Search

Here we reported the deuteration of the metal‐binding equatorial water molecules in a reported HoIII single‐molecule magnet (SMM) with pentagonal‐bipyramidal geometry, from [Ho(CyPh2PO)2(H2O)5]3+ to [Ho(CyPh2PO)2(D2O)5]3+. The hyperfine structures originating from the nuclear spin of 165HoIII can be clearly observed. Moreover, the resulting magnetization dynamics revealed the switch of the relative relaxation rates for the two isotope‐isomorphic complexes—respectively faster/slower at low/high temperature. The noticeable isotope effect arises from not only the paramagnetic metal center but also the diamagnetic ligands, which can be explained by the ab initio calculated tunnel splitting and the involvement of the super‐hyperfine interaction related to the difference in the nuclear spin number of protium (1H, I=1/2) and deuterium (2H, I=1). [ABSTRACT FROM AUTHOR]

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‐MCCu‐5] (1‐Dy) SMM, where a DyIII ion is held in a central pseudo‐D5h pocket of a rigid and planar Cu5 metallacrown (MC). Linking two Dy[15‐MCCu‐5] units with a single hydroxide bridge yields the double‐decker {Dy[15‐MCCu‐5]}2 (2‐Dy) SMM where the anisotropy axes of the two DyIII 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 YIII‐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. [ABSTRACT FROM AUTHOR]

An extremely rare non-Kramers holmium(III) single-ion magnet (SIM) is reported to be stabilized in the pentagonal-bipyramidal geometry by a phosphine oxide with a high energy barrier of 237(4) cm−1. The suppression of the quantum tunneling of magnetization (QTM) at zero field and the hyperfine structures originating from field-induced QTMs can be observed even from the field-dependent alternating-current magnetic susceptibility in addition to single-crystal hysteresis loops. These dramatic dynamics were attributed to the combination of the favorable crystal-field environment and the hyperfine interactions arising from 165Ho ( I=7/2) with a natural abundance of 100 %. [ABSTRACT FROM AUTHOR]

Hyperfine interaction, isotope effect, magnetization dynamics, single-molecule magnets, super-hyperfine interaction Inside Cover: Magnetization Dynamics on Isotope-Isomorphic Holmium Single-Molecule Magnets (Angew. Keywords: hyperfine interaction; isotope effect; magnetization dynamics; single-molecule magnets; super-hyperfine interaction EN hyperfine interaction isotope effect magnetization dynamics single-molecule magnets super-hyperfine interaction 26870 26870 1 12/15/21 20211220 NES 211220 B Nuclear-spin driven relaxation b collaborating with the ligands in lanthanide single molecule magnets (SMMs) remains ambiguous. [Extracted from the article]