Modulating the relaxation dynamics via structural transition from a dinuclear dysprosium cluster to a nonanuclear cluster

Abstract

A dinuclear dysprosium cluster [Dy₂(NO₃)₄(H₂O)₂(L)₂]·2CH₃CN was successfully prepared by employing HL (HL = 2,6-dimethoxyphenol) and Dy(NO₃)₃·6H₂O in a mixture of CH₃OH and CH₃CN. The conversion of this Dy₂ compound by reaction with additional deprotonated ligand generated a Dy₉ cluster [Dy₉(μ₄-OH)₂(μ₃-OH)₈(μ₂-OCH₃)₄(NO₃)₈(H₂O)₈(L)₄](OH)·2H₂O with the well-known “diabolo” topology. Magnetic investigation revealed that both of the clusters exhibit typical SMM characteristics, and variable magnetic relaxation with the energy barrier changing from 217.87 K to 9.24 K along with the transition from a dinuclear dysprosium cluster to a nonanuclear one. Ab initio calculations further confirm the corresponding structure–activity relationships that originate the different magnetic behaviours. This design may afford a feasible strategy for modulating the magnetic relaxation dynamics of polynuclear systems.