Chen Hui-Qing, Zhang Kun, Jin Chao, Huang Wei
State Key Laboratory of Coordination Chemistry, Nanjing National Laboratory of Microstructures, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, P. R. China.
Dalton Trans. 2014 Jun 14;43(22):8486-92. doi: 10.1039/c4dt00605d. Epub 2014 Apr 22.
Two novel pendant-armed dialdehydes (1a and 1b) were prepared by a one-step reaction between 5-chloro-3-(chloromethyl)-2-hydroxybenzaldehyde/5-methyl-3-(chloromethyl)-2-hydroxybenzaldehyde and cyclohexylamine involving two nucleophilic substitutions, and they were used to react with 1,3-propanediamine to prepare Schiff-base macrocyclic complexes in the presence of ZnX2 salts (X = Cl, Br, and I). As a result, five dinuclear (2a, 2b, 3b, 4a, and 4b) and one mononuclear (3a) [1 + 1] flexible macrocyclic Zn(II) complexes have been structurally and spectrally characterized. The zinc centers in three pairs of macrocyclic complexes have the common four-coordinate tetrahedral geometry with one or two coordinated halide ions, where the template Zn(II) cations and the auxiliary halide anions with different sizes and coordination abilities are believed to play important roles in forming the resulting macrocyclic complexes. In addition, subtle alterations of electron-withdrawing and electron-donating substituted groups (Cl versus CH3) in the macrocyclic backbone result in different (1)H NMR and UV-vis spectra.
通过5-氯-3-(氯甲基)-2-羟基苯甲醛/5-甲基-3-(氯甲基)-2-羟基苯甲醛与环己胺之间的一步反应，经两步亲核取代反应制备了两种新型的带有侧链的二醛(1a和1b)，并使其在ZnX2盐(X = Cl、Br和I)存在的情况下与1,3-丙二胺反应制备席夫碱大环配合物。结果，已对5种双核(2a、2b、3b、4a和4b)和1种单核(3a)[1 + 1]柔性大环Zn(II)配合物进行了结构和光谱表征。三对大环配合物中的锌中心具有常见的四配位四面体几何结构，带有一个或两个配位卤离子，其中模板Zn(II)阳离子和具有不同大小和配位能力的辅助卤离子被认为在形成所得大环配合物中起重要作用。此外，大环主链中吸电子和供电子取代基(Cl对CH3)的细微变化导致了不同的(1)H NMR和紫外可见光谱。
