Self-assembled nanotubes exhibit impressive biological functions that have always inspired supramolecular scientists in their efforts to develop strategies to build such structures from small molecules through a bottom-up approach. One of these strategies employs molecules endowed with self-recognizing motifs at the edges, which can undergo either cyclization-stacking or folding-polymerization processes that lead to tubular architectures. Which of these self-assembly pathways is ultimately selected by these molecules is, however, often difficult to predict and even to evaluate experimentally. We show here a unique example of two structurally related molecules substituted with complementary nucleobases at the edges (i.e., G:C and A:U) for which the supramolecular pathway taken is determined by chelate cooperativity, that is, by their propensity to assemble in specific cyclic structures through Watson-Crick pairing. Because of chelate cooperativities that differ in several orders of magnitude, these molecules exhibit distinct supramolecular scenarios prior to their polymerization that generate self-assembled nanotubes with different internal monomer arrangements, either stacked or coiled, which lead at the same time to opposite helicities and chiroptical properties.

Department of Inorganic Chemistry Universidad Complutense de Madrid 28040 Madrid Spain

Department of Molecular and Translational Medicine University of Brescia Viale Europa 11 25123 Brescia Italy

Division of Theoretical Chemistry and Biology School of Engineering Sciences in Chemistry Biotechnology and Health KTH Royal Institute of Technology SE 100 44 Stockholm Sweden

Institute for Advanced Research in Chemical Sciences Universidad Autónoma de Madrid 28049 Madrid Spain

Laboratory of Organic Electronics and Scientific Visualization Group ITN Campus Norrköping; Swedish e Science Research Centre Linköping University 58183 Linköping Sweden

Nanostructured Molecular Systems and Materials Group Organic Chemistry Department Universidad Autónoma de Madrid 28049 Madrid Spain

Regional Centre of Advanced Technologies and Materials Czech Advanced Technology and Research Institute Palacký University Olomouc 779 00 Olomouc Czech Republic

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