Mixed metal CoII1−xZnIIx–organic frameworks based on chains with mixed carboxylate and azide bridges: magnetic coupling and slow relaxation

Abstract

A series of isomorphous three-dimensional metal–organic frameworks [Co^II_1−xZn^II_x(L)(N₃)]·H₂O (x = 0.26, 0.56 and 0.85) based on bimetallic Co^II_1−xZn^II_x (x = 0.26, 0.56 and 0.85) chains with random metal sites have been synthesized and magnetically characterized. The Co^II_1−xZn^II_x series, which intrinsically feature random anisotropic/diamagnetic sites, shows complex magnetic interactions. By gradually introducing the diamagnetic Zn^II ions into the pure anisotropic Co^II single-chain magnets system, the ferromagnetic interactions between Co^II ions are gradually diluted. Moreover, the slow magnetic relaxation behaviour of the mixed metal Co^II_1−xZn^II_x systems also changes. In this bimetallic series Co^II_1−xZn^II_x, the Co-rich materials exhibit slow relaxation processes that may arise from SCM mechanism, while the Zn^II-rich materials show significantly low slow magnetic relaxation. A general trend is that the activation energy and the blocking temperature decrease with the increase in diamagnetic Zn^II content, emphasizing the importance of anisotropy for slow relaxation of magnetization.