Opening Magnetic Hysteresis by Axial Ferromagnetic Coupling: From Mono‐Decker to Double‐Decker Metallacrown
Jin Wang, Quan‐Wen Li, Si‐Guo Wu, Yan‐Cong Chen, Rui‐Chen Wan, Guo‐Zhang Huang, Yang Liu, Jun‐Liang Liu, Daniel Reta, Marcus J. Giansiracusa, Zhenxing Wang, Nicholas F. Chilton, Ming‐Liang Tong
Abstract
Abstract Combining Ising‐type magnetic anisotropy with collinear magnetic interactions in single‐molecule magnets (SMMs) is a significant synthetic challenge. Herein we report a Dy[15‐MC Cu ‐5] ( 1‐Dy ) SMM, where a Dy III ion is held in a central pseudo‐ D 5 h pocket of a rigid and planar Cu 5 metallacrown (MC). Linking two Dy[15‐MC Cu ‐5] units with a single hydroxide bridge yields the double‐decker {Dy[15‐MC Cu ‐5]} 2 ( 2‐Dy ) SMM where the anisotropy axes of the two Dy III ions are nearly collinear, resulting in magnetic relaxation times for 2‐Dy that are approximately 200 000 times slower at 2 K than for 1‐Dy in zero external field. Whereas 1‐Dy and the Y III ‐diluted Dy@ 2‐Y analogue do not show remanence in magnetic hysteresis experiments, the hysteresis data for 2‐Dy remain open up to 6 K without a sudden drop at zero field. In conjunction with theoretical calculations, these results demonstrate that the axial ferromagnetic Dy–Dy coupling suppresses fast quantum tunneling of magnetization (QTM). The relaxation profiles of both complexes curiously exhibit three distinct exponential regimes, and hold the largest effective energy barriers for any reported d–f SMMs up to 625 cm −1 .