| Sumario: | We demonstrate a general method for the construction of ML tubular complexes via subcomponent self-assembly, starting from Cu or Ag 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 (D2d or D2 D4) 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 AuI, the D4-symmetric hosts were able to bind linear Au(Au(CN)) (with two different configurations) as the best-fitting guest. Substitution of dicyanoargentate(I) for dicyanoaurate(I) resulted in the formation of Ag(Au(CN))as the optimal guest through transmetalation. Density functional theory was employed to elucidate the host–guest chemistries of the tubes.
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