Isolation and single-molecule magnetism of neutral rare-earth(III) sandwich complexes supported by compact aromatic rings
Liu, Ming; Chen, Yan-Cong; Zheng, Jieyu; Peng, Xiao-Han; Tong, Ming-Liang; Mansikkamaeki, Akseli; Guo, Fu-Sheng (2025-01-07)
Springer
07.01.2025
Liu, M., Chen, YC., Zheng, J. et al. Isolation and single-molecule magnetism of neutral rare-earth(III) sandwich complexes supported by compact aromatic rings. Sci. China Chem. (2025). https://doi.org/10.1007/s11426-024-2413-6
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© The Author(s) 2025. This article is distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made.
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© The Author(s) 2025. This article is distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made.
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Julkaisun pysyvä osoite on
https://urn.fi/URN:NBN:fi:oulu-202504172754
https://urn.fi/URN:NBN:fi:oulu-202504172754
Tiivistelmä
Abstract
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.
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.
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