Remarkable Energy Barrier for Magnetization Reversal in 3D and 2D Dysprosium‐Chloranilate‐Based Coordination Polymers.

Herein, two coordination polymers (CPs) [{Dy(Cl2An)1.5(CH3OH)}⋅4.5 H2O]n (1) and [Dy(Cl2An)1.5(DMF)2]n (2), in which Cl2An is chloranilate (2,5‐dihydroxy‐1,4‐benzoquinone dianion), exhibiting field‐induced single‐molecule magnet behavior with moderate barrier of magnetization reversal are reported. Detailed structural and topological analysis disclosed that 1 has a 3D network, whereas 2 has a 2D layered‐type structure. In both CPs, magnetic measurements showed weak antiferromagnetic exchange interaction between the dysprosium centers and field‐induced slow magnetic relaxation with barriers of 175(9)K and 145(7)K for 1 and 2, respectively. Notably, the energy barriers of magnetization reversal of 1 and 2 are remarkable for metal–chloranilate‐based 3D (1) and 2D (2) CPs. The temperature and field dependence of relaxation time indicate the presence of multiple relaxation pathways, such as direct, quantum tunneling of magnetization, Raman, and Orbach processes, in both CPs. Ab initio theoretical calculations reinforced the experimentally observed higher energy barrier in 1 as compared with 2 due to the presence of large transverse anisotropy in the ground state in the latter. The average transition magnetic moment between the computed low‐lying spin–orbit states also rationalized the relaxation as Orbach and Raman processes through the first excited state. BS‐DFT calculations were carried out for both CPs to provide more insight into the exchange interaction. [ABSTRACT FROM AUTHOR]