Marcos Ismael, Domarco Olaya, Peinador Carlos, Fenández Alberto, Fernández Jesús J, Vázquez-García Digna, García Marcos D
Departamento de Química Fundamental and Centro de Investigacións Científicas Avanzadas (CICA), Facultade de Ciencias, Universidade da Coruña, E-15071 A Coruña, Spain.
Dalton Trans. 2017 Mar 27;46(13):4182-4190. doi: 10.1039/c6dt04476j.
We report herein the self-assembly of a series of new square and rectangular-shaped dinuclear ML metallacycles (M = Pd(ii)/Pt(ii)), receptors self-assembled in water from four different N-monoalkyl-4,4'-bipyridinium derivatives as ligands and square-planar Pd(ii) and Pt(ii) metal centers having the chelating N-heterocyclic carbene 1,1'-di(methyl)-3,3'-methylene-4-diimidazolin-2,2'-diylidene. The concentration-dependent PdL metallacycles were successfully obtained and characterized by means of NMR experiments in aqueous media. Due to the strong trans effect exerted by the carbene ligands, the synthesis of the PtL receptors was achieved as well by self-assembly of the components at room temperature in a few hours, in clear contraposition to the harsh reaction conditions usually required for the labilization of other kinetically inert Pt(ii)-N(pyridine) bonds. X-ray diffraction studies of suitable single crystals of two of the obtained receptors offered additional information on the structure of the obtained supramolecules, whose ability as receptors has been explored by the preparation and study of the corresponding inclusion complexes in water with 1,5-dihydroxynaphthalene as the model substrate.
我们在此报告了一系列新型方形和矩形双核ML金属环（M = Pd(ii)/Pt(ii)）的自组装情况，这些受体是由四种不同的N-单烷基-4,4'-联吡啶鎓衍生物作为配体，与具有螯合N-杂环卡宾1,1'-二（甲基）-3,3'-亚甲基-4-二咪唑啉-2,2'-二亚基的平面正方形Pd(ii)和Pt(ii)金属中心在水中自组装而成。通过在水性介质中的NMR实验成功获得了浓度依赖性的PdL金属环并对其进行了表征。由于卡宾配体产生的强反位效应，通过在室温下将各组分自组装几个小时，也成功实现了PtL受体的合成，这与通常使其他动力学惰性的Pt(ii)-N(吡啶)键活化所需的苛刻反应条件形成了鲜明对比。对所获得的两种受体的合适单晶进行的X射线衍射研究提供了有关所得超分子结构的更多信息，通过制备和研究其在水中与1,5-二羟基萘作为模型底物形成的相应包合物，探索了它们作为受体的能力。
