Citation: Xiaoru LIU, Jinlian SHI, Yajia ZHENG, Shuangcun MO, Zhongxuan XU. Two Ni-based frameworks with helices and dinuclear units constructed from semi-rigid carboxylic acid and imidazole derivatives[J]. Chinese Journal of Inorganic Chemistry, ;2025, 41(4): 797-808. doi: 10.11862/CJIC.20240328 shu

Two Ni-based frameworks with helices and dinuclear units constructed from semi-rigid carboxylic acid and imidazole derivatives

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

Corresponding author: Zhongxuan XU, xuzhongxuan4201@163.com
Received Date: 8 September 2024
Revised Date: 22 February 2025

Figures(8)

Under hydrothermal conditions, semi-rigid 4-(1-carboxyethoxy)benzoic acid (H₂cba) and Ni(Ⅱ) ions reacted with imidazole derivatives 1,4-di(1H-imidazol-1-yl)benzene (1,4-dib) and 4,4'-di(1H-imidazol-1-yl)-1,1'-biphenyl (4, 4' dib) to form complexes {[Ni(cba)(1, 4 dib)(H₂O)_0.5] ·0.5H₂O}n (HU21) and {[Ni(cba)(4, 4' dib)(H₂O)_0.5] · 0.5H 2O}n (HU22), respectively. Singlecrystal X-ray diffraction analysis revealed that both complexes HU21 and HU22 contain binuclear [Ni₂(CO₂)₂(H₂O)]²⁺ units, which are further bridged together via cba^2- anions to form 1D [Ni₂(H₂O)(cba)₂]_n chains in HU21 and HU22. In addition to the [Ni₂(H₂O)(cba)₂]_n chains, large right-handed and lefthanded helical chains were constructed by Ni(Ⅱ) ions, water molecules, and 1,4-dib ligands in HU21, with diameters of up to 1.6 nm along the b-axis. These helical chains are further joined together in a 1∶1 ratio to form a 3D framework. Subsequently, the [Ni₂(H₂O)(cba)₂]_n chains are incorporated into the 3D framework to build a six-connected dense network with a point symbol of (4⁴.6¹¹) in HU21. In complex HU22, left-and right-handed helical chains were also observed. However, unlike the 3D framework constructed by helical chains in HU21, these helical chains in HU22 can only form a 2D layer. Adjacent layers are packed together in an ABAB pattern to form a six-connected framework in the presence of [Ni₂(H₂O) (cba)₂]_n chains. UV-Vis absorption experiments indicated that complexes HU21 and HU22 are semiconductor materials with strong light absorption capacities in the ultraviolet and visible regions. Moreover, magnetic experiments showed that HU21 and HU22 exhibit similar antiferromagnetic behaviors.
- Ni-based complex,
- binuclear unit,
- helical chain,
- semiconductor material,
- antiferromagnetic property
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