Initial Use of Dioximate Ligands in 3d/4f Cluster Chemistry: Synthesis, Structure, and Magnetic Studies of an Unusual [Gd^III₂Mn^IVO]⁸⁺ Complex

An unusual [MnIVGdIII2(μ3-O2−)]8+ triangular complex has been prepared from the initial use of 2,6-diacetylpyridine dioxime (dapdoH2) in 3d/4f cluster chemistry. The complex has an S = 13/2 ground state, with exchange parameters J = +0.49 cm−1 and J′ = −0.12 cm−1 [ℋ = −2J(Ŝi·Ŝj) convention] for the GdIII···MnIV and GdIII···GdIII interactions, respectively. The origin of this ground state has been rationalized by consideration of the spin frustration occurring within the complex as a function of the relative magnitude of the competing interactions.在3d/4f簇合物化学研究中，科研人员首次以2,6-二乙酰吡啶二肟（2,6-diacetylpyridine dioxime，dapdoH2）作为配体，合成了一种罕见的[Mn^IVGd^III2(μ3-O2^−)]^8+三角形金属配合物。该配合物的基态自旋为S=13/2；针对Gd^III与Mn^IV、Gd^III与Gd^III之间的磁相互作用，其交换参数分别为J=+0.49 cm⁻¹和J′=−0.12 cm⁻¹（采用哈密顿量ℋ = −2J(Ŝi·Ŝj)的约定形式）。通过考量该配合物内部由竞争相互作用相对强度所诱发的自旋阻挫效应，合理解释了该基态的起源。