Driven Evolution of a Constitutional Dynamic Library of Molecular Helices Toward the Selective Generation of [2 × 2] Gridlike Arrays under the Pressure of Metal Ion Coordination

• Published in: Journal of the American Chemical Society Vol. 128; no. 51; pp. 16748 - 16763
• Main Authors: Giuseppone, Nicolas, Schmitt, Jean-Louis, Lehn, Jean-Marie
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 27.12.2006; Amer Chemical Soc
• Subjects: Chemical Sciences; Chemistry; Chemistry, Multidisciplinary; Coordination compounds; Exact sciences and technology; General and physical chemistry; Inorganic chemistry and origins of life; Kinetics and mechanisms; Organic chemistry; Physical Sciences; Preparations and properties; Reactivity and mechanisms; Science & Technology; NEURAMINIDASE INHIBITORS; AMPLIFICATION; STRANDS; LIGANDS; SUPRAMOLECULAR ASSEMBLIES; COMBINATORIAL LIBRARIES; CHEMISTRY; RECEPTOR; DIVERSITY; SELF-ORGANIZATION; Self assembly; Complexation; Catalytic reaction; Regioselectivity; Ligand; Microwave; Metal ion; Polymerization; Molecular interaction; Transition metal; Selectivity; Zinc; Depolymerization; Molecular assembly; Chemical compound library; Transimination; Reaction mechanism; Helical structure; Folding
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja0666452

Constitutional dynamics, self-assembly, and helical-folding control are brought together in the efficient Sc(OTf)3/microwave-catalyzed transimination of helical oligohydrazone strands, yielding highly diverse dynamic libraries of interconverting constituents through assembly, dissociation, and exchange of components. The transimination-type mechanism of the ScIII-promoted exchange, as well as its regioselectivity, occurring only at the extremities of the helical strands, allow one to perform directional terminal polymerization/depolymerization processes when starting with dissymmetric strands. A particular library is subsequently brought to express quantitatively [2 × 2] gridlike metallosupramolecular arrays in the presence of ZnII ions by component recombination generating the correct ligand from the dynamic set of interconverting strands. This behavior represents a process of driven evolution of a constitutional dynamic chemical system under the pressure (coordination interaction) of an external effector (metal ions).