Luminescent and Sublimable Binaphthyl-Based Field-Induced Lanthanide Single-Molecule Magnets

Fabrice Pointillart, Pierre‐Antoine Bouit, F. Riobé, Carlo Andrea Mattei, Thomas Delouche, B. Lefeuvre, Marie Dallon-Cordier, C. Lalli, O. Cador, Laura Abad Galán, O. Maury
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Abstract

The association of the [Ln(hfac)3(H2O)2] metallic building blocks with the new ligand [1,1’-binaphthalene]-8,8’-diylbis(diphenylphosphine oxide) (L) led to the formation of three mononuclear complexes of formula [Ln(hfac)3(L)] (LnIII = Eu (1), Dy (2) and Yb (3)). The mononuclear character of the compounds is due to the bidentate coordination mode adopted by L to link the metal. L allows the observation of the characteristic visible 5D0  7FJ (J = 0-4) EuIII- and near infrared 2F5/2  2F7/2 YbIII- emissions while 2 is only weakly emissive due to the mismatch between the energy positions of the triplet excited state of the ligand and DyIII emissive state. The magnetic data reveal a field-induced Single-Molecule Magnet (SMM) behavior for 2 and 3 with an efficient suppression of the Quantum Tunneling of the Magnetization (QTM). The slow magnetic relaxation occurs through a Raman process while the Orbach contribution is discarded as confirmed by the correlation with the MJ states energy splitting provided by the luminescence spectrum of 3.
发光和可升华的联苯基场致镧单分子磁体
[Ln(hfac)3(H2O)2]金属构建块与新配体[1,1'-联萘]-8,8'-二基双(二苯基氧化膦)(L)的结合导致形成三种单核配合物,其通式为[Ln(hfac)3(L)](LnII=Eu(1)、Dy(2)和Yb(3))。化合物的单核性质是由于L采用双齿配位模式连接金属。L允许观察可见的特性5D0 7FJ(J=0-4)EuIII-和近红外2F5/2 2F7/2 YbIII-发射,而2由于配体的三重态激发态和DyIII发射态的能量位置之间的失配而仅是弱发射。磁性数据揭示了2和3的场诱导单分子磁体(SMM)行为,有效抑制了磁化的量子隧道(QTM)。慢磁弛豫通过拉曼过程发生,而Orbach贡献被丢弃,这通过与由3的发光光谱提供的MJ态能量分裂的相关性来证实。
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