Journal of the American Chemical Society, Vol.136, No.10, 3972-3980, 2014
Empirical and Theoretical Insights into the Structural Features and Host-Guest Chemistry of M8L4 Tube Architectures
We demonstrate a general method for the construction of M8L4 tubular complexes via subcomponent self-assembly, starting from Cu-I or Ag-I precursors together with suitable elongated tetraamine and 2-formylpyridine subcomponents. The tubular architectures were often observed as equilibrium mixtures of diastereomers having two different point symmetries (D-2d or D2 reversible arrow D-4) in solution. The equilibria between diastereomers were influenced through variation in ligand length, substituents, metal ion identity, counteranion, and temperature. In the presence of dicyanoaurate(I) and Au-I, the D-4-syrnmetric hosts were able to bind linear Au(Au(CN)(2))(2)(-) (with two different configurations) as the best-fitting guest. Substitution of dicyanoargentate(I) for dicyanoaurate(I) resulted in the formation of Ag(Au(CN)(2))(2)(-) as the optimal guest through transmetalation. Density fiinctional theory was employed to elucidate the host-guest chemistries of the tubes.