Electronic Effects on Narcissistic Self-Sorting in Multicomponent Self-Assembly of Fe-Iminopyridine meso-Helicates.

Small changes in the electron donating ability of coordinating groups have substantial effects on the multicomponent self-assembly of Fe (II)-iminopyridine-based meso-helicate complexes. Both the nature of the internal diamine core and the terminal formylpyridine reactants control the rate of the assembly process, the thermodynamic favorability of the meso-helicate products, and the selective incorporation of different aldehyde termini into the assembly. Steric congestion at the coordinating ligands can prevent assembly altogether, and favorable incorporation of electron-rich aldehyde termini is observed, even though the rate of reaction is accelerated by the use of electron-poor aldehyde reactants.

Narcissistic self-sorting in self-assembled cages of rare Earth metals and rigid ligands.

Highly selective, narcissistic self-sorting can be achieved in the formation of self-assembled cages of rare earth metals with multianionic salicylhydrazone ligands. The assembly process is highly sensitive to the length of the ligand and the coordination geometry. Most surprisingly, high-fidelity sorting is possible between ligands of identical coordination angle and geometry, differing only in a single functional group on the ligand core, which is not involved in the coordination.