Anion-(π)n-π Catalytic Micelles

Anion-pi catalysis operates by stabilizing anionic transition states on pi-acidic aromatic surfaces. In anion-(pi)(n)-pi catalysis, pi stacks add polarizability to strengthen interactions. In search of synthetic methods to extend pi stacks beyond the limits of foldamers, the self-assembly of micelles from amphiphilic naphthalenediimides (NDIs) is introduced. To interface substrates and catalysts, charge-transfer complexes with dialkoxynaphthalenes (DANs), a classic in supramolecular chemistry, are installed. In pi-stacked micelles, the rates of bioinspired ether cyclizations exceed rates on monomers in organic solvents by far. This is particularly impressive considering that anion-pi catalysis in water has been elusive so far. Increasing rates with increasing pi acidity of the micelles evince operational anion-(pi)(n)-pi catalysis. At maximal pi acidity, autocatalytic behavior emerges. Dependence on position and order in confined micellar space promises access to emergent properties. Anion-(pi)(n)-pi catalytic micelles in water thus expand supramolecular systems catalysis accessible with anion-pi interactions with an inspiring topic of general interest and great perspectives.