Recent achievements in experimental and theoretical chemistry of reduced corannulene and sumanene (two smallest prototypic fragments of fullerene, aka buckybowls) revealed a tendency of highly reduced curved polyaromatic molecules to form sandwich-like aggregates in their convex-convex orientation and show remarkable stability in solution. Then, it was found that step-by-step replacement of small lithium by potassium or larger alkali metals leads to so-called “clamshell” effect resulting in occupation by lithium cation of the last available site – the space between two 5-membered rings. Subsequent theoretical investigations revealed that this lithium center shows unprecedentedly large chemical shift of ~-25ppm, further confirmed by experiment. The same strategy, applied to sumanene, resulted in formation of similar type of sandwich-like aggregates, but with higher M:C ratio (M – alkali metal), which makes them even more promising candidates for building blocks for the constructing batteries with extremely high capacity. In this talk, we show how modern theoretical/computational chemistry can help and guide experimentalists and present the results of very successful combination of theory and experiment, which made possible all recent achievements in the field. Moreover, recent theoretical predictions of complete encapsulation of metal cation between two endo-surfaces of buckybowls were successfully realized in experiment, leading to the discovery of the new type of sandwich-like supramolecular assemblies. This opens the way to new materials and possible applications.

Supramolecular chemistry of highly reduced buckybowls

254th National Meeting (2017)

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