层复合体的自旋动力学性质。自旋声子相互作用以及直接和拉曼机理解释了自旋动力学。我们相信，可以使用超分子方法来控制沿C4旋转轴的磁各向异性和双核Ln3 + -Pc多层复合体的自旋动力学性质。

更新日期：2020-03-27

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