Triple Self-Sorting in Constitutional Dynamic Networks: Parallel Generation of Imine-Based CuI, FeII, and ZnII Complexes

Abstract

Three imine-based metal complexes, having no overlap in terms of their compositions, have been simultaneously generated from the self-sorting of a constitutional dynamic library (CDL) containing three amines, three aldehydes, and three metal salts. The hierarchical ordering of the stability of the three metal complexes assembled and the leveraging of the antagonistic and agonistic relationships existing between the constituents within the constitutional dynamic network corresponding to the CDL were pivotal in achieving the sorting. Examination of the process by NMR spectroscopy showed that the self-sorting of the FeII and ZnII complexes depended on an interplay between the thermodynamic driving forces and a kinetic trap involved in their assembly. These results also exemplify the concept of “simplexity”—the fact that the output of a self-assembling system may be simplified by increasing its initial compositional complexity—as the two complexes could self-sort only in the presence of the third pair of organic components, those of the CuI complex.