Lefeuvre Bertrand, Galangau Olivier, Gonzalez Jessica Flores, Montigaud Vincent, Dorcet Vincent, Ouahab Lahcène, Le Guennic Boris, Cador Olivier, Pointillart Fabrice
Univ Rennes, CNRS, ISCR (Institut des Sciences Chimiques de Rennes)-UMR 6226, Rennes, France.
Front Chem. 2018 Nov 13;6:552. doi: 10.3389/fchem.2018.00552. eCollection 2018.
Tetrathiafulvalene and 1,10-phenanthroline moieties present, respectively remarkable redox-active and complexation activities. In this work, we investigated the coordination reaction between the bis(1,10-phenanthro[5,6-b])tetrathiafulvalene triad () and the Dy(hfac)·2HO metallo precursor. The resulting {[Dy(hfac)()]·CHCl·CH} () dinuclear complex showed a crystal structure in which the triad bridged two terminal Dy(hfac) units and the supramolecular co-planar arrangement of the triads is driven by donor-acceptor interactions. The frequency dependence of the out-of-phase component of the magnetic susceptibility highlights three distinct maxima under a 2000 Oe static applied magnetic field, a sign that displays a Single-Molecule Magnet (SMM) behavior with multiple magnetic relaxations. calculations rationalized the Ising character of the magnetic anisotropy of the Dy ions and showed that the main anisotropy axes are perpendicular to the co-planar arrangement of the triads. Single-crystal rotating magnetometry confirms the orientation of the main magnetic axis. Finally combining structural analysis and probability of magnetic relaxation pathways through Quantum Tunneling of the Magnetization (QTM) vs. excited states (Orbach), each Dy center has been attributed to one of the three observed magnetic relaxation times. Such coordination compound can be considered as an ideal candidate to perform redox-magnetic switching.
四硫富瓦烯和1,10-菲咯啉部分分别具有显著的氧化还原活性和络合活性。在本工作中,我们研究了双(1,10-菲咯[5,6-b])四硫富瓦烯三联体()与Dy(hfac)·2HO金属前体之间的配位反应。所得的{[Dy(hfac)()·CHCl·CH}()双核配合物显示出一种晶体结构,其中三联体桥连两个末端Dy(hfac)单元,并且三联体的超分子共面排列是由供体-受体相互作用驱动的。磁化率异相分量的频率依赖性在2000 Oe的静态外加磁场下突出显示了三个不同的最大值,这表明表现出具有多种磁弛豫的单分子磁体(SMM)行为。计算使Dy离子磁各向异性的伊辛特征合理化,并表明主要各向异性轴垂直于三联体的共面排列。单晶旋转磁力测量证实了主磁轴的取向。最后,通过结合结构分析以及通过磁化量子隧穿(QTM)与激发态(奥尔巴赫)的磁弛豫途径的概率,每个Dy中心都被归因于观察到的三个磁弛豫时间之一。这种配位化合物可被视为进行氧化还原-磁开关的理想候选物。