Molecular Design of Amphiphiles Containing Mixed Ligand Transition Metal Complexes

(1)新制备了具有烷基长链的钴（III）和镍（II）配合物。它们在表面张力-浓度曲线中显示出明显的断点，表明它们在水溶液中聚集。临界胶束浓度（cmc）和降低表面张力的能力在很大程度上取决于烷基链的长度、取代基在配体上的位置和反离子。结果表明，复合物部分的结构对聚集行为有很大的影响。因此，两亲性金属配合物有望用于构建各种聚集态。(2)含有N-十二烷基乙二胺和手性四胺的混合配体两亲性钴（III）配合物提供了一个新的例子，即八面体金属中心周围的手性影响配合物的聚集行为。(3)溶剂化显色的镍（II）-四胺配合物具有十二烷基链，由于顺磁性八面体（蓝色）和抗磁性正方形平面（橙子）镍配合物之间的相互转换。极性头的空间结构的相互转换将是有用的，在设计两亲分子，其聚集可以高度控制的外部刺激。

(1) Cobalt(III) and nickel(II) complexes having an alkyl long chain are newly prepared. They showed clear break points in the surface tension-concentration curves, indicating their aggregation in aqueous solutions. Critical micelle concentration (cmc) and surface tension reducing ability largely depended on the length of the alkyl-chain, the position of its substitution on the ligand, and counter ions. The results indicate that the structure of the complex part can influence the aggregation behavior considerably. Therefore, amphiphilic metal complexes are expected to be used to construct a variety of aggregation molphologies.(2) Mixed ligand amphiphilic cobalt(III) complexes containing N-dodecylethylenediamine and a chiral tetraamine provided a novel example that the chirality around the octahedral metal center affects the aggregation behavior of the complexes.(3) Solvatochromism was observed for a nickel(II)-tetraamine complex having a dodecyl chain, due to an interconversion between a paramagnetic octahedral (blue) and a diamagnetic square planar (orange) nickel complex. The interconversion of the steric structure of the polar head will be useful in designing amphiphiles whose aggregation can be highly controlled by external stimulations.