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 (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 Au(I), 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 Ag(Au(CN)2)2(-) as the optimal guest through transmetalation. Density functional theory was employed to elucidate the host-guest chemistries of the tubes.
Department of Chemistry, University of Cambridge , Lensfield Road, Cambridge, CB2 1EW, U.K.
Wenjing
W
Meng
Aaron B
AB
League
Tanya K
TK
Ronson
Jack K
JK
Clegg
William C
WC
Isley
David
D
Semrouni
Laura
L
Gagliardi
Christopher J
CJ
Cramer
Jonathan R
JR
Nitschke