Dynamic Helicates Self-Assembly from Homo- and Heterotopic Dynamic Covalent Ligand Strands.

The understanding and the application of reversible covalent reactions and coordination chemistry together with the proper design of the molecular frameworks, allow to achieve not only well-defined output architectures but also different grades of complex behavior. In this work, the dynamic nature of the helical systems offers an additional level of complexity by combining self-sorting on two levels: 1) the build-up of the ligand strand constituents from their components through dynamic covalent chemistry; 2) the assembly of the helicates from the ligands and the metal cations through dynamic metallo-supramolecular chemistry. The information encoded in the ligands constituent molecule was read differently (and accurately at the same time) by metal cations that varied in the coordination algorithms. It enabled the selective formation of a specific type of helicates from a wide library of helicates formed by the possible combination of subcomponents. Ligands containing dynamic tridentate and/or bidentate binding motifs in the same strand were studied to explore the helicates self-assembly with appropriate metal cations.