Can Non‐Kramers TmIII Mononuclear Molecules be Single‐Molecule Magnets (SMMs)? |
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| Authors: | Yin‐Shan Meng Yu‐Sen Qiao Prof?Dr Yi‐Quan Zhang Dr Shang‐Da Jiang Zhao‐Sha Meng Prof?Dr Bing‐Wu Wang Prof?Dr Zhe‐Ming Wang Prof?Dr Song Gao |
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| Institution: | 1. Beijing National Laboratory of Molecular Science, State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing, P. R. China;2. Jiangsu Key Laboratory for NSLSCS, School of Physical Science and Technology, Nanjing Normal University, Nanjing, P. R. China |
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| Abstract: | In recent years, plentiful lanthanide‐based (TbIII, DyIII, and ErIII) single‐molecule magnets (SMMs) were studied, while examples of other lanthanides, for example, TmIII are still unknown. Herein, for the first time, we show that by rationally manipulating the coordination sphere, two thulium compounds, 1 (Tp)Tm(COT)] and 2 (Tp*)Tm(COT)] (Tp=hydrotris(1‐pyrazolyl)borate; COT=cyclooctatetraenide; Tp*=hydrotris(3,5‐dimethyl‐1‐pyrazolyl)borate), can adopt the structure of non‐Kramers SMMs and exhibit their behaviors. Dynamic magnetic studies indicated that both compounds showed slow magnetic relaxation under dc field and a relatively high effective energy barrier (111 K for 1 , 46 K for 2 ). Magnetic diluted 1 a (Tp)Tm0.05Y0.95(COT)] and 2 a (Tp*)Tm0.05Y0.95(COT)] even exhibited magnetic relaxation under zero dc field. Relativistic ab initio calculations combined with single‐crystal angular‐resolved magnetometry measurements revealed the strong easy axis anisotropy and nearly degenerated ground doublet states. The comparison of 1 and 2 highlights the importance of local symmetry for obtaining Tm SMMs. |
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| Keywords: | magnetic anisotropy single-molecule magnets organometallics single-crystal angular resolved magnetometry |
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