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Formation of Defect-Dicubane-Type Ni II2 Ln III2 (Ln = Tb, Er) Clusters: Crystal Structures and Modeling of the Magnetic Properties

Type of publication Peer-reviewed
Publikationsform Original article (peer-reviewed)
Author You Zhonglu, Prsa Krunoslav, Mutschler Julius, Herringer Susan N., Wang Jiaqi, Luo Yingying, Zheng Boyang, Decurtins Silvio, Krämer Karl W., Waldmann Oliver, Liu Shi-Xia,
Project New materials for honeycomb-lattice and single-ion magnets
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Original article (peer-reviewed)

Journal ACS Omega
Volume (Issue) 6(1)
Page(s) 483 - 491
Title of proceedings ACS Omega
DOI 10.1021/acsomega.0c04930

Open Access

Type of Open Access Publisher (Gold Open Access)


In the field of molecular nanoclusters, cubane and defect-dicubane, or butterfly structures, are typical examples of tetranuclear metal core architectures. In this work, a halogenated and anionic Schiff-base ligand (L2−) is utilized as it is predisposed to chelate within a cluster core to both 3d and 4f metal ions, in different binding configurations (H2L = 4-chloro-2-(2-hydroxy-3-methoxybenzyliden amino)-phenol). The phenolate oxygen atoms of the deprotonated ligand can act in μ-O and μ3-O bridging binding modes for the intramolecular assembly of metal ions. Based on that, two tetranuclear and isostructural compounds [Ni2Tb2(L)4(NO3)2(DMF)2]·2CH3CN (1) and [Ni2Er2(L)4(NO3)2(DMF)2]·0.5CH3CN (2) were synthesized and structurally characterized. Magnetic susceptibility and magnetization data indicate the occurrence of dominant intramolecular ferromagnetic interactions between the spin centers. Particular emphasis is given to the theoretical description of the magnetic behavior, taking into account the Ln−Ni and Ni−Ni coupling paths and the magnetic anisotropy of the LnIII and NiII ions. The study is distinguished for its discussion of two distinct models, whereby model A relies on the uniaxial B20 Stevens term describing the lanthanide anisotropy and model B is based on point-charge model calculations. Importantly, the physical meaning of the obtained parameters for both models was critically scrutinized.