title: Can Non-Kramers Tm(III) Mononuclear Molecules be Single-Molecule Magnets (SMMs)?
abstract: In recent years, plentiful lanthanide-based (Tb(III) , Dy(III) , and Er(III) ) single-molecule magnets (SMMs) were studied, while examples of other lanthanides, for example, Tm(III) 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)Tm0.05 Y0.95 (COT)] and 2 a[(Tp*)Tm0.05 Y0.95 (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.
authors.affiliation: 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, 100871, P. R. China.
authors.forename: Yin-Shan
authors.initials: YS
authors.lastname: Meng
authors.affiliation: 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, 100871, P. R. China.
authors.forename: Yu-Sen
authors.initials: YS
authors.lastname: Qiao
authors.affiliation: Jiangsu Key Laboratory for NSLSCS, School of Physical Science and Technology, Nanjing Normal University, Nanjing, 210023, P. R. China.
authors.forename: Yi-Quan
authors.initials: YQ
authors.lastname: Zhang
authors.affiliation: 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, 100871, P. R. China.
authors.forename: Shang-Da
authors.initials: SD
authors.lastname: Jiang
authors.affiliation: 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, 100871, P. R. China.
authors.forename: Zhao-Sha
authors.initials: ZS
authors.lastname: Meng
authors.affiliation: 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, 100871, P. R. China. bwwang@pku.edu.cn.
authors.forename: Bing-Wu
authors.initials: BW
authors.lastname: Wang
authors.affiliation: 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, 100871, P. R. China.
authors.forename: Zhe-Ming
authors.initials: ZM
authors.lastname: Wang
authors.affiliation: 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, 100871, P. R. China. gaosong@pku.edu.cn.
authors.forename: Song
authors.initials: S
authors.lastname: Gao
keywords: magnetic anisotropy; organometallics; single-crystal angular resolved magnetometry; single-molecule magnets