Issue 15, 2024

Coordination-driven assembly of dysprosium layers into a framework featuring enhanced energy barriers and quantum tunneling of magnetization

Abstract

An orchestrated reaction of Dy(ClO4)3·6H2O with the organic ligand of N′-(2-hydroxybenzylidene)pyrazine-N-oxide-carbohydrazide (H2L) affords a layered building block, denoted as {[Dy(L)(H2O)(CH3OH)]ClO4·2CH3OH}n (1). Subsequently, the coordinated water and methanol molecules in 1 are efficaciously substituted by a di-topic ligand of 4,4′-bipyridine-N,N′-dioxide (bpdo), producing a unique three-dimensional framework labeled as {[Dy(L)(bpdo)]ClO4·2H2O}n (2). Magnetic measurements demonstrate the ferromagnetic interaction between the dysprosium ions, as well as the slow magnetic relaxation under a zero dc field with the effective spin-reversal barriers of 161(7) K and 203(6) K for 1 and 2, respectively. Further ab initio calculations indicate that the enhanced energy barrier of 2 is associated with the alteration of coordination environment around the Dy3+ ion, while the introduction of the bpdo bridging ligand leads to the stronger magnetic anisotropy of the Dy3+ ion and thus the magnetic relaxation pathway through the second excited state. Furthermore, the bpdo ligand also introduces stronger equatorial charge and may result in faster quantum tunneling of magnetization in 2.

Graphical abstract: Coordination-driven assembly of dysprosium layers into a framework featuring enhanced energy barriers and quantum tunneling of magnetization

Supplementary files

Article information

Article type
Research Article
Submitted
22 Mar 2024
Accepted
05 May 2024
First published
08 May 2024

Inorg. Chem. Front., 2024,11, 4686-4694

Coordination-driven assembly of dysprosium layers into a framework featuring enhanced energy barriers and quantum tunneling of magnetization

Z. Huang, R. Sun, F. Ma, J. Yang, X. Huang, H. Sun and S. Gao, Inorg. Chem. Front., 2024, 11, 4686 DOI: 10.1039/D4QI00737A

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