Self-sorting of multicomponent Pt(II) metallacages

Using a social self-sorting phenomenon, two Pt(II)←pyridyl, carboxylate heteroleptic metallacages cage 1 and cage 2 have been constructed in nearly quantitative yields from a single reaction that contained twenty-eight communicative precursors, including five unique species 3–7 in a 2:4:16:2:4 molar ratio. The success of this reaction has been established by multinuclear NMR (³¹P and ¹H), UV/Vis absorption and fluorescence emission spectroscopies. The process depends on various factors such as the energetic preference for Pt←N,O coordination over the Pt←N,N and Pt←O,O coordination motifs, the appropriate selection of stoichiometry and directionality of the precursors, as well as maximum site occupancy while keeping entropic costs as low as possible.