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<p>Over the past few decades, various types of metal-sandwich structures have been synthesized and reported, which significantly advanced organometallic chemistry and contributed to numerous applications. However, charge-neutral rare-earth(III) sandwich structures based on compact aromatic ligands still remained unexplored due to the challenges in their synthesis. Nevertheless, the immense potential of this type of structure in building high-performance single-molecule magnets (SMMs) has compelled us to overcome these synthetic obstacles. Herein, we aimed to isolate such complexes in a general formula of [(Ring1)RE<sup>III</sup>(Ring2)]. [(C<sub>4</sub>B)<sup>Et4Me2N</sup>RE<sup>III</sup>(Cp<sup><i>i</i>Pr5</sup>)] (<b>3-RE</b>, RE = Y, Dy; (C<sub>4</sub>B)<sup>Et4Me2N</sup> = 1-(<i>N,N</i>-dimethylamino)-2,3,4,5-tetraethylborolyl; Cp<sup><i>i</i>Pr5</sup> = pentaisopropylcyclopentadienyl) were successfully obtained via the salt-metathesis reaction of the precursor [RE<sup>III</sup>(Cp<sup><i>i</i>Pr5</sup>)(BH<sub>4</sub>)<sub>2</sub>-(THF)] (<b>1-RE</b>, RE = Y, Dy; THF = tetrahydrofuran) and the new aminoborolide ligand [Na<sub>2</sub>(C<sub>4</sub>B)<sup>Et4Me2N</sup>(THF)<sub>2</sub>]<sub>2</sub> (<b>2</b>), which represent the first neutral rare-earth(III)-sandwich complexes ligated by compact aromatic ligands. Both complexes <b>3-RE</b> were characterized by single-crystal X-ray diffraction, elemental analysis, UV-Vis-NIR and FTIR. Diamagnetic <b>3-Y</b> was studied by NMR spectroscopy. Static and dynamic magnetic properties of <b>3-Dy</b> were investigated by SQUID magnetometry, showing a high anisotropy barrier of 785(12) cm<sup>−1</sup> and open hysteresis loops up to 12 K. The bonding of nitrogen to dysprosium(III) near the equatorial plane lowers the anisotropy, and a bulkier ligand in the future should be able to avoid this. This work not only demonstrates that such type of neutral rare-earth(III)-sandwich complexes is totally synthetically feasible, but also paves the way for the development of high-performance SMMs.</p>

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Isolation and single-molecule magnetism of neutral rare-earth(III) sandwich complexes supported by compact aromatic rings

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2025年1月7日

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  • Ming Liu,
  • Yan-Cong Chen,
  • Jieyu Zheng,
  • Xiao-Han Peng,
  • Ming-Liang Tong,
  • Akseli Mansikkamäki,
  • Fu-Sheng Guo

摘要

Over the past few decades, various types of metal-sandwich structures have been synthesized and reported, which significantly advanced organometallic chemistry and contributed to numerous applications. However, charge-neutral rare-earth(III) sandwich structures based on compact aromatic ligands still remained unexplored due to the challenges in their synthesis. Nevertheless, the immense potential of this type of structure in building high-performance single-molecule magnets (SMMs) has compelled us to overcome these synthetic obstacles. Herein, we aimed to isolate such complexes in a general formula of [(Ring1)REIII(Ring2)]. [(C4B)Et4Me2NREIII(CpiPr5)] (3-RE, RE = Y, Dy; (C4B)Et4Me2N = 1-(N,N-dimethylamino)-2,3,4,5-tetraethylborolyl; CpiPr5 = pentaisopropylcyclopentadienyl) were successfully obtained via the salt-metathesis reaction of the precursor [REIII(CpiPr5)(BH4)2-(THF)] (1-RE, RE = Y, Dy; THF = tetrahydrofuran) and the new aminoborolide ligand [Na2(C4B)Et4Me2N(THF)2]2 (2), which represent the first neutral rare-earth(III)-sandwich complexes ligated by compact aromatic ligands. Both complexes 3-RE were characterized by single-crystal X-ray diffraction, elemental analysis, UV-Vis-NIR and FTIR. Diamagnetic 3-Y was studied by NMR spectroscopy. Static and dynamic magnetic properties of 3-Dy were investigated by SQUID magnetometry, showing a high anisotropy barrier of 785(12) cm−1 and open hysteresis loops up to 12 K. The bonding of nitrogen to dysprosium(III) near the equatorial plane lowers the anisotropy, and a bulkier ligand in the future should be able to avoid this. This work not only demonstrates that such type of neutral rare-earth(III)-sandwich complexes is totally synthetically feasible, but also paves the way for the development of high-performance SMMs.