Citation: Jinlian SHI, Xiaoru LIU, Zhongxuan XU. Ligand-directed construction of cobalt-oxo cluster-based organic frameworks: Structural modulation, semiconductor, and antiferromagnetic properties[J]. Chinese Journal of Inorganic Chemistry, ;2026, 42(1): 45-54. doi: 10.11862/CJIC.20250196 shu

Ligand-directed construction of cobalt-oxo cluster-based organic frameworks: Structural modulation, semiconductor, and antiferromagnetic properties

School of Chemical and Biological Engineering, Hechi University, Hechi, Guangxi 546300, China

Corresponding author: Zhongxuan XU, xuzhongxuan4201@163.com
Received Date: 9 June 2025
Revised Date: 3 November 2025

Figures(6)

Under hydrothermal and solvothermal conditions, two novel cobalt-based complexes, {[Co₂(CIA)(OH)(1, 4-dtb)]·2H₂O}_n (HU23) and {[Co₂(CIA)(OH)(1, 4-dib)]·3.5H₂O·DMF}_n (HU24), were successfully constructed by coordinatively assembling the semi-rigid multidentate ligand 5-(1-carboxyethoxy)isophthalic acid (H₃CIA) with the N-heterocyclic ligands 1, 4-di(4H-1, 2, 4-triazol-4-yl)benzene (1, 4-dtb) and 1, 4-di(1H-imidazol-1-yl)benzene (1, 4-dib), respectively, around Co²⁺ ions. Single-crystal X-ray diffraction analysis revealed that in both complexes HU23 and HU24, the CIA^3- anions adopt a κ⁷-coordination mode, bridging six Co²⁺ ions via their five carboxylate oxygen atoms and one ether oxygen atom. This linkage forms tetranuclear [Co₄(μ₃-OH)₂]⁶⁺ units. These Co-oxo cluster units were interconnected by CIA^3- anions to assemble into 2D kgd-type structures featuring a 3, 6-connected topology. The 2D layers were further connected by 1, 4-dtb and 1, 4-dib, resulting in 3D pillar-layered frameworks for HU23 and HU24. Notably, despite the similar configurations of 1, 4-dtb and 1, 4-dib, differences in their coordination spatial orientations lead to topological divergence in the 3D frameworks of HU23 and HU24. Topological analysis indicates that the frameworks of HU23 and HU24 can be simplified into a 3, 10-connected net (point symbol: (4¹⁰.6³.8²)(4³)₂) and a 3, 8-connected tfz-d net (point symbol: (4³)₂(4⁶.6¹⁸.8⁴)), respectively. This structural differentiation confirms the precise regulatory role of ligands on the topology of metal-organic frameworks. Moreover, the ultraviolet-visible absorption spectra confirmed that HU23 and HU24 have strong absorption capabilities for ultraviolet and visible light. According to the Kubelka-Munk method, their bandwidths were 2.15 and 2.08 eV, respectively, which are consistent with those of typical semiconductor materials. Variable-temperature magnetic susceptibility measurements (2-300 K) revealed significant antiferromagnetic coupling in both complexes, with their effective magnetic moments decreasing markedly as the temperature lowered.
- semi-rigid carboxylic acid ligands,
- three-dimensional framework,
- tetranuclear cobalt-oxo cluster,
- semiconductor material,
- antiferromagnetic magnetism
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