Self-assembly of dinuclear Pd(ii)/Pt(ii) metallacyclic receptors incorporating N-heterocyclic carbene complexes as corners.

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.