High-Fidelity, Narcissistic Self-Sorting in the Synthesis of Organometallic Assemblies from Poly-NHC Ligands.

Highly selective, narcissistic self-sorting has been observed in the one-pot synthesis of three organometallic molecular cylinders of type [M3 {L-(NHC)3 }2 ](PF6 )3 (M=Ag+ , Au+ ; L=1,3,5-benzene, triphenylamine, or 1,3,5-triphenylbenzene) from L-(NHC)3 and silver(I) or gold(I) ions. The molecular cylinders contain only one type of tris-NHC ligand with no crossover products detectable. Transmetalation of the tris-NHC ligands from Ag+ to Au+ in a one-pot reaction with retention of the supramolecular structures is also demonstrated. High-fidelity self-sorting was also observed in the one-pot reaction of benzene-bridged tris-NHC and tetrakis-NHC ligands with Ag2 O. This study for the first time extends narcissistic self-sorting in metal-ligand interactions from Werner-type complexes to organometallic derivatives.