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A simple approach to generating in situ metal-templated tris-(2-picolyl)amine-like multicomponent assemblies with potential applications in molecular recognition and sensing is reported. The assembly is based on the reversible covalent association between di-(2-picolyl)amine and aldehydes. Zinc ion is best for inducing assembly among the metal salts investigated, whereas 2-picolinaldehyde is the best among the heterocyclic aldehydes studied. Although an equilibrium constant of 6.6×10(3) M(-1) was measured for the assembly formed by 2-picolinaldehdye, di-(2-picolyl)amine, and zinc triflate, the equilibrium constants for other systems are in the 10(2) M(-1) range. X-ray structural analysis revealed that zinc adopts trigonal-bipyramidal geometry within the assembled ligand. The diversity and equilibrium of the assemblies are readily altered by simply changing concentrations, varying components, or adding counteranions.
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You et al. (2011) studied this question.
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