| 两个由半刚性羧酸和咪唑衍生物构建的具有螺旋和双核单元的镍基配合物 |
| Two Ni-based frameworks with helices and dinuclear units constructed from semi-rigid carboxylic acid and imidazole derivatives |
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| 摘要: 在水热条件下，4-(1-羧基乙氧基)苯甲酸(H2cba)和Ni (Ⅱ)离子分别与咪唑衍生物1，4-二(1H-咪唑-1-基)苯(1，4-dib)和4，4'-二(1H-咪唑-1-基)-1，1'-联苯(4，4'-dib)反应得到配合物{[Ni (cba)(1，4-dib)(H2O)0.5]·0.5H2O}n(HU21)和{[Ni (cba)(4，4'-dib)(H2O)0.5]·0.5H2O}n(HU22)。单晶衍射结构分析表明配合物HU21和HU22都含有双核的[Ni2(CO2)2(H2O)]2+单元。在HU21和HU22中，[Ni2(CO2)2(H2O)]2+单元都通过cba2-离子桥接在一起形成一维[Ni2(H2O)(cba)2]n链。进一步分析发现，在配合物HU21中除[Ni2(H2O)(cba)2]n链外，Ni (Ⅱ)离子、水分子和1，4-dib配体还沿b轴形成直径达1.6 nm的右旋和左旋螺旋链。这些右手和左手链按照1∶1的比例连接在一起，构建出HU21所属的空旷的三维结构。[Ni2(H2O)(cba)2]n链填充到该空旷结构中，得到具有点符号为(44.611)的六连接网络框架。不同于HU21中螺旋链可直接形成三维框架，在配合物HU22中，基于Ni (Ⅱ)离子、水分子和4，4'-dib的螺旋链只能够构建出二维结构层。这些二维结构通过[Ni2(H2O)(cba)2]n链作用以ABAB模式堆叠在一起，形成最终六连接网络特征的三维框架。此外，紫外可见吸收光谱证实配合物HU21和HU22属半导体材料，在紫外和可见光区具有较强的光吸收能力。磁性测试则揭示HU21和HU22具有相似的反铁磁性行为。 |
| 关键词: 镍基配合物 双核单元 螺旋链 半导体材料 反铁磁性 |
| 基金项目: 国家自然科学基金(No.21761036)和广西大学生创新训练项目(No.202410605029)资助。 |
| Abstract: 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 cba2- 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. |
| Keywords: Ni-based complex binuclear unit helical chain semiconductor material antiferromagnetic property |
| 投稿时间：2024-09-08 修订日期：2025-02-22 |
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| 刘晓茹,石金莲,郑亚佳,莫双存,徐中轩.两个由半刚性羧酸和咪唑衍生物构建的具有螺旋和双核单元的镍基配合物[J].无机化学学报,2025,41(4):797-808. |
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