A hard molecular nanomagnet from confined paramagnetic 3d-4f spins inside a fullerene cage

Chenli Huang; Rong Sun; Lipiao Bao; Xinyue Tian; Changwang Pan; Mengyang Li; Wangqiang Shen; Kun Guo; Bingwu Wang; Xing Lu; Song Gao

doi:10.1038/s41467-023-44194-y

A hard molecular nanomagnet from confined paramagnetic 3d-4f spins inside a fullerene cage

Nat Commun. 2023 Dec 19;14(1):8443. doi: 10.1038/s41467-023-44194-y.

Authors

Chenli Huang^#¹, Rong Sun^#², Lipiao Bao³, Xinyue Tian¹, Changwang Pan¹, Mengyang Li⁴, Wangqiang Shen¹, Kun Guo¹, Bingwu Wang⁵, Xing Lu^{6

7}, Song Gao^{2

8}

Affiliations

¹ State Key Laboratory of Materials Processing and Die & Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, 1037, Luoyu Road, Wuhan, 430074, P. R. China.
² 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.
³ State Key Laboratory of Materials Processing and Die & Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, 1037, Luoyu Road, Wuhan, 430074, P. R. China. baol@hust.edu.cn.
⁴ School of Physics, Xidian University, Xi'an, 710071, China.
⁵ 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. wangbw@pku.edu.cn.
⁶ State Key Laboratory of Materials Processing and Die & Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, 1037, Luoyu Road, Wuhan, 430074, P. R. China. lux@hust.edu.cn.
⁷ College of Chemistry and Chemical Engineering, Hainan University, No. 58, Renmin Avenue, Haikou, 570228, P. R. China. lux@hust.edu.cn.
⁸ Spin-X Institute, School of Chemistry and Chemical Engineering, State Key Laboratory of Luminescent Materials and Devices, Guangdong-Hong Kong-Macao Joint Laboratory of Optoelectronic and Magnetic Functional Materials, South China University of Technology, Guangzhou, 510641, P. R. China.

^# Contributed equally.

Abstract

Reducing inter-spin distance can enhance magnetic interactions and allow for the realization of outstanding magnetic properties. However, achieving reduced distances is technically challenging. Here, we construct a 3d-4f metal cluster (Dy₂VN) inside a C₈₀ cage, affording a heretofore unseen metallofullerene containing both paramagnetic 3d and 4f metal ions. The significantly suppressed 3d-4f (Dy-V) distances, due to the unique cage confinement effect, were observed by crystallographic and theoretical analysis of Dy₂VN@I_h(7)-C₈₀. These reduced distances result in an enhanced magnetic coupling (J_{total, Dy-V} = 53.30 cm^-1; J_{total, Dy-Dy} = -6.25 cm^-1), leading to a high magnetic blocking temperature compared to reported 3d-4f single-molecule magnets and strong coercive field of 2.73 Tesla. Our work presents a new class of single-molecule magnets with both paramagnetic 3d and 4f metals confined in a fullerene cage, offering superior and tunable magnetic properties due to the unique cage confinement effect and the diverse composition of the entrapped magnetic core.

Abstract

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