Magneto-structural relationships in paddle-wheel dinuclear copper(II) complexes with tunable dimensionality (0D→1D→2D)

作者：Bing Zhao, Yi‐Chen Wang, Ximeng Jia, Zhong‐Yi Li · 发表于：Journal of Molecular Structure · 年份：2025 · DOI：10.1016/j.molstruc.2025.144561 · 被引用次数：2 · 研究领域：Magnetism in coordination complexes、Organic and Molecular Conductors Research、Supramolecular Chemistry and Complexes

Paddle-wheel dinuclear Cu(II) complexes serve as an ideal platform to elucidate the assembly of coordination clusters into 1D chains or 2D layers while preserving structural integrity. This study reports the synthesis, structural characterization, and magnetic properties of four paddle-wheel dinuclear copper(II) complexes, [Cu₂(dpa)₄(DMF)₂]∙DMF ( 1 , 0D, Hdpa=diphenylacetic acid), [Cu₂(dpa)₄(pyz)₂]ₙ ( 2 , 1D, pyz =pyrazine), [Cu₂(ita)₂(DMF)₂]ₙ ( 3 , 1D, H 2 ita =itaconic acid), and [Cu₂(ita)₂( pyz)₂]ₙ ( 4 , 2D) with tunable dimensionality (0D→1D→2D). By tuning carboxylate ligands (Hdpa vs. H₂ita) and auxiliary linkers (DMF vs. pyz), precise control over framework dimensionality was achieved, with all complexes retaining the paddle-wheel [Cu₂] core featuring syn - syn carboxylate bridging. Single-crystal X-ray diffraction analysis revealed variations in intra-cluster Cu···Cu distances, distortions in coordination geometry (trigonality parameter τ ), and differences in inter-cluster connectivity. Magnetic susceptibility measurements show all complexes exhibit strong antiferromagnetic (AFM) coupling ( J = –144.7 to –176.4 cm⁻¹), with Weiss constants ( θ , reflecting inter-dimer magnetic interactions) ranging from –1.47 K (0D) to –1057 K (2D). Key findings indicate that four factors—shorter intra-cluster Cu···Cu distances, the presence of π-conjugated pyrazine (pyz) linkers, higher structural dimensionality, and reduced distortion in coordination geometries—act synergistically to...