Kaczmarek Malgorzata T, Skrobanska Monika, Zabiszak Michal, Wałęsa-Chorab Monika, Kubicki Maciej, Jastrzab Renata
Faculty of Chemistry, Adam Mickiewicz University Umultowska 89b 61-614 Poznań Poland
RSC Adv. 2018 Sep 4;8(54):30994-31007. doi: 10.1039/c8ra03565b. eCollection 2018 Aug 30.
Template reaction between 5-methylsalicylaldehyde and 2-hydroxy-1,3-propanediamine in the presence of copper ion led to dinuclear and mononuclear copper(ii) complexes CuL(CHCOO)(CHOH) (1) and CuHL (2), where HL is ,'-bis(5-methylsalicylidene)-2-hydroxy-1,3-propanediamine. The result of the reactions between 5-methylsalicylaldehyde and 2-hydroxy-1,3-propanediamine in the presence of lanthanide ions and/or copper(ii) ion was ,'-bis(5-methylsalicylidene)-2-hydroxy-1,3-propanediamine (HL B) or CuHL (2), respectively. Structures of the compounds were determined by single-crystal X-ray diffraction and physicochemical methods. The microstructures and phase compositions of crystals were studied by scanning electron microscopy (SEM). In dinuclear complex CuL(CHCOO)(CHOH) (1), two copper(ii) ions are bond to one HL ligand and one acetate ion. Coordination modes of the two copper centers are different: the geometry of copper 1 is almost ideal square-planar, while that for copper 2 can be described as tetragonal pyramidal. In complex CuHL (2), the copper(ii) ion is four coordinated and the coordination, rather than square-planar, can be described as flattened tetrahedral. Formation of complexes between copper(ii) or lanthanide ions with ,'-bis(5-methylsalicylidene)-2-hydroxy-1,3-propanediamine (HL) was also studied in solution by pH potentiometry. It should be mentioned that the complexes of lanthanide ions exist only in solution. Additionally, the salen-type ligand HL and its dinuclear and mononuclear copper(ii) complexes were studied by cyclic voltammetry, and their spectroelectrochemical properties were examined.
在铜离子存在下，5-甲基水杨醛与2-羟基-1,3-丙二胺之间的模板反应生成了双核和单核铜（II）配合物CuL(CHCOO)(CHOH) (1) 和CuHL (2)，其中HL是，'-双（5-甲基水杨基亚甲基）-2-羟基-1,3-丙二胺。在镧系离子和/或铜（II）离子存在下，5-甲基水杨醛与2-羟基-1,3-丙二胺的反应结果分别是，'-双（5-甲基水杨基亚甲基）-2-羟基-1,3-丙二胺（HL B）或CuHL (2)。通过单晶X射线衍射和物理化学方法确定了化合物的结构。通过扫描电子显微镜（SEM）研究了晶体的微观结构和相组成。在双核配合物CuL(CHCOO)(CHOH) (1)中，两个铜（II）离子与一个HL配体和一个乙酸根离子键合。两个铜中心的配位模式不同：铜1的几何形状几乎是理想的平面正方形，而铜2的几何形状可描述为四方锥。在配合物CuHL (2)中，铜（II）离子是四配位的，其配位方式不是平面正方形，而是可描述为扁平四面体。还通过pH电位滴定法在溶液中研究了铜（II）或镧系离子与，'-双（5-甲基水杨基亚甲基）-2-羟基-1,3-丙二胺（HL）之间配合物的形成。应该提到的是，镧系离子的配合物仅存在于溶液中。此外，通过循环伏安法研究了salen型配体HL及其双核和单核铜（II）配合物，并研究了它们的光谱电化学性质。
