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Empirical and Theoretical Insights into the Structural Features and Host-guest Chemistry of M8L4 Tube Architectures

Meng, W.; League, A. B.; Ronson, T. K.; Clegg, J. K.; Isley, W. C., III; Semrouni, D.; Gagliardi, L.; Cramer, C. J.; Nitschke, J. R.
J. Am. Chem. Soc. 2014, 136, 3972 (doi:10.1021/ja412964r).

We demonstrate a general method for the construction of M8L4 tubular complexes via subcomponent self-assembly, starting from CuI or AgI precursors together with suitable elongated tetraamine and 2-pyridine-carboxaldehyde subcomponents. The tubular architectures were often observed as equilibrium mixtures of diastereomers having two different point symmetries (D2d or D2D4) in solution. The equilibria between diastereomers were influenced through variation in ligand length, substituents, metal ion identity, counter-anion, and temperature. In the presence of dicyanoaurate(I) and AuI, the D4-symmetric 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 Au(Au(CN)2)2– as the optimal guest through transmetalation. Density functional theory was employed to elucidate the host-guest chemistries of the tubes.