Influencing the properties of dysprosium single-molecule magnets with phosphorus donor ligands.
Influencing the properties of dysprosium single-molecule magnets with phosphorus donor ligands.
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DOI：
10.1038/ncomms8492
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发表时间：
2015-07-01
影响因子：
16.6
通讯作者：
Layfield RA
中科院分区：
文献类型：
--
作者：
Pugh T;Tuna F;Ungur L;Collison D;McInnes EJ;Chibotaru LF;Layfield RA
单分子磁体是一种可以在低温下保留磁信息的配位化合物。基于镧系元素的单分子磁体已经取得了许多重要的进展，包括具有非常大的磁化反转势垒的系统，以及表现出高达14 K的磁滞和很强的矫顽力的双稀土络合物。配基设计对于新的单分子磁体的发展至关重要：有机金属化学为使用非常规配基提供了可能性，特别是那些具有软给电子基团的配基。在这里，我们报道了带有中性和阴离子磷给体配体的镝单分子磁体，并表明当配体从磷化氢到磷化物再到亚磷烯时，它们的性质发生了显著的变化。一种磷化物连接的三金属镝单分子磁体通过二次激发的Kramers双重态驰豫，当在单离子水平上掺杂到抗磁基质中时，产生256Cm −1的大能垒和高达4.4kBt的磁滞回线。配体设计有助于决定La基单分子磁体的磁性。在这里，作者报道了一系列的磷连接的镝配合物，并表明了动态磁性随着配体的变化而变化，从膦到膦再到亚膦。
Single-molecule magnets are a type of coordination compound that can retain magnetic information at low temperatures. Single-molecule magnets based on lanthanides have accounted for many important advances, including systems with very large energy barriers to reversal of the magnetization, and a di-terbium complex that displays magnetic hysteresis up to 14 K and shows strong coercivity. Ligand design is crucial for the development of new single-molecule magnets: organometallic chemistry presents possibilities for using unconventional ligands, particularly those with soft donor groups. Here we report dysprosium single-molecule magnets with neutral and anionic phosphorus donor ligands, and show that their properties change dramatically when varying the ligand from phosphine to phosphide to phosphinidene. A phosphide-ligated, trimetallic dysprosium single-molecule magnet relaxes via the second-excited Kramers' doublet, and, when doped into a diamagnetic matrix at the single-ion level, produces a large energy barrier of 256 cm−1 and magnetic hysteresis up to 4.4 K. Ligand design contributes to dictating the magnetic properties of lanthanide-based single-molecule magnets. Here, the authors report a series of phosphorus-ligated dysprosium complexes, and show that the dynamic magnetic properties change as the ligand is varied from phosphine to phosphide to phosphinidene.