Departamento de Química Inorgánica, Centro Singular de Investigación en Química Biolóxica e Materiais Moleculares (CIQUS), Universidade de Santiago de Compostela, Santiago de Compostela, Galicia, E-15782, Spain.
Dalton Trans. 2012 Nov 21;41(43):13395-404. doi: 10.1039/c2dt31770b.
We have studied the factors that affect the formation of different metallosupramolecular architectures by metal direct self-assembly. A synthetic route has been developed to obtain mesocates or dihelicates selectively. For this purpose a series of five bisthiosemicarbazone ligands derived from 1,3-diacetylbenzene were designed and synthesised. Namely H(2)L(Me), H(2)L(Et), H(2)L(Ph), H(2)L(PhN) and H(2)L(PhOMe) with different substituents on the 4-N terminal position of the thiosemicarbazone strands. The Co(II), Zn(II) and Cd(II) complexes of these ligands were prepared by an electrochemical procedure. Crystallographic studies revealed the formation of mesocates for Co(II) and Zn(II) metal ions whereas the Cd(II) complexes gave a bishelical supramolecular structure. Therefore these bisthiosemicarbazone ligands enable the selective isolation of mesocate or dihelicate complexes by using a specific metal ion.
我们研究了通过金属直接自组装影响不同金属超分子结构形成的因素。已经开发出一种合成途径来有选择性地获得介观或双螺旋体。为此，设计并合成了一系列衍生自 1,3-二乙酰基苯的五对双硫代半卡巴腙配体。即 H(2)L(Me)、H(2)L(Et)、H(2)L(Ph)、H(2)L(PhN)和 H(2)L(PhOMe)，它们在硫代半卡巴腙链的 4-N 末端位置具有不同的取代基。这些配体的 Co(II)、Zn(II)和 Cd(II)配合物通过电化学程序制备。晶体学研究表明 Co(II)和 Zn(II)金属离子形成介观体，而 Cd(II)配合物则给出双螺旋超分子结构。因此，这些双硫代半卡巴腙配体可以通过使用特定的金属离子选择性地分离出介观或双螺旋体配合物。
