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, Bing‐Wu Wang, Xing Lü, Song Gao
Abstract
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 (Dy 2 VN) inside a C 80 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 Dy 2 VN@ I h (7)-C 80 . 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.