Tianjin Key Laboratory of Structure and Performance for Functional Molecules, Ministry of Education, College of Chemistry, Tianjin Normal University, Tianjin 300387, China.
Dalton Trans. 2013 Apr 28;42(16):5902-15. doi: 10.1039/c3dt33013c.
Eight metal complexes, {Co(bibim-4)2(H2O)22}n (1), {Cu(bibim-4)2(NO3)}n (2), [Co(bibim-3)(TP)]n (3), [Zn2(bibim-3)]2(OAc)4] (4), [Co(bibim-2)(NO3)2]n (5), [Zn(bibim-4)(NO3)2]n (6), [Zn(bibim-4)(OAc)2]n (7) and [Cd(bibim-4)(NO3)2(DMF)]n (8) (bibim-2 = 1,2-bis(benzimidazol-l-yl)ethane, bibim-3 = 1,3-bis(benzimidazol-l-yl)propane, bibim-4 = 1,4-bis(benzimidazol-l-yl)butane and TP = terephthalate) have been prepared by means of the self-assembly of Co(II), Cu(II), Zn(II) or Cd(II) salts, dibenzimidazolyl bidentate ligands bearing alkanyl linkers and terephthalic acid. These complexes are structurally characterized by X-ray diffraction analyses. In complexes 1 and 2, 2D network layers with macrometallocycles are formed via metal centers and the ligand bibim-4. A 2D network layer with macrometallocycles in 3 is formed via Co(II) centers, the ligand bibim-3 and terephthalate molecules. In complex 4, a 20-membered macrometallocycle is formed by two bibim-3 ligands and two Zn(II) atoms. In complexes 5–8, 1D polymeric chains are formed via metal centers and the bibim-2 or bibim-4 ligands. In the crystal packings of complexes 1–8, 2D supramolecular layers and 3D supramolecular frameworks are formed via intermolecular weak interactions, including π–π interactions and hydrogen bonds. The different types of π–π interactions from the benzimidazole ring as well as the conformations of the ligands and metal complexes are described. Additionally, the fluorescence emission spectra of the ligands and metal complexes are reported.
八个金属配合物，{Co(bibim-4)2(H2O)22}n (1), {Cu(bibim-4)2(NO3)}n (2), [Co(bibim-3)(TP)]n (3), [Zn2(bibim-3)]2(OAc)4] (4), [Co(bibim-2)(NO3)2]n (5), [Zn(bibim-4)(NO3)2]n (6), [Zn(bibim-4)(OAc)2]n (7) 和 [Cd(bibim-4)(NO3)2(DMF)]n (8)（bibim-2 = 1,2-双(苯并咪唑-1-基)乙烷，bibim-3 = 1,3-双(苯并咪唑-1-基)丙烷，bibim-4 = 1,4-双(苯并咪唑-1-基)丁烷，TP = 对苯二甲酸）是通过 Co(II)、Cu(II)、Zn(II) 或 Cd(II) 盐、带有烷烃连接体的二苯并咪唑基双齿配体和对苯二甲酸的自组装制备的。这些配合物的结构通过 X 射线衍射分析进行了表征。在配合物 1 和 2 中，通过金属中心和配体 bibim-4 形成具有大环金属配合物的 2D 网络层。在 3 中，通过 Co(II) 中心、配体 bibim-3 和对苯二甲酸分子形成具有大环金属配合物的 2D 网络层。在配合物 4 中，通过两个 bibim-3 配体和两个 Zn(II) 原子形成一个 20 元大环金属配合物。在配合物 5-8 中，通过金属中心和 bibim-2 或 bibim-4 配体形成 1D 聚合链。在配合物 1-8 的晶体堆积中，通过分子间弱相互作用，包括π-π 相互作用和氢键，形成 2D 超分子层和 3D 超分子框架。描述了来自苯并咪唑环的不同类型的π-π 相互作用以及配体和金属配合物的构象。此外，还报道了配体和金属配合物的荧光发射光谱。
