👤 Olivier Fleischel

AbstractCoordination‐driven self‐assembly has been established as an effective strategy for the efficient construction of intricate architectures in both natural and artificial systems, for applications ranging from gene regulation to metal–organic frameworks. Central to these systems is the need for carefully designed organic ligands, generally with rigid components, that can undergo self‐assembly with metal ions in a predictable manner. Herein, we report the synthesis and study of three novel organic ligands that feature 3,6‐disubstituted acridine as a rigid spacer connected to two 2‐(1,2,3‐triazol‐4‐yl)pyridine “click” chelates through hinges of the same length but differing flexibility. The flexibility of these “three‐atom” hinges was modulated by i) moving from secondary to tertiary amide functional groups and ii) replacing an sp2 amide carbon with an sp3 methylene carbon. In an effort to understand the role of hinge flexibility in directing self‐assembly into mononuclear loops or dinuclear cylinders, the impact of these changes on self‐assembly outcomes with zinc(II), iron(II), and copper(II) ions is described. Show less

AbstractThe 2‐(1,2,3‐triazol‐4‐yl)pyridine motif, with its facile “click” synthesis and remarkable coordinative properties, is an attractive chelate for applications in the metal‐directed self‐assembly of intricate three‐dimensional structures. Organic ligands that bear two such chelates bridged by flexible hinge moieties readily undergo self‐assembly with metal ions of different coordination geometries to generate a series of topologically diverse metallomacrocycles that can be used for numerous applications. Herein, the synthesis and self‐assembly of one such ligand with zinc(II), copper(II), and palladium(II) ions is reported, and the stability of the resulting metallomacrocycles described. An investigation into the use of these metallomacrocycles for the recognition of both small‐molecule substrates, such as deoxyguanosine monophosphate, and larger biological assemblies, such as DNA and RNA guanine quadruplexes, is also described. Show less